JPH04169554A - Production of neo acid ester - Google Patents
Production of neo acid esterInfo
- Publication number
- JPH04169554A JPH04169554A JP2296673A JP29667390A JPH04169554A JP H04169554 A JPH04169554 A JP H04169554A JP 2296673 A JP2296673 A JP 2296673A JP 29667390 A JP29667390 A JP 29667390A JP H04169554 A JPH04169554 A JP H04169554A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- neo
- ester
- polyol
- lubricating oil
- 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.)
- Pending
Links
- 239000002253 acid Substances 0.000 title claims abstract description 24
- 150000002148 esters Chemical class 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- 229920005862 polyol Polymers 0.000 claims abstract description 14
- 150000003077 polyols Chemical class 0.000 claims abstract description 14
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 8
- -1 phosphorous ester Chemical class 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 11
- 150000003460 sulfonic acids Chemical class 0.000 claims description 3
- 239000010687 lubricating oil Substances 0.000 abstract description 12
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 abstract description 3
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 2
- 150000007513 acids Chemical class 0.000 abstract 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 abstract 1
- 229940092714 benzenesulfonic acid Drugs 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 238000005406 washing Methods 0.000 description 8
- 210000003127 knee Anatomy 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- VUAXHMVRKOTJKP-UHFFFAOYSA-N 2,2-dimethylbutyric acid Chemical compound CCC(C)(C)C(O)=O VUAXHMVRKOTJKP-UHFFFAOYSA-N 0.000 description 2
- CXOWYJMDMMMMJO-UHFFFAOYSA-N 2,2-dimethylpentane Chemical compound CCCC(C)(C)C CXOWYJMDMMMMJO-UHFFFAOYSA-N 0.000 description 2
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 2
- ZRYCZAWRXHAAPZ-UHFFFAOYSA-N alpha,alpha-dimethyl valeric acid Chemical compound CCCC(C)(C)C(O)=O ZRYCZAWRXHAAPZ-UHFFFAOYSA-N 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- CBQQWWYZSKCIRS-UHFFFAOYSA-N 2,2,3,3-tetramethylpentanoic acid Chemical compound CCC(C)(C)C(C)(C)C(O)=O CBQQWWYZSKCIRS-UHFFFAOYSA-N 0.000 description 1
- NHBUGGCJRMEOCC-UHFFFAOYSA-N 2,2,4-trimethylpentanoic acid Chemical compound CC(C)CC(C)(C)C(O)=O NHBUGGCJRMEOCC-UHFFFAOYSA-N 0.000 description 1
- JLCYYQOQSAMWTA-UHFFFAOYSA-N 2,3,3,4-tetramethylpentane Chemical compound CC(C)C(C)(C)C(C)C JLCYYQOQSAMWTA-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 1
- AAOISIQFPPAFQO-UHFFFAOYSA-N 7:0(6Me,6Me) Chemical compound CC(C)(C)CCCCC(O)=O AAOISIQFPPAFQO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OHDBYQSGLSTIHF-UHFFFAOYSA-N benzenesulfonic acid;methanesulfonic acid Chemical compound CS(O)(=O)=O.OS(=O)(=O)C1=CC=CC=C1 OHDBYQSGLSTIHF-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は潤滑油に適するネオ酸エステルの製造方法に関
する
〈従来の技術〉
従来、トリメチロールプロパントリヘキサノエート、ト
リメチロールプロパントリオレートなどのヒンダードエ
ステルが各種潤滑油として使用されているが、耐加水分
解性、１ヒ安定性等についてはまだまだ問題が多い。そ
こでトリメチロールプロパン等のポリオールに分解しに
くいネオ酸を反応せしめたネオエステルが検討されてい
るがポリオール側の未反応部分が残るため製品は高い水
酸基価を示す。水酸基価が高いと潤滑油の電気的特性及
び耐加水分解性が劣り、冷蔵庫等の冷凍機油には使用で
きない。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a method for producing a neoacid ester suitable for lubricating oil. Hindered esters have been used as various lubricating oils, but there are still many problems with regard to hydrolysis resistance, 1H stability, etc. Therefore, neoesters, which are made by reacting neoacids that are difficult to decompose with polyols such as trimethylolpropane, are being considered, but because the unreacted portion of the polyol remains, the products exhibit high hydroxyl values. If the hydroxyl value is high, the electrical properties and hydrolysis resistance of the lubricating oil will be poor, and it cannot be used as a refrigerating machine oil for refrigerators and the like.
く本発明が解決しようとする課題〉
本発明は反応を充分に行なわしめ、未反応部分のほとん
どないポリオールのネオ酸エステルを製造することをｌ
１題とする。Problems to be Solved by the Present Invention The present invention aims to sufficiently carry out the reaction and produce a polyol neoacid ester with almost no unreacted portion.
There will be one topic.
＜ｍ題を解決するための手段〉
本発明者らは、上記課題を解決する為、反応触媒につい
て種々検討した結果、水酸基を３個以上含有するポリオ
ールとネオ酸をほぼ完全に反応させるには、反応触媒と
して無機酸又は有機スルホン酸から選ばれる少なくとも
一種と亜リン酸エステルとの併用が優れていることを見
比した。<Means for solving problem m> In order to solve the above problem, the present inventors have conducted various studies on reaction catalysts, and have found that in order to almost completely react a polyol containing three or more hydroxyl groups with a neoacid, It has been found that the combined use of at least one selected from inorganic acids or organic sulfonic acids and phosphite as a reaction catalyst is excellent.
従来からエステル化の触媒として無機酸又は有機スルホ
ン１よ使用されているが、この触媒を水酸基価を３個以
上含有するポリオールとネオ酸の反応に適用してもポリ
オール中の一部が未反応のまま残ってしまう。Conventionally, inorganic acids or organic sulfones1 have been used as catalysts for esterification, but even when this catalyst is applied to the reaction of a neoacid with a polyol containing three or more hydroxyl groups, a portion of the polyol remains unreacted. It remains as it is.
一方、触媒として亜リン酸エステルを単独使用する場合
は非常に反応が進みにくい。On the other hand, when a phosphite ester is used alone as a catalyst, the reaction progresses very slowly.
ところが無機又は有機スルホン酸と亜リン酸エステルを
併用する場合はポリオール部分はほぼ完全に反応し水酸
基価で表示すると３以下のものかえられる。併用するこ
とによフて反応が進む理由については明解には分ってい
ない。However, when an inorganic or organic sulfonic acid and a phosphite are used together, the polyol portion reacts almost completely and the hydroxyl value can be changed to 3 or less. The reason why the reaction progresses when used together is not clearly understood.
ここで使用される無機酸としては硫酸、＠酸等があげら
れ、また有機スルホン酸としてはトルエンスルホン酸、
ベンゼンスルホントメタンスルホン酸等があげられる。Inorganic acids used here include sulfuric acid, @ acid, etc., and organic sulfonic acids include toluenesulfonic acid,
Examples include benzenesulfonate methanesulfonic acid.
又亜リン酸エステルとしてはトリフェニルフォスファイ
ト、トリメチルフォスファイト、トリオクチルフォスフ
ァイト等が例示される。Examples of the phosphite include triphenylphosphite, trimethylphosphite, trioctylphosphite, and the like.
本発明で使用される水酸基を３個以上含有するポリオー
ルとしてはグリセロール、ジグリセロール、トリメチロ
ールエタン、ジ（トリメチロールエタン）、トリメチロ
ールプロパン、ジ（トリメチロールプロパン）、ペンタ
エリスリトール、ジ（ペンタエリスリトール）、トリ
（ペンタエリスリトール）等があげられる。Polyols containing three or more hydroxyl groups used in the present invention include glycerol, diglycerol, trimethylolethane, di(trimethylolethane), trimethylolpropane, di(trimethylolpropane), pentaerythritol, and di(pentaerythritol). ),bird
(pentaerythritol), etc.
又１本発明で使用されるネオ酸としてはカルボキシル基
の隣の炭素に３個のアルキルを有するものを意味してい
るが、具体的にはピバリンｉ！、２゜２−ジメチルブタ
ンＥ ２，２−ジメチルペンタン酸、２−エチル２−メ
チルブｆｆｌ！、 ２．２−ジメチルへブタン酸、２，
２，４．４−テトラメチルブタン酸、２−イソプロピル
２．３−ジメチルブタンａ、２−エチル２，３．３−Ｉ
−ジメチルブタン１．２，２，３．４−テトラメチルペ
ンタン酸、２，２，３．３−テトラメチルペンタン酸又
はこれらの混合物であるネオペンタンＬネオへブタン酸
、ネオノナン酸、ネオデカン酸等が例示される。一般に
反応させようとするネオ酸の仕込量は水酸基を３個以上
含有するポリオールに対して当量比で３％〜３５％過剰
に用い、反応後のその過剰のネオ酸は加温減圧下に１去
し回収される。Furthermore, the neoacid used in the present invention refers to one having three alkyl atoms on the carbon next to the carboxyl group, and specifically, pivalin i! , 2゜2-dimethylbutane E 2,2-dimethylpentanoic acid, 2-ethyl 2-methylbuffl! , 2.2-dimethylhebutanoic acid, 2,
2,4.4-tetramethylbutanoic acid, 2-isopropyl 2,3-dimethylbutane a, 2-ethyl 2,3.3-I
-dimethylbutane 1.2,2,3.4-tetramethylpentanoic acid, 2,2,3.3-tetramethylpentanoic acid or a mixture thereof neopentane L neohebutanoic acid, neononanoic acid, neodecanoic acid, etc. Illustrated. Generally, the amount of neoacid to be reacted is 3% to 35% excess in equivalent ratio to the polyol containing 3 or more hydroxyl groups, and after the reaction, the excess neoacid is heated and decompressed by 1%. removed and collected.
又、本発明で使用される混合触媒の添加量は無機酸又は
有機スルホン酸が反応系全重量に対して０゜１％〜１．
０％、又亜リン酸エステルが０゜５％〜５．０％である
のが通常である。使用した触媒の無機酸又は有機スルホ
ン酸はアルカリ水洗等により最終的には製品から除去さ
れる。Further, the amount of the mixed catalyst used in the present invention is 0.1% to 1.0% of the inorganic acid or organic sulfonic acid based on the total weight of the reaction system.
0%, and the phosphorous acid ester content is usually 0.5% to 5.0%. The inorganic acid or organic sulfonic acid of the catalyst used is finally removed from the product by washing with alkaline water or the like.
又、反応温度としては使用されるネオ酸の沸点等によっ
ても異なるが、通常１５０〜２５０℃で実施される。許
される限りにおいては２００〜２５０℃で実施される方
が好ましい。Although the reaction temperature varies depending on the boiling point of the neoacid used, it is usually carried out at 150 to 250°C. It is preferable to carry out the reaction at a temperature of 200 to 250°C as long as it is permissible.
〈実施例〉
以下に本発明を実施例により具体的に説明するが、本発
明はこれらの実施例に限定されるものではない。<Examples> The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples.
尚、潤滑油としての特性は下記の試験法で測定した。The properties as a lubricating oil were measured by the following test method.
１）１００℃及び４０℃における動粘度；ＪＩＳ２）流
動点；ＪＩＳ Ｋ２２６９
３）Ｒ−１３４ａとの相溶性；供試油とＲ−１３４８と
を７＝３（重量）で混合し一４０℃に冷却し、分離する
ものをＸ、分離しないものをＯとする。1) Kinematic viscosity at 100°C and 40°C; JIS 2) Pour point; JIS K2269 3) Compatibility with R-134a; Mix the test oil and R-1348 at 7=3 (weight) and heat to -40°C. Let X be the thing that is cooled and separated, and O be the thing that is not separated.
４）耐加水分解性；ＡＳ”ｒＭ Ｄ２６１９の試験に
おいて供試油の酸価に変化のないものを０、酸価の変化
率が５％以内のものを△、５％を越える物を×とする。4) Hydrolysis resistance: AS”rM D2619 test: 0 if there is no change in the acid value of the sample oil, △ if the acid value change rate is within 5%, × if it exceeds 5%. do.
実施例１
トリメチロールプロパン１３４ｇと２．２−ジメチルブ
タン５１３７１ ｇを２．０ｇのパラトルエンスルホン
酸と５．０ｇのトリフェニルフォスファイトの触媒存在
下に２００〜２３０℃で水酸基価が１以下になるまで反
応させる。反応終了後、過剰酸を系外に除き、３％炭酸
ナトリウム洗浄、水洗浄、脱水及び液通を行なう、得ら
れた物の潤滑油としての特性を測定すると次のとおりで
あった。Example 1 134 g of trimethylolpropane and 51,371 g of 2,2-dimethylbutane were reduced to a hydroxyl value of 1 or less at 200 to 230°C in the presence of a catalyst of 2.0 g of para-toluenesulfonic acid and 5.0 g of triphenylphosphite. Let it react until the reaction is complete. After the reaction was completed, excess acid was removed from the system, followed by washing with 3% sodium carbonate, washing with water, dehydration, and liquid passage.The properties of the obtained product as a lubricating oil were measured as follows.
１００℃における動粘度：５．８ｃＳｔ４０℃における
動粘度 ： ５５ｃＳｔ流動点ニー３０℃ 水酸基価
：Ｏ，Ｏ！５ＫＯＨＩＩｇ１ｇ １９価： ０ 、
ＯＩ ＫＯＨｗｇ／ｇ 体積固有抵抗：４．４本１０
１４Ωｌ附加水分解性二〇Ｒ−１３４ａとの相溶性：Ｏ
実施例２
ジトリメチロールプロパン２５０ｇと２，２−ジメチル
ペンタン９５５９ ｇを０．８１ｇの硫酸と４．０５ｇ
のトリエチルフォスファイトの触媒存在下に２００〜２
３０’Ｃで水酸基価が１以下になるまで反応させる。反
応終了後過剰酸を系外に除き、３％炭酸ナトリウム洗浄
、水洗浄、脱水及び濾過を行う。得られた物の潤滑油と
しての特性を測定すると次の通りであった。Kinematic viscosity at 100°C: 5.8 cSt Kinematic viscosity at 40°C: 55 cSt Pour point at knee 30°C Hydroxyl value: O, O! 5KOHIIg1g 19 value: 0,
OI KOHwg/g Volume resistivity: 4.4 pieces 10
Compatibility with hydrolyzable 20R-134a with 14Ωl: O Example 2 250 g of ditrimethylolpropane and 9559 g of 2,2-dimethylpentane were mixed with 0.81 g of sulfuric acid and 4.05 g.
200-2 in the presence of a catalyst of triethyl phosphite.
The reaction is carried out at 30'C until the hydroxyl value becomes 1 or less. After the reaction is completed, excess acid is removed from the system, and the mixture is washed with 3% sodium carbonate, washed with water, dehydrated, and filtered. The properties of the obtained product as a lubricating oil were measured and were as follows.
１００℃における動粘度 ニー２０ｃＳｔ４０℃に右け
る動粘度 ： ４００ｃＳｔ流動点ニー２０”Ｃ水酸
基価：０．０２ＫＯＨｍｇ１ｇ １ｍ価： ０ 、０
２ ＫＯＨｍｇ／ｇ 体積固有抵抗：５，２本１０１
４Ω■ 加水分解性二０Ｒ−１３４ａとの相溶性：○
実施例３
トリメチロールエタン１２０ｇと２，２−ジメチルペン
タン酸３７１ｇを２．０ｇのパラトルエンスルホン酸と
５．０ｇのトリオクチルフォスファイトの触媒存在下に
２００〜２３０℃で水酸基価が１以下になるまで反応さ
せる。反応終了後過剰酸を系外に除き、３％炭酸ナトリ
ウム洗浄、水洗浄、脱水、及び濾過を行う。得られた物
の潤滑油としての物性を測定すると次の通りであった。Kinematic viscosity at 100°C Knee 20cSt Kinematic viscosity at 40°C: 400cSt Pour point Knee 20”C Hydroxyl value: 0.02KOHmg1g 1m value: 0,0
2 KOHmg/g Volume resistivity: 5, 2 101
4Ω■ Compatibility with hydrolyzable 20R-134a: ○ Example 3 120 g of trimethylolethane and 371 g of 2,2-dimethylpentanoic acid were mixed with 2.0 g of para-toluenesulfonic acid and 5.0 g of trioctyl phosphite. The reaction is carried out at 200 to 230°C in the presence of a catalyst until the hydroxyl value becomes 1 or less. After the reaction is completed, excess acid is removed from the system, followed by washing with 3% sodium carbonate, washing with water, dehydration, and filtration. The physical properties of the obtained product as a lubricating oil were measured and were as follows.
１００℃における動粘度 ： ４．６ｃＳｔ４０℃に
おける動粘度 ： ３０ｃＳｔ流動点ニー４０℃
水酸基価：０．０２ＫＯ）ＩＢ；／ｇ ！！［価：
０ 、０３ ＫＯＨｍｇ／ｇ 体積固有抵抗：４．
６本１０′４Ω国 加水分解性：０Ｒ−１３４ａとの相
溶性：Ｏ
比較例１
トリメチロールプロパン１３４ｇと２．２−ジメチルブ
タン酸を２．０ｇのパラトルエンスルホン酸触媒存在下
に２００〜２３０℃で反応させると赤褐色の生成物が得
られる。この反応物中から過剰酸を系外に除き、３％炭
酸ナトリウム洗浄。Kinematic viscosity at 100°C: 4.6cSt Kinematic viscosity at 40°C: 30cSt Pour point knee at 40°C
Hydroxyl value: 0.02KO)IB;/g! ! [Value:
0,03 KOHmg/g Volume resistivity: 4.
6 pieces 10'4 Ω Country Hydrolyzability: 0 Compatibility with R-134a: O Comparative Example 1 134 g of trimethylolpropane and 2,2-dimethylbutanoic acid were mixed in the presence of 2.0 g of p-toluenesulfonic acid catalyst to 200-230 When reacted at ℃, a reddish-brown product is obtained. Excess acid was removed from the reaction mixture and washed with 3% sodium carbonate.
水洗浄、脱水及び濾過を行う。得られた物の潤滑油とし
ての物性を測定すると次の通りであった。Perform water washing, dehydration and filtration. The physical properties of the obtained product as a lubricating oil were measured and were as follows.
１００℃における動粘度 ： ６．２ｃＳｔ４０℃に
おける動粘度 ： ６５ｃＳｔ流動点ニー２５℃ 水
酸基価＝３３、ＯＫＯＨｍ（／に 酸価： ０ 、０５
ＫＯＨｍｇ／Ｋ 体積固有抵抗：２．５本１０１０
Ω１ 加水分解性：ＸＲ−１３４ａとの相溶性：×
比較例２
トリメチロールエタン１３４ｇと２，２−ジメチルブタ
ン酸を５．０ｇのトリフェニルフォスファイト触媒存在
下に２００〜２３０”Ｃで２４時間厘広させる６反応終
了後過剰酸を系外に除き３％炭酸ナトリウム洗浄、水洗
浄、脱水及び濾過を行う、得られた物の潤滑油としての
物性を測定すると次の通りであった。Kinematic viscosity at 100°C: 6.2 cSt Kinematic viscosity at 40°C: 65 cSt Pour point knee 25°C Hydroxyl value = 33, OKOHm (/) Acid value: 0,05
KOHmg/K Volume resistivity: 2.5 pieces 1010
Ω1 Hydrolyzability: Compatibility with XR-134a: × Comparative Example 2 134 g of trimethylolethane and 2,2-dimethylbutanoic acid were heated at 200 to 230”C for 24 hours in the presence of 5.0 g of triphenylphosphite catalyst. 6 After the completion of the spreading reaction, excess acid was removed from the system, followed by washing with 3% sodium carbonate, washing with water, dehydration and filtration.The physical properties of the obtained product as a lubricating oil were measured as follows.
１００℃における動粘度 ： ６．３ｃＳｔ４０℃に
おける動粘度 ： ７ＱｃＳｔ流動点ニー２０℃ 水
酸基価： ｌ ７６ ＫＯＨＢ／ｚ酸価：０．１０ＫＯ
）Ｉｓ区／区 体積固有抵抗：１．０本１０’Ωｌ 加
水分解性：×
Ｒ−１３４ａとの相溶性：Ｘ
〈発明の効果〉
本発明で得られるネオ酸エステルは実施例等にも記した
ごとく製品酸価が低いばかりでなくポリオールの未反応
部分に基ずく水酸基価も非常に低い。従って、かくして
得られた物は潤滑油として用いた時電気的特性等に優れ
ている。又、得られ・たエステルはネオ酸エステルであ
るため２加水分解性及び酸価安定性にも優れている。又
１本発明で得られるネオ酸エステルはオゾン層破壊の問
題から代替フロン冷媒として注目されている１、１゜１
．２−テトラフルオロエタン（Ｒ−１３４ａ）との相溶
性にも優れている。Kinematic viscosity at 100°C: 6.3cSt Kinematic viscosity at 40°C: 7QcSt Pour point knee 20°C Hydroxyl value: l 76 KOHB/z Acid value: 0.10KO
)Is area/area Volume resistivity: 1.0 10'Ωl Hydrolyzability: × Compatibility with R-134a: As a result, not only the acid value of the product is low, but also the hydroxyl value, which is based on the unreacted portion of the polyol, is also very low. Therefore, the product thus obtained has excellent electrical properties when used as a lubricating oil. Furthermore, since the obtained ester is a neoacid ester, it has excellent dihydrolyzability and acid value stability. In addition, the neo acid ester obtained by the present invention is attracting attention as an alternative CFC refrigerant due to the problem of ozone layer depletion1,1゜1
．． It also has excellent compatibility with 2-tetrafluoroethane (R-134a).
Claims (1)
せるにおいて、触媒として無機酸又は有機スルホン酸か
ら選ばれる少なくとも一種と亜リン酸エステルを用いる
ことを特徴とするネオ酸エステルの製造方法A method for producing a neo-acid ester, which comprises using at least one selected from inorganic acids or organic sulfonic acids and a phosphorous ester as a catalyst in reacting a polyol containing three or more hydroxyl groups with a neo-acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2296673A JPH04169554A (en) | 1990-11-01 | 1990-11-01 | Production of neo acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2296673A JPH04169554A (en) | 1990-11-01 | 1990-11-01 | Production of neo acid ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04169554A true JPH04169554A (en) | 1992-06-17 |
Family
ID=17836595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2296673A Pending JPH04169554A (en) | 1990-11-01 | 1990-11-01 | Production of neo acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04169554A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5569450A (en) * | 1993-03-17 | 1996-10-29 | Minnesota Mining And Manufacturing Company | Aerosol formulation containing an ester-, amide-, or mercaptoester-derived dispersing aid |
| JP2009501142A (en) * | 2005-06-24 | 2009-01-15 | ヘキソン スペシャルティ ケミカルズ インコーポレーテッド | Method for esterifying polyols with tertiary alkyl-substituted acids |
-
1990
- 1990-11-01 JP JP2296673A patent/JPH04169554A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5569450A (en) * | 1993-03-17 | 1996-10-29 | Minnesota Mining And Manufacturing Company | Aerosol formulation containing an ester-, amide-, or mercaptoester-derived dispersing aid |
| JP2009501142A (en) * | 2005-06-24 | 2009-01-15 | ヘキソン スペシャルティ ケミカルズ インコーポレーテッド | Method for esterifying polyols with tertiary alkyl-substituted acids |
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