JPH093469A - Lubricant - Google Patents
LubricantInfo
- Publication number
- JPH093469A JPH093469A JP17419295A JP17419295A JPH093469A JP H093469 A JPH093469 A JP H093469A JP 17419295 A JP17419295 A JP 17419295A JP 17419295 A JP17419295 A JP 17419295A JP H093469 A JPH093469 A JP H093469A
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- value
- average molecular
- number average
- polyether
- 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
- 239000000314 lubricant Substances 0.000 title claims abstract description 14
- 229920000570 polyether Polymers 0.000 claims abstract description 24
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 10
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000005977 Ethylene Substances 0.000 claims abstract description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 3
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000002480 mineral oil Substances 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 9
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 abstract description 7
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000012644 addition polymerization Methods 0.000 abstract description 2
- 229920005862 polyol Polymers 0.000 abstract 1
- 150000003077 polyols Chemical class 0.000 abstract 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 15
- -1 n -Propyl Chemical group 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 239000010687 lubricating oil Substances 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000005555 metalworking Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 231100000241 scar Toxicity 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- BRMYZIKAHFEUFJ-UHFFFAOYSA-L mercury diacetate Chemical compound CC(=O)O[Hg]OC(C)=O BRMYZIKAHFEUFJ-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
Landscapes
- Lubricants (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ポリエーテル系潤滑剤
に関する。さらに詳しくは、ブレーキフルード、機械用
潤滑油、金属加工油、冷凍機用潤滑油、燃料又は燃料油
等に添加してスラッジの発生が少なく、摩擦低減や摩耗
防止効果などの潤滑性にすぐれた潤滑剤に関する。FIELD OF THE INVENTION The present invention relates to a polyether lubricant. More specifically, it is added to brake fluid, machine lubricating oil, metal working oil, refrigerator lubricating oil, fuel or fuel oil, etc. to reduce sludge generation, and has excellent lubricity such as friction reduction and wear prevention effect. Regarding lubricants.
【０００２】[0002]
【従来の技術】ポリエーテル系の潤滑油は、スラッジの
発生が少なく、潤滑性が良好であることが知られてい
る。中でもプロピレンオキシド（ＰＯ）またはブチレン
オキシド（ＢＯ）とエチレンオキシド（ＥＯ）とを共重
合させたものが摩擦低減や摩耗防止効果などの潤滑性に
良好である。また、高分子量体になるほど良好であり、
多官能のアルキレンオキシド付加体（ＡＯＡ）よりモノ
オールのＡＯＡが潤滑性能としては優れている。しかし
ながら、アルカリ金属を触媒にしてアルキレンオキシド
を付加重合させたものは、多分散体で潤滑性が発現する
ほどに十分な分子量のものが得られず不十分である。ま
た、一方これらのポリエーテルは鉱物油などの炭化水素
油とは相溶性が乏しく、特にＥＯリッチなもの程鉱物油
との相溶性が乏しくなる。そこで高級アルコールなどの
長鎖アルキル基を持つ化合物にＰＯ、ＢＯを付加させた
もの（特開昭４８−４０８０３）、副生ＰＰＧを少なく
したもの（公告昭４９−１４８４１）が油溶性の粘度指
数向上剤として提案されている。しかし、これらの化合
物もまた、多分散体で潤滑性が発現するほどに十分な分
子量のものではない。2. Description of the Related Art Polyether-based lubricating oils are known to have a small amount of sludge and good lubricity. Among them, those obtained by copolymerizing propylene oxide (PO) or butylene oxide (BO) and ethylene oxide (EO) are excellent in lubricity such as friction reduction and wear prevention effect. Also, the higher the molecular weight, the better,
The monool AOA is superior in lubricating performance to the polyfunctional alkylene oxide adduct (AOA). However, those obtained by addition-polymerizing an alkylene oxide with an alkali metal as a catalyst are not sufficient because a polydispersed product having a molecular weight sufficient to exhibit lubricity cannot be obtained. On the other hand, these polyethers have poor compatibility with hydrocarbon oils such as mineral oils, and the more EO rich, the poorer the compatibility with mineral oils. Therefore, a compound having PO or BO added to a compound having a long-chain alkyl group such as higher alcohol (JP-A-48-40803) and a compound having a small amount of by-product PPG (Publication No. 49-14841) are oil-soluble viscosity indexes. Proposed as an improver. However, these compounds are also not of sufficient molecular weight to exhibit lubricity in the polydisperse.
【０００３】[0003]
【発明が解決しようとする課題】従来のポリエーテル
は、分子量分布が多分散となり、また、分子量が大きく
伸ばせず、ポリプロピレングリコール系で分子量が３０
００程度のものしか得られなかった。したがって、これ
らのポリエーテルは潤滑油や燃料油に添加した場合、鉱
物油との溶解性に十分なものが得られず、且つ、摩擦係
数低減や摩耗防止に限界があった。鉱物油との溶解性を
上げ、潤滑性を向上させるためには分子量分布をできる
だけ単分散とし、分子量を大きくし、且つ副生するジオ
ールを少なくする必要があった。In the conventional polyether, the molecular weight distribution is polydisperse, the molecular weight does not greatly extend, and the polypropylene glycol type has a molecular weight of 30.
Only about 00 was obtained. Therefore, when these polyethers are added to lubricating oils and fuel oils, sufficient solubility with mineral oils cannot be obtained, and there is a limit in reducing the friction coefficient and preventing wear. In order to increase the solubility with mineral oil and improve the lubricity, it was necessary to make the molecular weight distribution as monodisperse as possible, to increase the molecular weight, and to reduce the diol produced as a by-product.
【０００４】[0004]
【課題を解決するための手段】本発明者は、摩擦低減や
摩耗防止性に優れ、かつスラッジ発生が少ないポリエー
テル系潤滑油を開発すべく研究を重ねた結果本発明に達
した。すなわち本発明は、下記一般式（１）で示され、
数平均分子量が２０００以上で、かつ、ＴＵ値が下記式
（２）を満たすポリエーテルを含有することを特徴とす
る潤滑剤。 Ｒ1Ｘ−［（ＥＯ）ｍ／（ＡＯ）ｎ］−Ｙ （１） ［式中、Ｒ1 は炭素数１〜２２のアルキルもしくはア
ルケニル基、Ｅはエチレン基、Ａは炭素数３〜４のアル
キレン基、ＸはＯ原子、Ｓ原子またはＣＯＯ基、Ｙは水
素原子、−Ｒ2またはＲ3ＣＯ−、｛ Ｒ2、Ｒ3 は炭素数
１〜２２のアルキルもしくはアルケニル基｝、ｍは０〜
１００、ｎは２０〜３００の整数を示す。［（ＥＯ）ｍ
／（ＡＯ）ｎ］はランダム付加もしくはブロック付加を
示す。］ ｙ≦２×１０-5×ｚ−０．０１５ （２） ［式中、ｚは数平均分子量、ｙはＴＵ値（ｍｅｑ／ｇ）
を示す。但し、Ｒ1に固有のＴＵ値を持つ場合は、それ
を差し引いた値］The inventor of the present invention has reached the present invention as a result of repeated research to develop a polyether-based lubricating oil which is excellent in friction reduction and wear resistance and has less sludge generation. That is, the present invention is represented by the following general formula (1),
A lubricant comprising a polyether having a number average molecular weight of 2000 or more and a TU value satisfying the following formula (2). R 1 X - [(EO) m / (AO) n] -Y (1) [ wherein, R 1 represents an alkyl or alkenyl group having 1 to 22 carbon atoms, E is ethylene, A is 3-4 carbon atoms Alkylene group, X is an O atom, S atom or COO group, Y is a hydrogen atom, —R 2 or R 3 CO—, {R 2 , R 3 Is an alkyl or alkenyl group having 1 to 22 carbon atoms, and m is 0
100 and n show the integer of 20-300. [(EO) m
/ (AO) n] indicates random addition or block addition. Y ≦ 2 × 10 −5 × z−0.015 (2) [wherein, z is a number average molecular weight, and y is a TU value (meq / g).
Is shown. However, if R 1 has a unique TU value, the value subtracted from it
【０００５】本発明において一般式（１）に示されるＲ
1は、炭素数１〜２２の直鎖もしくは分岐のアルキルも
しくはアルケニル基である。例えばメチル、エチル、ｎ
−プロピル、イソプロピル、アリル、ｎ−ブチル、ｓｅ
ｃ−ブチル、アミル、ヘキシル、イソヘキシル、ヘプチ
ル、イソヘプチル、ｎ−オクチル、２−エチルヘキシ
ル、ノニル、デシル、ラウリル、ミリスチル、セチル、
ステアリル、イソステアリル、オレイル、ウンデシル、
ドデセニル、リノール、アラキル等の基が挙げられる。
これらの内、好ましいのはセチル、ステアリル、オレイ
ル、イソステアリル基である。In the present invention, R represented by the general formula (1)
1 is a linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms. For example, methyl, ethyl, n
-Propyl, isopropyl, allyl, n-butyl, se
c-butyl, amyl, hexyl, isohexyl, heptyl, isoheptyl, n-octyl, 2-ethylhexyl, nonyl, decyl, lauryl, myristyl, cetyl,
Stearyl, isostearyl, oleyl, undecyl,
Examples thereof include groups such as dodecenyl, linole, and aralkyl.
Of these, preferred are cetyl, stearyl, oleyl and isostearyl groups.
【０００６】本発明において、一般式（１）に示される
Ｙは水素原子、−Ｒ2またはＲ3ＣＯ−、｛ Ｒ2、Ｒ3 は
炭素数１〜２２のアルキルもしくはアルケニル基｝であ
る。炭素数１〜２２のアルキルもしくはアルケニル基と
しては、例えばメチル、エチル、ｎ−プロピル、イソプ
ロピル、アリル、ｎ−ブチル、ｓｅｃ−ブチル、アミ
ル、ヘキシル、イソヘキシル、ヘプチル、イソヘプチ
ル、ｎ−オクチル、２−エチルヘキシル、ノニル、デシ
ル、ラウリル、ミリスチル、セチル、ステアリル、イソ
ステアリル、オレイル、ウンデシル、ドデセニル、リノ
ール、アラキル等の基が挙げられる。これらの内、好ま
しいのは水素原子およびメチル、エチル、プロピル、ブ
チル等のアルキル基である。In the present invention, Y represented by the general formula (1) is a hydrogen atom, —R 2 or R 3 CO—, {R 2 , R 3 Is an alkyl or alkenyl group having 1 to 22 carbon atoms}. Examples of the alkyl or alkenyl group having 1 to 22 carbon atoms include methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, sec-butyl, amyl, hexyl, isohexyl, heptyl, isoheptyl, n-octyl, 2- Examples thereof include groups such as ethylhexyl, nonyl, decyl, lauryl, myristyl, cetyl, stearyl, isostearyl, oleyl, undecyl, dodecenyl, linole and aralkyl. Of these, preferred are a hydrogen atom and alkyl groups such as methyl, ethyl, propyl and butyl.
【０００７】一般式（１）のＥＯはエチレンオキシドで
あり、付加モル数ｍは、０〜２０である。好ましくは０
〜１０である。一般式（１）のＡＯは炭素数３〜４のア
ルキレンオキシド（プロピレンオキシド、ブチレンオキ
シド）が挙げられ、好ましくはプロピレンオキシドであ
る。［（ＥＯ）ｍ／（ＡＯ）ｎ］はランダム付加もしく
はブロック付加を示す。具体例としては、ＰＯもしくは
ＢＯの単独付加、ＰＯとＢＯのランダムもしくはブロッ
ク付加、ＥＯとＰＯのランダム付加、ＥＯ，ＰＯ，ＢＯ
のランダム付加、ＥＯとＰＯのブロック付加、ＥＯとＰ
ＯとＥＯの３元ブロック付加などがあげられる。EO of the general formula (1) is ethylene oxide, and the number m of added moles is 0 to 20. Preferably 0
10 to 10. Examples of AO of the general formula (1) include alkylene oxides having 3 to 4 carbon atoms (propylene oxide, butylene oxide), and preferably propylene oxide. [(EO) m / (AO) n] indicates random addition or block addition. Specific examples are PO or BO alone addition, PO and BO random or block addition, EO and PO random addition, EO, PO, BO.
Random addition, block addition of EO and PO, EO and P
Examples include the addition of O and EO ternary blocks.
【０００８】本発明により得られる該ポリエーテルのＴ
Ｕ値は式（２）をみたすものである。 ｙ≦２×１０-5×ｚ−０．０１５ （２） ［式中、ｚは数平均分子量、ｙはＴＵ値（ｍｅｑ／ｇ）
を示す。但し、Ｒ1に固有のＴＵ値を持つ場合は、それ
を差し引いた値］ ＴＵ値が大であることは、副反応により低分子量成分が
反応の進行に伴い順次生成していることを意味し、数平
均分子量が増加しなくなる傾向を表わしている。一般的
触媒である水酸化カリウムによるポリエーテル類は、特
に数平均分子量が２０００を超えるとＴＵ値が０．１５
ｍｅｑ／ｇ程度以上となり、数平均分子量の増大が見ら
れなくなる。The T of the polyether obtained according to the invention
The U value satisfies the equation (2). y ≦ 2 × 10 −5 × z−0.015 (2) [wherein, z is number average molecular weight, y is TU value (meq / g)
Is shown. However, when R 1 has a unique TU value, the value obtained by subtracting the TU value] A large TU value means that low molecular weight components are sequentially produced by the side reaction as the reaction progresses. , The number average molecular weight does not increase. Polyethers using potassium hydroxide, which is a general catalyst, have a TU value of 0.15 especially when the number average molecular weight exceeds 2000.
It is about meq / g or more, and no increase in the number average molecular weight is observed.
【０００９】ポリエーテルが式（２）を満たさない場合
は、分子量分布が広くなり、かつ、不要な成分の含有量
が増加して、鉱物油への溶解性が低温で低下し、また、
摩擦低減や摩耗防止効果が悪くなる。When the polyether does not satisfy the formula (2), the molecular weight distribution is widened, the content of unnecessary components is increased, and the solubility in mineral oil is decreased at low temperature.
Friction reduction and wear prevention effects deteriorate.
【００１０】本発明において、該ポリエーテルの分子量
は、２０００以上であり、好ましくは２６００以上であ
る。一般的触媒である水酸化カリウムによるポリエーテ
ル類の数平均分子量は、通常水酸基あたり２０００未満
であり、３２００を越えることは困難である。数平均分
子量が２０００未満の場合摩擦低減および摩耗防止効果
が小さくなる。In the present invention, the molecular weight of the polyether is 2000 or more, preferably 2600 or more. The number average molecular weight of polyethers using potassium hydroxide, which is a general catalyst, is usually less than 2000 per hydroxyl group, and it is difficult to exceed 3200. When the number average molecular weight is less than 2000, the effect of reducing friction and the effect of preventing wear are reduced.
【００１１】式（２）を満たす低ＴＵ値のポリエーテル
を得るには、触媒として複合金属シアノ錯体、アルミニ
ウムポルフィリンおよび水酸化セシウムなどを使用して
アルキレンオキシドを吹き込む方法が挙げらる。好まし
くは重合後の触媒除去操作が簡単であるという点で水酸
化セシウムである。これらの触媒を最初から投入して作
成しても良いが、あらかじめＫＯＨ等のアルカリ金属触
媒で低分子量品を作成しておき、次に水酸化セシウム触
媒を投入して吹き込み高分子量化しても良い。In order to obtain a polyether having a low TU value which satisfies the formula (2), a method of blowing an alkylene oxide using a complex metal cyano complex, aluminum porphyrin, cesium hydroxide or the like as a catalyst can be mentioned. Cesium hydroxide is preferred because the catalyst removal operation after polymerization is simple. These catalysts may be added from the beginning to prepare, but a low molecular weight product may be prepared in advance with an alkali metal catalyst such as KOH, and then a cesium hydroxide catalyst may be added to blow it into a high molecular weight product. .
【００１２】本発明において、アルキレンオキシドの付
加重合反応に適用する条件としては、温度は通常６０〜
１５０℃であり、好ましくは８０〜１２０℃である。ま
た圧力は通常１〜８ｋｇ／ｃｍ2であり、好ましくは２
〜６ｋｇ／ｃｍ2である。In the present invention, as the conditions applied to the addition polymerization reaction of alkylene oxide, the temperature is usually 60 to
The temperature is 150 ° C, preferably 80 to 120 ° C. The pressure is usually 1 to 8 kg / cm 2 , preferably 2
~ 6 kg / cm 2 .
【００１３】本発明の潤滑剤は、通常、鉱物油、合成潤
滑油、ブレーキフルード、ギヤ油、金属加工油、機械工
業油、燃料および燃料油などに０．０１〜２０％添加し
て使用する。また、本発明の潤滑剤に酸化防止剤、固体
潤滑剤、油性向上剤、消泡剤および防錆剤などの任意成
分を加えてそのまま使用することも可能である。The lubricant of the present invention is usually used by adding 0.01 to 20% to mineral oil, synthetic lubricating oil, brake fluid, gear oil, metalworking oil, machine industry oil, fuel and fuel oil. . Further, the lubricant of the present invention may be used as it is after adding optional components such as an antioxidant, a solid lubricant, an oiliness improver, an antifoaming agent and a rust preventive.
【００１４】[0014]
【実施例】以下、実施例により本発明をさらに詳しく説
明するが、本発明はこれに限定されるものではない。な
お実施例および比較例中の部は重量部を示す。EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. Parts in Examples and Comparative Examples are parts by weight.
【００１５】実施例１ オートクレーブにセチルアルコール／ＰＯ付加物（数平
均分子量６００）１２０部、水酸化セシウム（５０％水
溶液、試薬特級、以下同じ）１６部を投入して１２０℃
にて減圧下攪拌して均一に溶解、脱水した。次いで、１
００℃にて系内を０〜１０ｍｍＨｇとした後、８８０部
のＰＯをゲージ圧で約４〜６ｋｇ／ｃｍ2に保つように
連続的に導入した。次いで同温度にて約３時間熟成して
粗ポリエーテルを得た。通常の吸着剤処理後のＴＵ値
０．０３０ｍｅｑ／ｇ、ＧＰＣ分析の結果は、数平均分
子量約３，０５０、低分子量成分含有量は０．０４１
％、分子量の分散度（Ｍｗ／Ｍｎ）は１．２３であっ
た。ＴＵ値は下記に準拠して測定した。（以下同じ）。
表１に潤滑剤としての評価結果を記載する（以下同
じ）。 ＴＵ値：ＡＳＴＭＤ−２８４９−６９（酢酸第二水銀
法）Example 1 120 parts of cetyl alcohol / PO adduct (number average molecular weight 600) and 16 parts of cesium hydroxide (50% aqueous solution, reagent grade, the same hereafter) were put into an autoclave and the temperature was 120 ° C.
The solution was stirred under reduced pressure to dissolve and dehydrate uniformly. Then 1
After setting the system to 0 to 10 mmHg at 00 ° C., 880 parts of PO was continuously introduced so as to maintain the gauge pressure at about 4 to 6 kg / cm 2 . Then, the mixture was aged at the same temperature for about 3 hours to obtain a crude polyether. The TU value after ordinary adsorbent treatment was 0.030 meq / g, the result of GPC analysis was a number average molecular weight of about 3,050, and a low molecular weight component content was 0.041.
%, The polydispersity degree (Mw / Mn) of the molecular weight was 1.23. The TU value was measured according to the following. (same as below).
Table 1 shows the evaluation results as a lubricant (the same applies hereinafter). TU value: ASTMD-2849-69 (mercuric acetate method)
【００１６】実施例２ オートクレーブにオレイルアルコール／ＥＯ付加物（数
平均分子量６００）８５部、水酸化セシウム１６部を投
入して１２０℃にて減圧下攪拌して均一に溶解、脱水し
た。次いで１００℃にて系内を０〜１０ｍｍＨｇとした
後、９１５部のＰＯをゲージ圧で約４〜６ｋｇ／ｃｍ2
に保つように連続的に導入した。次いで同温度にて約４
時間熟成して粗ポリエーテルを得た。通常の吸着剤処理
後のＴＵ値０．０４１ｍｅｑ／ｇ、ＧＰＣ分析の結果
は、数平均分子量約３，７５０、低分子量成分含有量は
０．０５８％、分子量の分散度は１．３４であった。Example 2 85 parts of oleyl alcohol / EO adduct (number average molecular weight 600) and 16 parts of cesium hydroxide were put into an autoclave and stirred at 120 ° C. under reduced pressure to uniformly dissolve and dehydrate. Next, after setting the inside of the system to 0 to 10 mmHg at 100 ° C., 915 parts of PO was measured at a gauge pressure of about 4 to 6 kg / cm 2.
Continuously introduced so as to keep. Then about 4 at the same temperature
After aging, a crude polyether was obtained. The TU value after the usual adsorbent treatment was 0.041 meq / g, and the GPC analysis showed that the number average molecular weight was about 3,750, the low molecular weight component content was 0.058%, and the polydispersity of the molecular weight was 1.34. It was
【００１７】実施例３ オートクレーブにｎ−ブタノール／ＰＯ付加物（数平均
分子量６００）８５部水酸化セシウム１６部を投入して
１２０℃にて減圧下攪拌して均一に溶解、脱水した。次
いで、１００℃にて系内を０〜１０ｍｍＨｇとした後、
９１５部のＰＯ／１，２−ブチレンオキシド＝８５／１
５（重量比）の混合アルキレンオキシドをゲージ圧で約
４〜６ｋｇ／ｃｍ2に保つように連続的に導入した。次
いで同温度にて約３時間熟成して粗ポリエーテルを得
た。通常の吸着剤処理後のＴＵ値０．０３８ｍｅｑ／
ｇ、ＧＰＣ分析の結果は、数平均分子量約３，８００、
低分子量成分含有量は０．０５２％、分子量の分散度は
１．２９であった。Example 3 85 parts of n-butanol / PO adduct (number average molecular weight 600) 16 parts of cesium hydroxide were placed in an autoclave and stirred at 120 ° C. under reduced pressure to uniformly dissolve and dehydrate. Then, after setting the system to 0 to 10 mmHg at 100 ° C.,
915 parts of PO / 1,2-butylene oxide = 85/1
5 (weight ratio) of mixed alkylene oxide was continuously introduced so as to keep the gauge pressure at about 4 to 6 kg / cm 2 . Then, the mixture was aged at the same temperature for about 3 hours to obtain a crude polyether. TU value after normal adsorbent treatment 0.038 meq /
g, the result of GPC analysis shows that the number average molecular weight is about 3,800,
The low molecular weight component content was 0.052%, and the molecular weight dispersity was 1.29.
【００１８】比較例１ オートクレーブにパルミチルアルコール／ＰＯ付加物
（数平均分子量６００）８５部、水酸化カリウム（試薬
特級粒状品、以下同じ）４部を投入して１２０℃にて減
圧下攪拌して均一に溶解、脱水した。次いで、１００℃
にて系内を０〜１０ｍｍＨｇとした後、９１５部のＰＯ
をゲージ圧で約４〜６ｋｇ／ｃｍ2に保つように連続的
に導入した。次いで同温度にて約４時間熟成して粗ポリ
エーテルを得た。通常の吸着剤処理後のＴＵ値０．０９
４ｍｅｑ／ｇ、ＧＰＣ分析の結果は、数平均分子量約
１，９００、低分子量成分含有量は０．１０２％、分子
量の分散度は１．４３であった。Comparative Example 1 85 parts of palmityl alcohol / PO adduct (number average molecular weight 600) and 4 parts of potassium hydroxide (reagent grade granular product, the same applies hereinafter) were placed in an autoclave and stirred at 120 ° C. under reduced pressure. It was uniformly dissolved and dehydrated. Then, at 100 ° C
After setting the system to 0-10 mmHg, 915 parts of PO
Was continuously introduced so as to be maintained at about 4 to 6 kg / cm 2 with a gauge pressure. Then, the mixture was aged at the same temperature for about 4 hours to obtain a crude polyether. TU value of 0.09 after normal adsorbent treatment
As a result of GPC analysis, the number average molecular weight was about 1,900, the low molecular weight component content was 0.102%, and the polydispersity of the molecular weight was 1.43.
【００１９】比較例２ オートクレーブにｎ−ブタノール／ＰＯ付加物（数平均
分子量６００）４０部、水酸化カリウム（試薬特級粒状
品、以下同じ）４部を投入して１２０℃にて減圧下攪拌
して均一に溶解、脱水した。次いで、１００℃にて系内
を０〜１０ｍｍＨｇとした後、９６０部のＰＯをゲージ
圧で約４〜６ｋｇ／ｃｍ2に保つように連続的に導入し
た。次いで同温度にて約５時間熟成して粗ポリエーテル
を得た。通常の吸着剤処理後のＴＵ値０．１８２ｍｅｑ
／ｇ、ＧＰＣ分析の結果は、数平均分子量約２，９０
０、低分子量成分含有量は０．２１５％、分子量の分散
度は１．５８であった。Comparative Example 2 40 parts of n-butanol / PO adduct (number average molecular weight 600) and 4 parts of potassium hydroxide (reagent grade granular product, hereinafter the same) were put into an autoclave and stirred at 120 ° C. under reduced pressure. It was uniformly dissolved and dehydrated. Then, after the system was adjusted to 0 to 10 mmHg at 100 ° C., 960 parts of PO was continuously introduced so as to maintain the gauge pressure at about 4 to 6 kg / cm 2 . Then, the mixture was aged at the same temperature for about 5 hours to obtain a crude polyether. TU value after ordinary adsorbent treatment 0.182 meq
/ G, the result of GPC analysis is a number average molecular weight of about 2,90
0, the content of the low molecular weight component was 0.215%, and the polydispersity of the molecular weight was 1.58.
【００２０】比較例３ オートクレーブにｎ−ラウリルアルコール／ＰＯ・ＥＯ
付加物（数平均分子量６００）１２０部、水酸化カリウ
ム４部を投入して１２０℃で減圧下攪拌して脱水した。
次いで１００℃にて系内を０〜１０ｍｍＨｇとした後、
１２０℃にて８８０部のＰＯをゲージ圧で約４〜６ｋｇ
／ｃｍ2に保つように連続的に導入した。次いで同温度
にて約３時間熟成して粗ポリエーテルを得た。通常の吸
着剤処理後のＴＵ値０．１５ｍｅｑ／ｇ、ＧＰＣ分析の
結果は、数平均分子量約２，５５０、低分子量成分含有
量は０．１２１％、分子量の分散度は１．３８であっ
た。Comparative Example 3 n-lauryl alcohol / PO.EO was added to an autoclave.
120 parts of an adduct (number average molecular weight 600) and 4 parts of potassium hydroxide were added and dehydrated by stirring at 120 ° C. under reduced pressure.
Then, after setting the system to 0 to 10 mmHg at 100 ° C.,
Approximately 4 to 6 kg of 880 parts of PO at 120 ° C under gauge pressure
/ Cm 2 It was introduced continuously so as to keep. Then, the mixture was aged at the same temperature for about 3 hours to obtain a crude polyether. The TU value after the usual adsorbent treatment was 0.15 meq / g, and the GPC analysis showed that the number average molecular weight was about 2,550, the low molecular weight component content was 0.121%, and the molecular weight dispersity was 1.38. It was
【００２１】[0021]
【表１】 ｛評価方法｝ 溶解性 ；Ｖｉｓ1.7cSt(40℃)の鉱物油へ１０％添加し均一に溶解させ 、−１０℃での溶解状態を観察した。 摩擦係数 ；Ｖｉｓ1.7cSt の鉱物油へ１％添加し均一に溶解させ測定し 振動摩擦摩耗試験機（ＳＲＶ試験機）を用いた。 荷重 ５０Ｎ、時間３０分、振動幅 ２．０ｍｍ，振動数 ５０Ｈｚ、 温度 ４０℃ 摩耗痕 ；摩擦係数と同様な方法で行い、鋼球の摩耗直径（ｍｍ）を測 定した。 [Table 1] {Evaluation method} Solubility: 10% was added to mineral oil of Vis1.7cSt (40 ° C) and uniformly dissolved, and the dissolved state at -10 ° C was observed. Friction coefficient: 1% was added to mineral oil of Vis1.7cSt and dissolved uniformly, and the measurement was performed using a vibration friction wear tester (SRV tester). Load 50 N, time 30 minutes, vibration width 2.0 mm, frequency 50 Hz, temperature 40 ° C. Wear scar; wear diameter (mm) of steel ball was measured by the same method as friction coefficient.
【００２２】[0022]
【発明の効果】ポリエーテルのＴＵ値を大幅に低下させ
ることで、不要な高分子量体を副成することなく、分子
量の分布が小さく、大きな数平均分子量のものが得られ
る為、低温での鉱物油への溶解性が良くなり、また、摩
擦係数や摩耗痕の小さい潤滑性の良い潤滑剤が得られ
る。したがって、本発明のポリエーテル系潤滑剤は、ブ
レーキフルード、機械用潤滑油、金属加工油、冷凍機用
潤滑油、燃料などに添加して使用でき工業的に極めて有
用である。EFFECTS OF THE INVENTION By significantly reducing the TU value of a polyether, it is possible to obtain a polymer having a large number average molecular weight with a small molecular weight distribution without by-producting an unnecessary high molecular weight substance. The solubility in mineral oil is improved, and a lubricant having a small friction coefficient and wear scar and good lubricity can be obtained. Therefore, the polyether lubricant of the present invention can be used by adding it to brake fluid, machine lubricating oil, metal working oil, refrigerator lubricating oil, fuel, etc., and is industrially very useful.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ１０Ｎ 40:25 40:30 (72)発明者 岩田 典子 京都市東山区一橋野本町11番地の１ 三洋 化成工業株式会社内Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical indication location C10N 40:25 40:30 (72) Inventor Noriko Iwata 1 Sanyo Kasei Kogyo Co., Ltd. 11 Hitotsubashi-honcho, Higashiyama-ku, Kyoto In the company
Claims (2)
量が２０００以上で、かつ、ＴＵ値が下記式（２）を満
たすポリエーテルを含有することを特徴とする潤滑剤。 Ｒ1Ｘ−［（ＥＯ）ｍ／（ＡＯ）ｎ］−Ｙ （１） ［式中、Ｒ1 は炭素数１〜２２のアルキルもしくはア
ルケニル基、Ｅはエチレン基、Ａは炭素数３〜４のアル
キレン基、ＸはＯ原子、Ｓ原子またはＣＯＯ基、Ｙは水
素原子、−Ｒ2またはＲ3ＣＯ−、｛ Ｒ2、Ｒ3 は炭素数
１〜２２のアルキルもしくはアルケニル基｝、ｍは０〜
１００、ｎは２０〜３００の整数を示す。［（ＥＯ）ｍ
／（ＡＯ）ｎ］はランダム付加もしくはブロック付加を
示す。］ ｙ≦２×１０-5×ｚ−０．０１５ （２） ［式中、ｚは数平均分子量、ｙはＴＵ値（ｍｅｑ／ｇ）
を示す。但し、Ｒ1に固有のＴＵ値を持つ場合は、それ
を差し引いた値］1. A lubricant comprising a polyether represented by the following general formula (1), having a number average molecular weight of 2000 or more and a TU value satisfying the following formula (2). R 1 X - [(EO) m / (AO) n] -Y (1) [ wherein, R 1 represents an alkyl or alkenyl group having 1 to 22 carbon atoms, E is ethylene, A is 3-4 carbon atoms Alkylene group, X is an O atom, S atom or COO group, Y is a hydrogen atom, —R 2 or R 3 CO—, {R 2 , R 3 Is an alkyl or alkenyl group having 1 to 22 carbon atoms, and m is 0
100 and n show the integer of 20-300. [(EO) m
/ (AO) n] indicates random addition or block addition. Y ≦ 2 × 10 −5 × z−0.015 (2) [wherein, z is a number average molecular weight, and y is a TU value (meq / g).
Is shown. However, if R 1 has a unique TU value, the value subtracted from it
が、０．８〜１．０である請求項１記載の潤滑剤。2. In the general formula (1), n / (m + n)
Is 0.8 to 1.0, The lubricant according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17419295A JP2873362B2 (en) | 1995-06-16 | 1995-06-16 | lubricant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17419295A JP2873362B2 (en) | 1995-06-16 | 1995-06-16 | lubricant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH093469A true JPH093469A (en) | 1997-01-07 |
| JP2873362B2 JP2873362B2 (en) | 1999-03-24 |
Family
ID=15974341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17419295A Expired - Fee Related JP2873362B2 (en) | 1995-06-16 | 1995-06-16 | lubricant |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2873362B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002285180A (en) * | 2001-03-28 | 2002-10-03 | Sanyo Chem Ind Ltd | Base oil for metal processing |
| JP2003526730A (en) * | 2000-03-16 | 2003-09-09 | ザ ルブリゾル コーポレイション | Lubricating composition for ammonia-based coolant with good sealing performance |
-
1995
- 1995-06-16 JP JP17419295A patent/JP2873362B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003526730A (en) * | 2000-03-16 | 2003-09-09 | ザ ルブリゾル コーポレイション | Lubricating composition for ammonia-based coolant with good sealing performance |
| JP2002285180A (en) * | 2001-03-28 | 2002-10-03 | Sanyo Chem Ind Ltd | Base oil for metal processing |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2873362B2 (en) | 1999-03-24 |
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