JPH05153984A - Production of higher saturated fatty acid fluorine-containing aliphatic alkyl ester - Google Patents
Production of higher saturated fatty acid fluorine-containing aliphatic alkyl esterInfo
- Publication number
- JPH05153984A JPH05153984A JP3349225A JP34922591A JPH05153984A JP H05153984 A JPH05153984 A JP H05153984A JP 3349225 A JP3349225 A JP 3349225A JP 34922591 A JP34922591 A JP 34922591A JP H05153984 A JPH05153984 A JP H05153984A
- Authority
- JP
- Japan
- Prior art keywords
- saturated fatty
- containing aliphatic
- fatty acid
- fluorine
- lipase
- 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.)
- Granted
Links
- 150000004671 saturated fatty acids Chemical class 0.000 title claims abstract description 30
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 27
- 239000011737 fluorine Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 102000004882 Lipase Human genes 0.000 claims abstract description 31
- 108090001060 Lipase Proteins 0.000 claims abstract description 31
- 239000004367 Lipase Substances 0.000 claims abstract description 31
- 235000019421 lipase Nutrition 0.000 claims abstract description 31
- 102000004190 Enzymes Human genes 0.000 claims abstract description 29
- 108090000790 Enzymes Proteins 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 238000005886 esterification reaction Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 5
- -1 aliphatic alcohols Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000002940 repellent Effects 0.000 abstract description 5
- 239000005871 repellent Substances 0.000 abstract description 5
- LPXWZLVHAPPUJK-UHFFFAOYSA-N 1-fluoro-9-methylhexacosan-9-ol Chemical compound CCCCCCCCCCCCCCCCCC(C)(O)CCCCCCCCF LPXWZLVHAPPUJK-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 238000005498 polishing Methods 0.000 abstract 2
- 230000009257 reactivity Effects 0.000 abstract 2
- 238000002474 experimental method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000002253 acid Substances 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
- 238000013329 compounding Methods 0.000 description 2
- 230000006837 decompression Effects 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
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment 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
- 241000894007 species Species 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- VHOCUJPBKOZGJD-UHFFFAOYSA-N triacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VHOCUJPBKOZGJD-UHFFFAOYSA-N 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
- 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
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 239000008173 hydrogenated soybean oil Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 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
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 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
- 239000007858 starting material Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000004753 textile 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)
Abstract
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。FIELD OF THE INVENTION The present invention relates to a method for producing a fluorine-containing aliphatic alkyl ester of a higher saturated fatty acid, which has excellent uses as a water repellent and a polish, in other words, a fluorine-containing aliphatic alcohol and a higher saturated fatty acid. The present invention relates to a method of esterifying and.
【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。BACKGROUND OF THE INVENTION Fluorine-containing aliphatic alkyl esters of higher saturated fatty acids are useful as polishes for automobile coatings or as water repellents for paper and textiles. It was produced by reacting an alcohol at a high temperature to esterify it. In this case, the problem that the reaction rate is low, the problem that the expensive fluorine-containing aliphatic alcohol, which easily escapes out of the system together with the water produced by the fluorine-containing aliphatic alcohol, must be used in excess, and an acid or alkali catalyst is used. Even so, the reaction rate is low and the removal of the catalyst is troublesome.Since the reaction rate is low, the purity cannot be improved unless it is purified by recrystallization, etc., so there are many steps and the cost is high and the production equipment for high temperature reaction is There was a problem that it cost.
【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及びリパーゼ関連
酵素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 present invention has been made for the purpose of developing a highly efficient production method as an alternative to the conventional production method by a high temperature reaction, which has many problems as described above. It is intended to provide a method for efficiently producing a fluorinated aliphatic alkyl ester of a higher saturated fatty acid at low temperature by using a lipase and a lipase-related enzyme 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、リパーゼ及びリパーゼ関連酵素を用いて、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-mentioned object, various studies were conducted on esterification reaction of higher saturated fatty acid and fluorinated aliphatic alcohol using lipase and lipase-related enzyme, and the following findings were obtained. I got it. The reaction can proceed even at 80 ° C or lower. If the reaction is carried out under reduced pressure, the reaction is almost completed, and no labor for purification is required. The removal of the catalyst is simple, and there is no harmful effect even if it remains.
【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及びリパーゼ関連酵
素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。Based on this finding, a higher saturated fatty acid having a large number of carbon atoms and a specified fluorine-containing aliphatic alcohol are
It has been found that an esterification reaction using a lipase and a lipase-related enzyme as a catalyst under a specified reaction condition leads to a very efficient reaction to produce a useful fluorine-containing aliphatic alkyl ester of higher saturated fatty acid. It was.
【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、リパーゼ及びリパーゼ関連酵
素の１種または２種以上を触媒として用いて反応温度８
０℃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、を要旨とするもので
ある。That is, the present invention is one or more kinds of higher saturated fatty acids having 18 or more carbon atoms and one or more kinds selected from fluorine-containing aliphatic alcohols represented by the general formula of the following chemical formula 1. At a reaction temperature of 8 using one or more of lipase and lipase-related enzymes as a catalyst.
The gist is a process for producing a fluorine-containing aliphatic alkyl ester of a higher saturated fatty acid, which is characterized in that an esterification reaction is carried out under a reduced pressure of 1 to 600 mmHg at 0 ° C or less.
【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。）Embedded image (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、リパーゼ及び
リパーゼ関連酵素から選ばれた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。That is, the present invention comprises one or more selected from higher saturated fatty acids having 18 or more carbon atoms and 2 to 2 carbon atoms.
1 or 2 or more selected from a fluorinated aliphatic alcohol having 12 perfluoroalkyl groups and having 1 to 5 methylene groups adjacent to a hydroxyl group is selected from a lipase and a lipase-related enzyme. It is a process for producing a fluorine-containing aliphatic alkyl ester of a higher saturated fatty acid, which comprises performing an esterification reaction under reduced pressure at a relatively low temperature using one or two or more species 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 a hydrolysis product of fats and oils obtained from animal and vegetable oils, synthetic fatty acids, or hydrogenation of double bonds in unsaturated fatty acids among these fatty acids. And the like, and examples thereof include stearic acid, behenic acid, montanic acid, melissic acid, hydrogenated beef 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。In the present invention, the reason why the higher saturated fatty acid is limited is that when unsaturated fatty acid is used as a starting material, glossiness,
This is because the water repellency is poor and the esterification reaction product is rarely used. The reason why the carbon number is limited to 18 or more is that the esterification reaction product is not often used when the carbon number is less than 18, which is industrial and economical. Because 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 general formula of the above chemical formula 1, but if the perfluoroalkyl group has less than 2 carbon atoms, the obtained product is This esterification reaction product has poor water repellency and is not used for many purposes. On the other hand, it is difficult to obtain a raw material having more than 12 carbon atoms, and at the same time, sufficient water repellency can be obtained with 12 carbon atoms, and a longer chain product It becomes unnecessary. Therefore, the carbon number of this perfluoroalkyl group is limited to 2-12.
【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 for limiting the number (n) of methylene groups in this fluorinated aliphatic alcohol to 1 to 5 is as follows.
When n is 0, the esterification reaction hardly occurs, while n is 5
When it is larger, the target 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 heptadecyl fluorooctyl ethanol, pentadecyl fluoroheptyl ethanol, undecyl fluoropentyl ethanol and the like.
【００１４】本発明において使用される酵素触媒、すな
わちリパーゼ及びリパーゼ関連酵素としては、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。Examples of the enzyme catalyst used in the present invention, that is, lipase and lipase-related enzyme include, for example, carboxylesterase, allylesterase, acylglycerol lipase, cholesterol lipase, lipoprotein lipase and the like, or immobilized ones thereof. Can be mentioned.
【００１５】このリパーゼ及びリパーゼ関連酵素の添加
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、リパーゼ及びリパーゼ関連酵素は固定化され
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 and the lipase-related enzyme added is not particularly limited, but is preferably 1 to 30% by weight based on the total amount of the reaction product (including the amount of the solvent when a solvent is used), and not so much. The reaction does not proceed sufficiently with a small addition amount (less than 1%), and a large amount (30%) of this enzyme is used.
Even if it is used), the effect is not improved beyond a certain level, and it becomes uneconomical to use an expensive enzyme of this kind in excess. The immobilized lipase and lipase-related enzyme are economical because they 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及
びリパーゼ関連酵素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３０〜７０℃であり、反応時間とし
ては４〜８時間が適当である。Next, the reason why the reaction temperature in the present invention is limited to 80 ° C. or lower is that the activity of lipase and lipase-related enzyme decreases at a temperature higher than 80 ° C. and the reaction does not proceed sufficiently. Also, if the temperature is higher than 80 ° C, the expensive enzyme cannot be reused. The preferable reaction temperature is 30 to 70 ° C., and the reaction time is 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。Further, in the present invention, the depressurizing condition is set to 1 to
The reason for limiting the pressure to 600 mmHg is that under reduced pressure of less than 1 mmHg, expensive fluorine-containing aliphatic alcohol is distilled under reduced pressure together with water produced by the reaction and discharged out of the system.
This is because if the pressure exceeds 00 mmHg, the water produced by the reaction becomes difficult to be discharged out of the system. It should be noted that the preferable depressurizing condition varies depending on the reaction temperature, but is 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 compounding ratio of the higher saturated fatty acid and the fluorinated aliphatic alcohol is preferably equimolar or slightly higher than the fluorinated aliphatic alcohol. Further, in the present invention, most of the higher saturated fatty acids and fluorine-containing aliphatic alcohols are solid, so that an organic solvent may be added if necessary for the purpose of helping dissolution. In this case, the organic solvent is added to assist dissolution of the higher saturated fatty acid, the fluorinated aliphatic alcohol, the produced ester and the like, and the smaller the amount, the more preferable. Of course, alcoholic solvents are not suitable because they compete with fluorine-containing aliphatic alcohols.
【００１９】反応完了後、触媒として用いたリパーゼ及
びリパーゼ関連酵素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８０℃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 completion of the reaction, the lipase used as a catalyst and the lipase-related enzyme can be easily removed by filtration and it is desirable to remove and reuse. However, depending on the purpose of use, heating to a high temperature of 80 ° C. or higher after the reaction is completed. After the enzyme activity is eliminated by using the above, the whole product may be used as it is as a water repellent or a polish.
【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或はリパー
ゼ関連酵素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. The higher saturated fatty acid and the fluorinated aliphatic alcohol undergo an esterification reaction by the action of lipase or a lipase-related enzyme and are reacted under reduced pressure, so that the produced water is the reaction system. The fluorinated aliphatic alkyl ester of higher saturated fatty acid is produced at a high reaction rate without being discharged to the outside and being hydrolyzed by the reverse reaction.
【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, and the enzyme catalyst used can be easily removed and reused.
Further, it can be easily inactivated, and very efficient production of a fluorine-containing 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 since it is not necessary to use the expensive fluorine-containing aliphatic alcohol in excess, it is a very advantageous manufacturing method in terms of cost, It 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。The fluorine-containing aliphatic alkyl ester of higher saturated fatty acid obtained by the present invention has a perfluoroalkyl group having 2 to 12 carbon atoms, and has a saturated alkyl group having 18 or more carbon atoms. It has excellent water repellency and gloss.
【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、及びリパーゼ或はリパーゼ関連酵素を、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 or a lipase-related enzyme were placed in a four-necked flask with a capacity of 300 ml equipped with a stirrer, a thermometer, a pressure reducing valve, and a condenser with a drainer. , Table 1 below
It was prepared with various compounding compositions as shown in. In addition,
The whole solution was prepared by using kerosene as a solvent in the smallest possible amount. The enzyme amount 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 Table 1 above, "R f -OH"
Indicates a fluorine-containing aliphatic ethyl alcohol, and the numerical value in that column indicates the carbon number of the perfluoroalkyl group.
Further, "OH / COOH" in Table 1 indicates the ratio of fluorine-containing 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
Company O) Paratase; PALATASE M1000L (NO
VO company)
【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。When the experimental compositions having the composition numbers as shown in Table 1 were reacted under various reaction temperatures, reaction times and reduced pressure conditions as shown in Table 2, the reaction rates shown in Table 2 were obtained. Good 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 described above, the following findings are recognized. (A) From Experiment Nos. 1 to 3, the reaction rate increases with an increase in the amount of enzyme, and the reaction is almost complete at 15% by weight. (B) Even if the amount of enzyme is smaller than in Experiment Nos. 2 and 9, the reaction rate is improved by increasing the pressure reduction 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) From Experiment Nos. 3 and 4, it is more effective to make the decompression condition stronger than to increase the enzyme amount too much. (D) From experiment numbers 3 and 5, IM-20 rather than paratase
Is more effective. (E) From Experiment Nos. 3 and 6, montanic acid and stearic acid have similar 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) From Experiment No. 7, without enzyme, the reaction rate is remarkably low even at high temperature. (G) The reaction rate is lower than that in Experiment No. 8 even when the pressure is not reduced. (H) It is very effective to make the decompression condition stronger than in Experiment Nos. 9 and 10, but the reaction rate decreases as the temperature decreases to near room temperature. (I) From Experiment No. 11, when the reaction temperature exceeds 80 ° C., 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 fluorine-containing aliphatic alcohol is very high, and the product That is, the fluorinated aliphatic alkyl ester of higher saturated fatty acid can be produced in high 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 can be reused, and in some cases, the enzyme activity can be simply raised to 80 ° C. or higher. Since it can be eliminated, there is no need to remove it, which simplifies the process and greatly improves the manufacturing efficiency.
【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。The cost of the product is significantly reduced by not using an excessive amount of expensive fluorine-containing aliphatic alcohol in combination with the improvement of the above-mentioned reaction rate and the simplification of the process. Can be provided at low cost,
It is extremely useful for this type of industry.
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、リパーゼ及びリパーゼ関連酵素の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、１〜６
００mmＨｇ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】 （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 fluorine-containing aliphatic alcohols represented by the general formula of the following chemical formula 1. One or two of lipase and lipase-related enzymes
Using 1 or more species as a catalyst, the reaction temperature is 80 ° C. or less, 1 to 6
A process for producing a fluorine-containing aliphatic alkyl ester of a higher saturated fatty acid, which comprises performing an esterification reaction under a reduced pressure of 00 mmHg. [Chemical 1] (However, Rf in the said general formula represents a C2-C12 perfluoroalkyl group, and n shows the integer of 1-5.)
Priority Applications (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 |
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 |
|---|---|
| JPH05153984A true JPH05153984A (en) | 1993-06-22 |
| JP3093403B2 JP3093403B2 (en) | 2000-10-03 |
Family
ID=18402326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03349225A Expired - Lifetime JP3093403B2 (en) | 1991-12-05 | 1991-12-05 | Preparation of fluorinated aliphatic alkyl esters of higher saturated fatty acids |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3093403B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015531236A (en) * | 2012-10-10 | 2015-11-02 | ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ | A three-step method for the enzymatic synthesis of fatty acid esters |
-
1991
- 1991-12-05 JP JP03349225A patent/JP3093403B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015531236A (en) * | 2012-10-10 | 2015-11-02 | ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ | A three-step method for the enzymatic synthesis of fatty acid esters |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3093403B2 (en) | 2000-10-03 |
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