JP3093403B2 - Preparation of fluorinated aliphatic alkyl esters of higher saturated fatty acids - Google Patents
Preparation of fluorinated aliphatic alkyl esters of higher saturated fatty acidsInfo
- Publication number
- JP3093403B2 JP3093403B2 JP03349225A JP34922591A JP3093403B2 JP 3093403 B2 JP3093403 B2 JP 3093403B2 JP 03349225 A JP03349225 A JP 03349225A JP 34922591 A JP34922591 A JP 34922591A JP 3093403 B2 JP3093403 B2 JP 3093403B2
- Authority
- JP
- Japan
- Prior art keywords
- saturated fatty
- fluorinated aliphatic
- reaction
- higher saturated
- fatty acids
- 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 - Lifetime
Links
- 150000004671 saturated fatty acids Chemical class 0.000 title claims description 27
- 235000003441 saturated fatty acids Nutrition 0.000 title claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 102000004882 Lipase Human genes 0.000 claims description 16
- 108090001060 Lipase Proteins 0.000 claims description 16
- 239000004367 Lipase Substances 0.000 claims description 16
- 235000019421 lipase Nutrition 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 238000005886 esterification reaction Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 7
- -1 fluorinated aliphatic alcohols Chemical class 0.000 claims description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical class C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 16
- 102000004190 Enzymes Human genes 0.000 description 15
- 108090000790 Enzymes Proteins 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 230000002940 repellent Effects 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- BMOUGNXFACXHRG-UHFFFAOYSA-N 1-fluoro-6-methylheptadecan-6-ol Chemical compound CCCCCCCCCCCC(C)(CCCCCF)O BMOUGNXFACXHRG-UHFFFAOYSA-N 0.000 description 1
- KCIZEIXERBJHCR-UHFFFAOYSA-N 1-fluoro-8-methyltricosan-8-ol Chemical compound CCCCCCCCCCCCCCCC(C)(CCCCCCCF)O KCIZEIXERBJHCR-UHFFFAOYSA-N 0.000 description 1
- LPXWZLVHAPPUJK-UHFFFAOYSA-N 1-fluoro-9-methylhexacosan-9-ol Chemical compound CCCCCCCCCCCCCCCCCC(C)(O)CCCCCCCCF LPXWZLVHAPPUJK-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 102000013392 Carboxylesterase Human genes 0.000 description 1
- 108010051152 Carboxylesterase Proteins 0.000 description 1
- 102000017055 Lipoprotein Lipase Human genes 0.000 description 1
- 108010013563 Lipoprotein Lipase Proteins 0.000 description 1
- 108010048733 Lipozyme Proteins 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008173 hydrogenated soybean oil Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- FCCDDURTIIUXBY-UHFFFAOYSA-N lipoamide Chemical compound NC(=O)CCCCC1CCSS1 FCCDDURTIIUXBY-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、撥水剤や艶出し剤とし
ての優れた用途を有する高級飽和脂肪酸の含フッ素脂肪
族アルキルエステルの製法、換言すれば含フッ素脂肪族
アルコールと高級飽和脂肪酸とをエステル化反応させる
方法に関するものである。The present invention relates to a process for producing a fluorinated aliphatic alkyl ester of a higher saturated fatty acid having an excellent use as a water repellent or a polishing agent, in other words, a fluorinated aliphatic alcohol and a higher saturated fatty acid. And an esterification reaction of
【0002】[0002]
【従来の技術】高級飽和脂肪酸の含フッ素脂肪族アルキ
ルエステルは自動車塗装面の艶出し剤或は紙や繊維類の
撥水剤などとして有用であるが、従来では高級飽和脂肪
酸と含フッ素脂肪族アルコールを高温反応させエステル
化することにより製造されていた。この場合、反応率が
低いという問題、含フッ素脂肪族アルコールが生成した
水と共に系外に逃げやすく高価な含フッ素脂肪族アルコ
ールを過剰に使用しなければならないという問題、酸や
アルカリ触媒を使用してもなお反応率が低くかつ触媒の
除去が煩わしいという問題、反応率が低いので再結晶等
により精製しなければ純度が上がらないため、工程が多
くて価格が高くなりかつ高温反応用生産設備を要すると
いう問題等があった。2. Description of the Related Art Fluorinated aliphatic alkyl esters of higher saturated fatty acids are useful as polishes on painted surfaces of automobiles or water repellents for papers and fibers. It has been produced by reacting alcohol at a high temperature and esterifying it. In this case, the reaction rate is low, the fluoroaliphatic alcohol is liable to escape from the system together with the water produced, and the expensive fluoroaliphatic alcohol must be used in excess. However, the reaction rate is still low and the removal of the catalyst is troublesome.Because the reaction rate is low, the purity cannot be increased unless it is purified by recrystallization or the like. There was a problem that it required.
【0003】[0003]
【発明が解決しようとする課題】本発明は上記の様な問
題点の多い従来の高温反応による製造方法に代る効率の
高い製法を開発することを目的としてなされたものであ
り、エステル化の触媒としてリパーゼを用いることによ
って、高級飽和脂肪酸の含フッ素脂肪族アルキルエステ
ルを低温で効率的に製造する方法を提供しようとするも
のである。SUMMARY OF THE INVENTION The object of the present invention is to develop a highly efficient production method which can replace the conventional production method by a high temperature reaction which has many problems as described above. An object of the present invention is to provide a method for efficiently producing a fluorinated aliphatic alkyl ester of a higher saturated fatty acid at a low temperature by using lipase as a catalyst.
【0004】[0004]
【課題を解決するための手段】上記の目的を達成するた
めに、リパーゼを用いて、高級飽和脂肪酸と含フッ素脂
肪族アルコールのエステル化反応について種々検討した
ところ、下記の知見を得たのである。 80℃以下で
も反応の進行は可能である。 減圧下であれば反応は
ほぼ完結し、精製の手間は不要である。 触媒の除去
は簡単であり、残存しても弊害はない。Means for Solving the Problems In order to achieve the above object, various studies were made on the esterification reaction of higher saturated fatty acids and fluorinated aliphatic alcohols using lipase, and the following findings were obtained. . The reaction can proceed even at 80 ° C. or lower. Under reduced pressure, the reaction is almost complete and no purification is required. The removal of the catalyst is simple and there is no harm if left.
【0005】この知見に基づいて、炭素数の多い高級飽
和脂肪酸と特定された含フッ素脂肪族アルコールとを、
特定された反応条件下にてリパーゼを触媒として用いて
エステル化反応させると、極めて効率的に反応して有用
な高級飽和脂肪酸の含フッ素脂肪族アルキルエステルの
製法となることを見い出したのである。[0005] Based on this finding, higher saturated fatty acids having a large number of carbon atoms and the specified fluorine-containing aliphatic alcohol are
It has been found that when the esterification reaction is carried out using lipase as a catalyst under the specified reaction conditions, the reaction takes place extremely efficiently to produce a useful method for producing a fluorine-containing aliphatic alkyl ester of a higher saturated fatty acid.
【0006】すなわち本発明は、炭素数18以上の高級
飽和脂肪酸の1種または2種以上と、下記の化1の一般
式にて示される含フッ素脂肪族アルコールから選ばれる
1種または2種以上とを、リパーゼの1種または2種以
上を触媒として用いて反応温度80℃以下、1〜600
mmHgの減圧下の条件でエステル化反応させることを特
徴とする高級飽和脂肪酸の含フッ素脂肪族アルキルエス
テルの製法、を要旨とするものである。That is, the present invention relates to one or more of the higher saturated fatty acids having 18 or more carbon atoms and one or more of the fluorine-containing aliphatic alcohols represented by the following general formula: At a reaction temperature of 80 ° C. or lower using one or more lipases as a catalyst,
A method for producing a fluorinated aliphatic alkyl ester of a higher saturated fatty acid, wherein the esterification reaction is carried out under reduced pressure of mmHg.
【0007】[0007]
【化1】(但し、上記一般式中のRf は炭素数2〜12
のパーフルオロアルキル基を表わし、nは1〜5の整数
を示す。)(Wherein, R f in the above general formula has 2 to 12 carbon atoms)
Represents a perfluoroalkyl group, and n represents an integer of 1 to 5. )
【0008】つまり本発明は、炭素数18以上の高級飽
和脂肪酸から選ばれた1種又は2種以上と、炭素数2〜
12のパーフルオロアルキル基を有しかつ水酸基に隣接
する1〜5個のメチレン基を有する含フッ素脂肪族アル
コールより選ばれた1種又は2種以上を、リパーゼから
選ばれた1種または2種以上を触媒として用いて、比較
的低温で減圧下にエステル化反応させることを特徴とす
る高級飽和脂肪酸の含フッ素脂肪族アルキルエステルの
製法である。[0008] That is, the present invention relates to one or more selected from higher saturated fatty acids having 18 or more carbon atoms,
One or two or more selected from fluorinated aliphatic alcohols having 12 perfluoroalkyl groups and having 1 to 5 methylene groups adjacent to a hydroxyl group, and one or two selected from lipases This is a method for producing a fluorinated aliphatic alkyl ester of a higher saturated fatty acid, which comprises conducting an esterification reaction under reduced pressure at a relatively low temperature using the above as a catalyst.
【0009】本発明に用いられる炭素数18以上の高級
飽和脂肪酸は、動植物油より得られる油脂の加水分解生
成物、合成脂肪酸、或はこれら脂肪酸の中でも不飽和脂
肪酸における2重結合への水素添加などの反応により誘
導された脂肪酸を意味し、例えばステアリン酸、ベヘン
酸、モンタン酸、メリシン酸、水添牛脂脂肪酸、水添大
豆油脂肪酸などが挙げられる。The higher saturated fatty acid having 18 or more carbon atoms used in the present invention is obtained by hydrolyzing a double bond in a fatty acid or a hydrolyzate obtained from animal or vegetable oil, synthetic fatty acid, or unsaturated fatty acid among these fatty acids. And the like, and include, for example, stearic acid, behenic acid, montanic acid, melicic acid, hydrogenated tallow fatty acid, hydrogenated soybean oil fatty acid, and the like.
【0010】本発明において高級飽和脂肪酸に限定した
理由は、不飽和脂肪酸を出発原料とすれば、艶出し性、
撥水性に劣り、エステル化反応物の用途があまりないた
めであり、その炭素数を18以上に限定した理由も、炭
素数18未満ではエステル化反応物の用途があまりな
く、工業的かつ経済的価値に劣るからである。The reason why the present invention is limited to higher saturated fatty acids in the present invention is that if unsaturated fatty acids are used as a starting material, polishing properties,
This is because water repellency is inferior and there are not many uses of the esterification reactant. The reason why the number of carbon atoms is limited to 18 or more is that if the number of carbon atoms is less than 18, there are few uses of the esterification reactant, which is industrial and economical It is inferior in value.
【0011】次に、本発明に用いる含フッ素脂肪族アル
コールは前記した化1の一般式にて示される化合物であ
るが、このパーフルオロアルキル基の炭素数が2未満で
は得られた生成物の撥水性が劣りこのエステル化反応物
の用途があまりなく、一方、この炭素数が12をこえる
原料は入手しにくくなると同時に炭素数12で充分な撥
水性が得られこれ以上の長鎖のものは不要となるのであ
る。したがって、このパーフルオロアルキル基の炭素数
を2〜12と限定したのである。Next, the fluorinated aliphatic alcohol used in the present invention is a compound represented by the above-mentioned general formula (1), but if the perfluoroalkyl group has less than 2 carbon atoms, the resulting product This esterification reaction product is inferior in water repellency and has few uses. On the other hand, raw materials having more than 12 carbon atoms are difficult to obtain, and at the same time, sufficient water repellency is obtained with 12 carbon atoms, and those with longer chains are used. It is no longer necessary. Therefore, the number of carbon atoms of the perfluoroalkyl group was limited to 2 to 12.
【0012】また、この含フッ素脂肪族アルコールにお
けるメチレン基の数(n)を1〜5と限定した理由は、
nが0ではエステル化反応が起こりにくく、一方nが5
より大きくなると通常の加熱によるエステル化反応によ
っても目的物が得られ、本発明のような高価な酵素触媒
は不要となるのである。The reason why the number (n) of methylene groups in this fluorinated aliphatic alcohol is limited to 1 to 5 is as follows.
When n is 0, the esterification reaction hardly occurs, while n is 5
When the size is larger, the desired product can be obtained by the esterification reaction by ordinary heating, and the expensive enzyme catalyst as in the present invention becomes unnecessary.
【0013】この含フッ素脂肪族アルコールの例として
は、ヘプタデシルフルオロオクチルエタノール、ペンタ
デシルフルオロヘプチルエタノール、ウンデシルフルオ
ロペンチルエタノールなどが挙げられる。Examples of the fluorinated aliphatic alcohol include heptadecylfluorooctylethanol, pentadecylfluoroheptylethanol, undecylfluoropentylethanol and the like.
【0014】本発明において使用される酵素触媒、すな
わちリパーゼとしては、例えばカルボキシルエステラー
ゼ、アリルエステラーゼ、アシルグリセロールリパー
ゼ、コレステロールリパーゼ、リポプロティンリパーゼ
など、或はこれらの固定化したもの等が挙げられる。The enzyme catalyst used in the present invention, that is, lipase, includes, for example, carboxylesterase, allylesterase, acylglycerol lipase, cholesterol lipase, lipoprotein lipase and the like, or immobilized products thereof.
【0015】このリパーゼの添加量は、特に限定する必
要はないが、反応物全量(溶剤を用いた場合はこの溶剤
量も含む)に対して1〜30重量%が好ましく、あまり
少ない添加量(1%未満)では反応は充分に進行しない
し、またこの酵素を多く(30%以上)用いてもその効
果は一定以上には向上せず高価なこの種の酵素を過剰に
使用するのは不経済となるのである。なおリパーゼは固
定化されているものを使用すれば、再利用できるので経
済的である。The amount of the lipase to be added is not particularly limited, but is preferably 1 to 30% by weight based on the total amount of the reactants (including the amount of the solvent when a solvent is used). (Less than 1%), the reaction does not proceed sufficiently, and even if a large amount of this enzyme (30% or more) is used, its effect is not improved to a certain level and it is impossible to use an expensive enzyme of this kind in excess. It becomes an economy. If lipase is used, it is economical because it can be reused.
【0016】次に本発明における反応温度を80℃以下
と限定した理由は、80℃より高温になるとリパーゼの
活性が低下して反応が充分進行しないためである。そし
てまた、80℃より高温では高価な酵素の再利用も出来
なくなるのである。なお、好ましい反応温度としては3
0〜70℃であり、反応時間としては4〜8時間が適当
である。The reason why the reaction temperature in the present invention is limited to 80 ° C. or lower is that if the temperature is higher than 80 ° C., the activity of lipase decreases and the reaction does not proceed sufficiently. If the temperature is higher than 80 ° C., expensive enzymes cannot be reused. The preferred reaction temperature is 3
The temperature is 0 to 70 ° C, and the reaction time is suitably 4 to 8 hours.
【0017】また本発明において、その減圧条件を1〜
600mmHgと限定した理由は、1mmHg未満の減圧下
では高価な含フッ素脂肪族アルコールが反応により生成
した水と共に減圧蒸留され系外に排出されるし、一方6
00mmHgをこえると反応により生成した水が系外に排
出されにくくなるからである。なお、好ましい減圧条件
としては反応温度によっても異なるが、約3〜150mm
Hg位である。In the present invention, the decompression condition is 1 to
The reason for limiting the pressure to 600 mmHg is that under a reduced pressure of less than 1 mmHg, an expensive fluorinated aliphatic alcohol is distilled under reduced pressure together with water produced by the reaction and discharged out of the system.
If the pressure exceeds 00 mmHg, the water generated by the reaction becomes difficult to be discharged out of the system. In addition, although preferable pressure reduction conditions vary depending on the reaction temperature, about 3 to 150 mm
Hg position.
【0018】本発明において、高級飽和脂肪酸と含フッ
素脂肪族アルコールの配合比は、等モル或は含フッ素脂
肪族アルコールを若干多い目にするのが好ましい。ま
た、本発明において高級飽和脂肪酸、含フッ素脂肪族ア
ルコールの多くは、固形状であるため溶解を助けること
を目的として、必要に応じて有機溶剤を添加しても良
い。この場合、有機溶剤は高級飽和脂肪酸、含フッ素脂
肪族アルコール、生成したエステル等の溶解を助けるた
めに加えるものであって、少ない程好ましいものであ
る。なお、アルコール系溶剤は含フッ素脂肪族アルコー
ルとの競争反応が起こるので、適切でないことは勿論で
ある。In the present invention, the blending ratio of the higher saturated fatty acid to the fluorinated aliphatic alcohol is preferably equimolar or slightly larger than that of the fluorinated aliphatic alcohol. Further, in the present invention, since many of higher saturated fatty acids and fluorinated aliphatic alcohols are in a solid state, an organic solvent may be added as needed for the purpose of assisting dissolution. In this case, the organic solvent is added to assist the dissolution of the higher saturated fatty acid, the fluorinated aliphatic alcohol, the formed ester, and the like, and the smaller the amount, the more preferable. It is needless to say that an alcohol-based solvent is not suitable because a competitive reaction occurs with the fluorinated aliphatic alcohol.
【0019】反応完了後、触媒として用いたリパーゼは
濾過によって簡単に除去できるので取除いて再利用する
ことが望ましいが、使用目的によっては反応終了後に8
0℃以上の高温に加熱して酵素活性を無くしてしまって
から、そのまま生成物全体を撥水剤或は艶出し剤として
使用しても良いものである。After the completion of the reaction, the lipase used as a catalyst can be easily removed by filtration. Therefore, it is desirable to remove and reuse the lipase.
After heating to a high temperature of 0 ° C. or higher to eliminate the enzyme activity, the whole product may be used as it is as a water repellent or a polishing agent.
【0020】[0020]
【作用】本発明は以上の様な構成からなり、高級飽和脂
肪酸と含フッ素脂肪族アルコールがリパーゼの作用によ
りエステル化反応を起こし、減圧下に反応させるので生
成水が反応系外に排出され、逆反応の加水分解を受ける
ことはなく、高反応率で高級飽和脂肪酸の含フッ素脂肪
族アルキルエステルが生成されるのである。The present invention has the above-mentioned constitution, and the higher saturated fatty acid and the fluorinated aliphatic alcohol cause an esterification reaction by the action of lipase, and are reacted under reduced pressure, so that the produced water is discharged out of the reaction system. It does not undergo hydrolysis of the reverse reaction, and a fluorinated aliphatic alkyl ester of higher saturated fatty acid is produced at a high conversion.
【0021】本発明の製法によれば、反応率が高く生成
物を再結晶により精製する必要はなく、しかも使用した
酵素触媒は容易に除去して再利用することも出来るし、
また簡単に不活性化することも可能で、非常に効率的な
高級飽和脂肪酸の含フッ素脂肪族アルキルエステルの製
造が達成できるのである。このように反応率が高くしか
も工程上の簡略化が達成され、その上に高価な含フッ素
脂肪族アルコールを過剰に使用しなくても良いので、コ
スト上非常に有利な製造方法であって、経済性の極めて
高い製法と云えるものである。According to the production method of the present invention, the reaction rate is high and it is not necessary to purify the product by recrystallization. Further, the used enzyme catalyst can be easily removed and reused.
In addition, it can be easily inactivated, and very efficient production of a fluorinated aliphatic alkyl ester of a higher saturated fatty acid can be achieved. In this way, the reaction rate is high and simplification in the process is achieved, and it is not necessary to use an excessive amount of expensive fluorinated aliphatic alcohol. This is a very economical manufacturing method.
【0022】本発明によって得られた高級飽和脂肪酸の
含フッ素脂肪族アルキルエステルは炭素数2〜12のパ
ーフルオロアルキル基を有するため、及び炭素数18以
上の飽和アルキル基を有しているため、非常にすぐれた
撥水性・艶出し性を具有するものである。Since the fluorinated aliphatic alkyl ester of higher saturated fatty acid obtained by the present invention has a perfluoroalkyl group having 2 to 12 carbon atoms and a saturated alkyl group having 18 or more carbon atoms, It has excellent water repellency and glazing properties.
【0023】[0023]
【実施例】撹拌装置、温度計、減圧調整弁、及び水抜き
装置付きコンデンサーを付した容量300mlの4つ口フ
ラスコに、高級飽和脂肪酸、含フッ素脂肪族アルコー
ル、及びリパーゼを、下記の表1に示したような種々な
る配合組成にて仕込んだ。なお、溶剤としてケロシンを
できるだけ少量使用する様にして全体を溶液状にした。
また表1における酵素量は、上記溶剤を含めた全量に対
する重量%である。EXAMPLE A higher saturated fatty acid, a fluorinated aliphatic alcohol, and a lipase were placed in a 300 ml four-necked flask equipped with a stirrer, a thermometer, a pressure reducing valve, and a condenser equipped with a drainage device. In various compositions as shown in Table 1. The whole was made into a solution by using kerosene as a solvent as little as possible.
The amount of enzyme in Table 1 is% by weight based on the total amount including the solvent.
【0024】[0024]
【表1】 [Table 1]
【0025】なお、上記の表1において「Rf −OH」
は含フッ素脂肪族のエチルアルコールを示し、その欄の
数値はパーフルオロアルキル基の炭素数を表している。
また、表1における「OH/COOH」は、含フッ素脂
肪族アルコール/高級飽和脂肪酸の割合を示している。In the above Table 1, "R f -OH"
Indicates a fluorinated aliphatic ethyl alcohol, and the numerical value in the column indicates the carbon number of the perfluoroalkyl group.
“OH / COOH” in Table 1 indicates the ratio of fluorinated aliphatic alcohol / higher saturated fatty acid.
【0026】さらに、表1における酵素種は下記の通り
である。 IM−20 ;LIPOZYME IM−20(NOV
O社) パラターゼ ;PALATASE M1000L(NO
VO社)Further, the enzyme species in Table 1 are as follows. IM-20; LIPOZYME IM-20 (NOV
O) Paratase; PALATASE M1000L (NO
VO)
【0027】表1の如き配合組成の各実験番号のもの
を、表2に示した様な種々なる反応温度、反応時間、減
圧条件にて反応させたところ、表2の反応率に示した様
な結果が得られた。なお、反応率は生成物の酸価を測定
することにより求めた。The compositions of each experiment number having the composition shown in Table 1 were reacted at various reaction temperatures, reaction times, and reduced pressure conditions as shown in Table 2, and the reaction rates were as shown in Table 2. Results were obtained. The reaction rate was determined by measuring the acid value of the product.
【0028】[0028]
【表2】 [Table 2]
【0029】以上の表1及び表2のデータから、次のよ
うな知見が認められるのである。 (a)実験番号1〜3より酵素量の増加に伴ない反応率
は向上し、15重量%でほぼ完全に反応する。 (b)実験番号2と9より酵素量が少なくても、減圧条
件を強くすることにより反応率は向上する。From the data in Tables 1 and 2, the following findings are found. (A) From Experiment Nos. 1 to 3, the reaction rate increases with an increase in the amount of enzyme, and almost complete reaction occurs at 15% by weight. (B) Even if the amount of the enzyme is smaller than that of Experiment Nos. 2 and 9, the reaction rate is improved by increasing the reduced pressure condition.
【0030】(c)実験番号3と4より酵素量をあまり
多くするよりも減圧条件を強くする方が有効である。 (d)実験番号3と5よりパラターゼよりもIM−20
の方が有効である。 (e)実験番号3と6よりモンタン酸とステアリン酸と
は同程度の優れた効果があり、炭素数は18以上で充分
である。(C) It is more effective to increase the depressurization condition than to increase the amount of enzyme much more than in Experiment Nos. 3 and 4. (D) Experiment Nos. 3 and 5 show IM-20 rather than paratase.
Is more effective. (E) According to Experiment Nos. 3 and 6, montanic acid and stearic acid have the same excellent effects, and a carbon number of 18 or more is sufficient.
【0031】(f)実験番号7より酵素なしでは高温に
しても反応率は著しく低い。 (g)実験番号8より減圧しない場合も反応率は低い。 (h)実験番号9と10より減圧条件を強くすることは
非常に有効であるが、温度が常温近くまで下がると反応
率は低下する。 (i)実験番号11より80℃をこえる反応温度にする
と反応率は低下する。(F) According to Experiment No. 7, the reaction rate is remarkably low even at a high temperature without the enzyme. (G) Even when the pressure is not reduced as compared with Experiment No. 8, the reaction rate is low. (H) It is very effective to increase the pressure reduction conditions as compared with Experiment Nos. 9 and 10, but the reaction rate decreases when the temperature drops to near normal temperature. (I) If the reaction temperature is higher than 80 ° C. as compared with Experiment No. 11, the reaction rate decreases.
【0032】[0032]
【発明の効果】本発明の効果は、作用欄において詳述し
た通りであって、高級飽和脂肪酸と含フッ素脂肪族アル
コールとのエステル化反応の反応率が非常に高いという
ことであり、生成物である高級飽和脂肪酸の含フッ素脂
肪族アルキルエステルが収率よく製造でき精製する必要
もないと云うことである。The effect of the present invention is as described in detail in the section of action, that is, the reaction rate of the esterification reaction between the higher saturated fatty acid and the fluorinated aliphatic alcohol is extremely high. Fluorinated aliphatic alkyl esters of higher saturated fatty acids can be produced in good yield and need not be purified.
【0033】しかも、この反応に使用した酵素触媒は容
易に濾過によって除去することもでき、これを再利用す
ることも可能であり、また場合によっては単に80℃以
上に加熱するだけでその酵素活性を消失させることがで
きるので取り除く必要もなくなるなど、工程が簡略化し
製造能率が大幅に向上するのである。Moreover, the enzyme catalyst used in this reaction can be easily removed by filtration, and it can be reused. In some cases, the enzyme activity can be easily increased by simply heating to 80 ° C. or higher. Can be eliminated, so that there is no need to remove it, so that the process is simplified and the production efficiency is greatly improved.
【0034】さらに高価な含フッ素脂肪族アルコールを
過剰に使用しないことと、上記の反応率向上や工程の簡
略化とが相まって生成物のコストを大幅に下げ、有用な
撥水剤や艶出し剤を安価に提供することが可能となり、
この種の産業に極めて高度な有用性を発揮するものであ
る。Further, not using excessively expensive fluorine-containing aliphatic alcohol, and the above-mentioned improvement in the reaction rate and simplification of the process, significantly reduce the cost of the product, and provide useful water repellents and polishing agents. Can be provided at low cost,
It is extremely useful for this kind of industry.
フロントページの続き (72)発明者 有本 邦夫 兵庫県高砂市荒井町蓮池2丁目10番23号 (58)調査した分野(Int.Cl.7,DB名) C12P 7/64 CA(STN) REGISTRY(STN)Continuation of the front page (72) Inventor Kunio Arimoto 2-10-23, Hasuike, Arai-machi, Takasago-shi, Hyogo (58) Field surveyed (Int. Cl. 7 , DB name) C12P 7/64 CA (STN) REGISTRY ( STN)
Claims (1)
または2種以上と、下記の化1の一般式にて示される含
フッ素脂肪族アルコールから選ばれる1種または2種以
上とを、リパーゼの1種または2種以上を触媒として用
いて反応温度80℃以下、1〜600mmHgの減圧下の
条件でエステル化反応させることを特徴とする高級飽和
脂肪酸の含フッ素脂肪族アルキルエステルの製法。 【化1】Rf−(CH2)n−OH (但し、上記一般式中のRfは炭素数2〜12のパーフ
ルオロアルキル基を表わし、nは1〜5の整数を示
す。)1. One or more kinds of higher saturated fatty acids having 18 or more carbon atoms and one or more kinds selected from fluorinated aliphatic alcohols represented by the following general formula: reaction temperature 80 ° C. below using one lipase or two or more as a catalyst, preparation of fluorinated aliphatic alkyl esters of higher saturated fatty acids, wherein the esterification reaction under the conditions of reduced pressure of 1~600mmHg . Embedded image R f — (CH 2 ) n —OH (wherein, R f in the above general formula represents a perfluoroalkyl group having 2 to 12 carbon atoms, and n represents an integer of 1 to 5)
Priority Applications (1)
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---|---|---|---|
JP03349225A JP3093403B2 (en) | 1991-12-05 | 1991-12-05 | Preparation of fluorinated aliphatic alkyl esters of higher saturated fatty acids |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP03349225A JP3093403B2 (en) | 1991-12-05 | 1991-12-05 | Preparation of fluorinated aliphatic alkyl esters of higher saturated fatty acids |
Publications (2)
Publication Number | Publication Date |
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JPH05153984A JPH05153984A (en) | 1993-06-22 |
JP3093403B2 true JP3093403B2 (en) | 2000-10-03 |
Family
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KR20150063527A (en) * | 2012-10-10 | 2015-06-09 | 바스프 에스이 | Three-stage method for the enzymatic synthesis of fatty acid esters |
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