JP4365944B2 - Anionic polyether and method for producing the same - Google Patents

Description

【００２４】
本発明のアニオン性ポリエーテル１〜４及び比較対象として下記の比較品１〜５を用いて、以下のように潤滑性及び排水処理性の評価を行った。
（比較品１） アデカカーポールＧＨ−２００
（比較品２） アデカカーポールＧＨ−５
（比較品３） アデカポリエーテルＰＲ−３００７
（比較品４） ポリプロピレングリコールモノブチルエーテル（分子量１，０００）とモノクロロ酢酸ナトリウムから製造されたカルボキシル変性ポリエーテル。
（比較品５） ポリプロピレングリコールモノブチルエーテルリン酸エステルナトリウム塩
尚、本発明のポリエーテル１〜４及び比較品１〜５について塩素含量を分析したところ、比較品４のみ、４５０ｐｐｍの塩素原子が検出されたが、他は何れも１００ｐｐｍ以下であった。
【００２５】
＜潤滑性試験＞
本発明のアニオン性ポリエーテル１〜４又は比較品１〜５の夫々の２０％水溶液を用いて、シェル式高速四球試験機にて、荷重５０ｋｇｆ／ｃｍ、室温、回転数１，５００ｒｐｍ、時間６０秒間の条件で潤滑性試験を行い、平均摩擦係数及びボールの摩耗痕径を測定した。その結果を表２及び表３に示す。
【００２６】
【表２】

【００２７】
【表３】

【００２８】
＜排水処理性試験＞
各試料の１％水溶液に、ポリアクリル酸ナトリウム０．０５％を加えた後、塩化カルシウム０．１％を加えて混合し、室温で１時間静置した。静置後の水溶液の外観を観察して下記の基準で排水処理性を判断した。又、各試料溶液について、沈殿物をろ過した後、ＣＯＤを測定し、排水処理前のＣＯＤ値と比較した。
○：沈殿物があり、上澄み液が透明である
×：処理液を静置した後も、外観に特に変化が無い
これらの結果を表４及び５に示す。
【００２９】
【表４】

【００３０】
【表５】

【００３１】
＜作動油としての評価＞
下記の組成からなる水系作動油を用意した。
(配合) （部）
本発明品又は比較品のポリエーテル ２０
プロピレングリコール ４０
オクチル酸 １．５
トリエタノールアミン ２．０
水 残部
この作動油を、ベッカース製ベーンポンプ（Ｖ−１０４Ｃ）の作動油として使用し、回転数１，２００ｒｐｍ、吐出圧１４０ｋｇ／ｃｍ²、ポンプ入り口温度５０℃、運転時間５００時間で運転した。運転後、スラッジの付着状況と、ベーンとカムリングの摩耗量を測定した。
スラッジの付着状況は以下の基準で評価した。
○：付着量が少ない
△：付着量がやや多い
×：付着量が著しく多い
これらの結果を表６及び表７に示す。
【００３２】
【表６】

【００３３】
【表７】

【００３４】
＜切削油としての評価＞
下記の組成からなる水系作動油を用意した。
(配合) （部）
本発明品又は比較品のポリエーテル ２．５
オクチル酸 ０．１
セバシン酸 ０．２
トリエタノールアミン １．２
水 残部
この切削油について、ファレックス型摩擦試験機を使用して以下の条件でピンの摩耗量を測定し評価した。
回転数：２９０ｒｐｍ
荷 重：６００ｌｂ
試験片（ピン）：ＡＩＳＩ３１３５
試験片（ブロック）：ＡＩＳＩ１１３７
試験時間：１時間
これらの結果を表８及び表９に示す。
【００３５】
【表８】

【００３６】
【表９】

【００３７】
【発明の効果】
本発明の効果は、加水分解しにくく、且つ、排水から容易に分離できて排水処理に悪影響を及ぼすことがない、アニオン性のポリエーテル類及びその製造方法を提供したことである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to novel anionic polyethers and a method for producing the same.
[0002]
[Prior art]
In water-based lubricating oils such as hydraulic oils and metalworking oils, polyether compounds are used as lubricity improvers and thickeners. A water-based lubricant blended with a polyether compound has advantages such as a transparent appearance, nonflammability, high stability at high temperatures, and no fear of separation or decay. However, since polyether compounds have a strong affinity for water, it is difficult to separate them from the medium (usually water) when treating wastewater containing such polyethers. Even if COD does not drop, it may adversely affect wastewater treatment.
On the other hand, anionic substances such as fatty acid soaps and acidic phosphate ester salts are hardly soluble in water or are hardly soluble under acidic conditions. It has the advantage that it can be easily separated from the medium. However, fatty acid soaps and acidic phosphoric acid ester salts, etc. have a problem in that they form metal soaps that are sparingly soluble in hard water.
Therefore, attempts have been made to solve the disadvantages of both by introducing an anionic group such as a carboxyl group or a phosphate group into the polyether. For example, Japanese Patent Application Laid-Open No. 59-38295 proposes a hydraulic oil using a compound having a phosphate ester group introduced at the end of a polyoxyalkylene ether. Japanese Laid-Open Patent Publication No. 7-53985 discloses a flame retardant hydraulic fluid containing a polyether having a carboxyl group or a phosphate ester group.
[0004]
[Problems to be solved by the invention]
However, when the anionic group is a phosphate group, hydrolysis may occur in an aqueous system, which may reduce the pH of the solution or cause microorganisms to be spoiled. Polyethers whose anionic groups are carboxyl groups introduce a carboxyl group by reacting the polyether with chlorocarboxylic acid, so that it is possible to avoid a trace amount of chlorine atoms remaining in the product even after purification. Can not. If chlorine atoms are present as impurities in the product, the metal may rust or increase metal wear when used as an aqueous lubricant.
In addition, a method for obtaining an anionic polyether by adding an alkylene oxide to a fatty acid having a hydroxyl group such as ricinoleic acid or 12-hydroxystearic acid is also conceivable, but the alkylene oxide is also added to a carboxyl group. The number of anionic groups in the resulting polyether is reduced.
Accordingly, an object of the present invention is to provide anionic polyethers that are difficult to hydrolyze and that can be easily separated and removed in wastewater treatment and a method for producing the same.
[0005]
[Means for Solving the Problems]
That is, the present invention relates to an anionic polyether obtained by adding a polyether having a hydroxyl group to an epoxy group of an epoxidized fatty acid ester to obtain an intermediate product, and further saponifying the intermediate product, and production thereof. Is the method.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The epoxidized fatty acid ester which is a raw material of the anionic polyether of the present invention is an ester of an unsaturated fatty acid having a carbon-carbon double bond such as oleic acid, linoleic acid, linolenic acid and alcohol, hydrogen peroxide, It is obtained by epoxidizing a carbon-carbon double bond by acting an epoxidizing agent such as peracetic acid or perbenzoic acid. As such an epoxidized fatty acid ester, a commercially available resin plasticizer or stabilizer can be used.
[0007]
Specific examples of esters of unsaturated fatty acids and alcohols include vegetable oils (glycerides) containing a large amount of unsaturated fatty acids such as soybean oil and linseed oil, or unsaturated fatty acids obtained from these vegetable oils. Short chain alkyl esters such as methyl ester and butyl ester.
The epoxidized fatty acid ester used in the present invention is obtained by epoxidizing an unsaturated bond of a short-chain alkyl ester of these vegetable oils or unsaturated fatty acids with an epoxidizing agent. In addition, this epoxidized fatty acid ester does not need to have all double bonds epoxidized. The preferable epoxy equivalent of the epoxidized fatty acid ester is about 10 to 2,000, more preferably about 50 to 1,000.
[0008]
The polyether containing a hydroxyl group used in the present invention is not particularly limited as long as it has a polyether chain and a hydroxyl group. For example, a polyether monool or polyol obtained by adding an alkylene oxide to a monool. And polyether polyols having an alkylene oxide added thereto.
Examples of monools include methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, pentanol, 2-pentanol, 3-pentanol, isopentyl alcohol, 2-methyl-4-pentanol, and hexanol. Secondary hexanol, isohexanol, heptanol, secondary heptanol, octanol, 2-ethylhexanol, secondary octanol, isooctanol, nonanol, secondary nonanol, 1-decanol, isodecyl alcohol, secondary decanol, undecanol, secondary Undecanol, 2-methyldecanol, lauryl alcohol, secondary dodecanol, 1-tridecanol, isotridecyl alcohol, secondary tridecanol, myristyl alcohol, secondary tetradecanol, penta Canol, secondary pentadecanol, cetyl alcohol, palmityl alcohol, secondary hexadecanol, heptadecanol, secondary heptadecanol, stearyl alcohol, isostearyl alcohol, secondary octadecyl alcohol, oleyl alcohol, behenyl alcohol, eicosanol, Docosanol, tetracosanol, hexacosanol, octacosanol, myricyl alcohol, lasserol, tetratriacontanol, allyl alcohol, cyclopentanol, cyclohexanol, 2-butyloctanol, 2-butyldecanol, 2-hexyloctanol, 2-hexyl decanol, 2-hexyl decanol, 2-octyl decanol, 2-octyl decanol, 2-octyl tetradecanol, 2-decyl Decanol, 2-decyltetradecanol, 2-decylhexadecanol, 2-dodecyltetradecanol, 2-dodecylhexadecanol, 2-dodecyloctadecanol, 2-tetradecyloctadecanol, 2-tetradecylico Monohydric alcohols such as sanol, 2-hexadecyloctadecanol, 2-hexadecylicosanol; phenol, cresol, ethylphenol, tertiary butylphenol, hexylphenol, octylphenol, nonylphenol, decylphenol, undecylphenol, dodecyl Phenols such as phenol, tridecylphenol, tetradecylphenol, phenylphenol, benzylphenol, styrenated phenol, p-cumylphenol and the like can be mentioned.
[0009]
Examples of the polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,2-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2-octanediol, 1,8-octanediol, Such as isoprene glycol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, sorbite, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, dimer diol, etc. Diol; glycerin, trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butane Triol, 2-ethyl 1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl-2,3 Trivalent alcohols such as 4-pentanetriol, pentamethylglycerin, pentaglycerin, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolethane, trimethylolpropane; pentaerythritol, erythritol, 1, 2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,3,4,5-hexanetetrol, diglycerin, sorbitan Tetrahydric alcohols such as adonitol, arabitol, xylitol, triglycerin, etc .; dipe Data erythritol, sorbitol, mannitol, iditol, inositol, dulcitol, talose, hexavalent alcohols such as allose; 8 monohydric alcohols such as sucrose, polyglycerol or these dehydrated condensates and the like.
[0010]
Among these, preferred are monool, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol and the like.
Examples of the alkylene oxide added to the monool or polyol include ethylene oxide, propylene oxide, butylene oxide, and long chain α-olefin oxide. Examples of the form of addition include forms such as single addition of one type of alkylene oxide, block-type addition of two or more types of alkylene oxide, random addition, or a mixture of block-type addition and random-type addition.
[0011]
There is no restriction | limiting in particular in the molecular weight of polyethers containing said hydroxyl group. Usually, it is about 100 to 100,000, preferably about 300 to 50,000, and it is preferable to select appropriately according to the purpose of use of the anionic polyether of the present invention.
The number of anionic groups in the anionic polyether of the present invention is theoretically the same as the number of hydroxyl groups in the polyether containing the hydroxyl group.
[0012]
The anionic polyether of the present invention can be obtained by reacting the epoxidized fatty acid ester with a polyether containing a hydroxyl group and saponifying the resulting intermediate product. First, the reaction of the epoxidized fatty acid ester and the polyether containing a hydroxyl group can be performed under the same conditions as in a normal method in which a hydroxy compound and an epoxide are reacted. That is, as a preferable reaction method, a method of gradually adding an epoxidized fatty acid ester to a hydroxyl group-containing polyether to which a catalyst has been added at a temperature of about 0 to 150 ° C. is preferable. If a too large amount of epoxidized fatty acid ester is added at one time, the epoxy groups may react with each other to form a gel, which is not preferable.
[0013]
As a catalyst that can be used for the reaction of the epoxidized fatty acid ester and a polyether containing a hydroxyl group, a catalyst that reacts a normal hydroxy compound with an epoxide can be used. For example, acidic catalysts such as sulfuric acid, boron trifluoride ether complex (trifluoroborate / etherate), hydrotalcite, activated clay, etc .; sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, water Calcium oxide, barium hydroxide, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, sodium methoxide, potassium methoxide, rubidium methoxide, cesium methoxide, magnesium methoxide, calcium methoxy And basic catalysts such as barium methoxide.
[0014]
If the intermediate product thus obtained is saponified, for example, by treatment in an aqueous alkali solution, the anionic polyethers of the present invention can be obtained. As the alkali that can be used for the saponification, those similar to the above basic catalyst can be used, and among them, the alkali that can be most preferably used is sodium hydroxide or potassium hydroxide. A preferable temperature for carrying out the saponification is about 15 to 80 ° C. When saponification is completed, the alcohol derived from the epoxidized fatty acid ester remains in the product, but this alcohol can be easily removed by distillation under reduced pressure, but it remains in the polyether as it is. It can be left in the room.
[0015]
Since the anionic polyethers of the present invention are obtained by saponifying the intermediate product as described above, they are usually obtained in the form of carboxylate. If necessary, the anionic polyethers of the present invention can be obtained in a free carboxylic acid state by treating them under acidic conditions.
[0016]
Unlike conventional sulfate-based and phosphate-based anionic polyethers, the anionic polyethers of the present invention have no fear of hydrolysis even when used in an aqueous system. In addition, since it has a carboxyl group, after using an aqueous liquid containing the anionic polyethers of the present invention, an alkaline earth metal such as calcium chloride, When an iron group compound is added to this effluent, the anionic polyethers undergo a metathesis reaction and precipitate as insoluble metal salts. If this is filtered as it is or if it is aggregated with a flocculant, it can be easily separated and removed from the drainage. Further, when the pH of the liquid is made acidic, it becomes insoluble and precipitates similarly, so that it can be easily separated and removed. Accordingly, the anionic polyethers of the present invention can be easily separated / removed from various aqueous liquids including them by a simple operation, so that the burden of the waste liquid treatment is small. .
[0017]
The anionic polyethers of the present invention can be used in the same manner for all applications where conventional polyalkylene glycols have been used. For example, use as a surfactant, a lubricant, a working fluid, an antistatic agent, a resin additive, an adhesive and the like can be mentioned.
In particular, the anionic polyethers of the present invention are non-flammable and safe when used as aqueous lubricants such as hydraulic fluids and aqueous metalworking oils. However, it has many advantages such as no hydrolysis and easy wastewater treatment.
[0018]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. In the following examples,% and ppm are based on weight unless otherwise specified.
[0019]
(Production Example 1)
In a four-necked flask, 300 g of polyethylene glycol (molecular weight 600) was charged, 0.2% boron trifluoride ether complex was added to polyethylene glycol, dissolved, and then heated to 40 ° C. There, 280 g of epoxidized soybean oil (epoxy equivalent 280) was dropped over 3 hours. After completion of dropping, the mixture was aged at 50 ° C. for 2 hours, and then the crude product was treated with an adsorbent and filtered. To 500 g of the filtered product, 84 g of a 48% sodium hydroxide aqueous solution was gradually added at 50 ° C., and saponified to obtain a brown paste-like bifunctional anionic polyether 1 of the present invention.
[0020]
(Production Example 2)
Adeka Carpol GH-200 (Random addition of ethylene oxide (EO) and propylene oxide (PO) to glycerol. EO / PO = 50/50 (weight ratio), molecular weight 2,500). 250 g was charged, 0.2% of boron trifluoride ether complex was added to GH-200, dissolved, and then heated to 40 ° C. There, 99 g of epoxidized methyl oleate (epoxy equivalent 330) was dropped over 3 hours. After completion of dropping, the mixture was aged at 50 ° C. for 2 hours, and then the crude product was treated with an adsorbent and filtered. Saponification was performed by gradually adding 16 g of a 48% aqueous sodium hydroxide solution at 50 ° C. to 300 g of the filtered product, and the generated methanol was distilled off under reduced pressure to obtain a brown paste-like trifunctional anionic polyether 2 of the present invention. Obtained.
[0021]
(Production Example 3)
To a four-necked flask, 500 g of Adeka Carpol GH-5 (with EO and PO randomly added to glycerin, EO / PO = 65/35 (weight ratio), molecular weight 5,000) was charged, boron trifluoride The ether complex was added to 0.2% of GH-5, dissolved, and then heated to 40 ° C. There, 99 g of epoxidized methyl oleate (epoxy equivalent 330) was dropped over 3 hours. After completion of dropping, the mixture was aged at 50 ° C. for 2 hours, and then the crude product was treated with an adsorbent and filtered. Saponification was performed by gradually adding 14 g of 48% aqueous sodium hydroxide solution at 50 ° C. to 300 g of the filtered product, and the produced methanol was distilled off under reduced pressure to obtain a brown pasty trifunctional anionic polyether 3 of the present invention. It was.
[0022]
(Production Example 4)
A four-necked flask was charged with 300 g of ADEKA polyether PR-3007 (obtained by random addition of EO and PO to propylene glycol. EO / PO = 70/30 (weight ratio), molecular weight 3,000). The boron ether complex was added to 0.2% of PR-3007, dissolved, and then heated to 40 ° C. There, 84 g of epoxidized soybean oil fatty acid methyl (epoxy equivalent 280) was dripped over 3 hours. After completion of dropping, the mixture was aged at 50 ° C. for 2 hours, and then the crude product was treated with an adsorbent and filtered. Slowly add 15 g of 48% aqueous sodium hydroxide solution at 50 ° C. to 300 g of the filtered product, and distill off the produced methanol under reduced pressure to obtain a brown paste-like bifunctional anionic polyether 4 of the present invention. Obtained.
Table 1 shows the physical property values of the anionic polyethers 1 to 4 of the present invention obtained as described above.
[0023]
[Table 1]

[0024]
Using the anionic polyethers 1 to 4 of the present invention and the following comparative products 1 to 5 as comparative objects, the lubricity and waste water treatment properties were evaluated as follows.
(Comparative product 1) Adeka Carpole GH-200
(Comparative product 2) Adeka Carpole GH-5
(Comparative product 3) Adeka polyether PR-3007
(Comparative product 4) A carboxyl-modified polyether produced from polypropylene glycol monobutyl ether (molecular weight 1,000) and sodium monochloroacetate.
(Comparative product 5) Polypropylene glycol monobutyl ether phosphate sodium salt In addition, when the chlorine content was analyzed for the polyethers 1 to 4 and the comparative products 1 to 5 of the present invention, 450 ppm of chlorine atoms were detected only in the comparative product 4. However, all others were 100 ppm or less.
[0025]
<Lubricity test>
Using a 20% aqueous solution of each of the anionic polyethers 1 to 4 of the present invention or the comparative products 1 to 5, using a shell-type high-speed four-ball tester, the load is 50 kgf / cm, the room temperature, the rotational speed is 1,500 rpm, and the time is 60. The lubricity test was conducted under the condition of seconds, and the average friction coefficient and the wear scar diameter of the ball were measured. The results are shown in Tables 2 and 3.
[0026]
[Table 2]

[0027]
[Table 3]

[0028]
<Wastewater treatment test>
After adding 0.05% sodium polyacrylate to 1% aqueous solution of each sample, 0.1% calcium chloride was added and mixed, and allowed to stand at room temperature for 1 hour. The appearance of the aqueous solution after standing was observed, and the wastewater treatment performance was judged according to the following criteria. Moreover, about each sample solution, after filtering the deposit, COD was measured and compared with the COD value before waste water treatment.
◯: There is a precipitate and the supernatant liquid is transparent. ×: These results are not particularly changed in appearance even after the treatment liquid is allowed to stand. Tables 4 and 5 show the results.
[0029]
[Table 4]

[0030]
[Table 5]

[0031]
<Evaluation as hydraulic oil>
An aqueous hydraulic oil having the following composition was prepared.
(Combination) (Part)
Polyether 20 of the present invention or comparative product
Propylene glycol 40
Octylic acid 1.5
Triethanolamine 2.0
The remainder of the water This hydraulic oil was used as the hydraulic oil for a Beckers vane pump (V-104C) and operated at a rotational speed of 1,200 rpm, a discharge pressure of 140 kg / cm ² , a pump inlet temperature of 50 ° C., and an operating time of 500 hours. After operation, sludge adhesion and vane and cam ring wear were measured.
Sludge adhesion was evaluated according to the following criteria.
○: Adhesion amount is small Δ: Adhesion amount is slightly large ×: Adhesion amount is remarkably large These results are shown in Tables 6 and 7.
[0032]
[Table 6]

[0033]
[Table 7]

[0034]
<Evaluation as cutting oil>
An aqueous hydraulic oil having the following composition was prepared.
(Combination) (Part)
Polyether of the present invention product or comparative product 2.5
Octylic acid 0.1
Sebacic acid 0.2
Triethanolamine 1.2
Remaining water This cutting oil was evaluated by measuring the wear amount of the pin under the following conditions using a Falex friction tester.
Rotation speed: 290rpm
Load: 600 lb
Test piece (pin): AISI3135
Test piece (block): AISI 1137
Test time: 1 hour These results are shown in Table 8 and Table 9.
[0035]
[Table 8]

[0036]
[Table 9]

[0037]
【The invention's effect】
The effect of the present invention is to provide anionic polyethers that are difficult to hydrolyze and that can be easily separated from wastewater and do not adversely affect wastewater treatment, and a method for producing the same.

Claims (3)

Anionic polyethers obtained by adding a polyether having a hydroxyl group to the epoxy group of an epoxidized fatty acid ester to obtain an intermediate product, and further saponifying the intermediate product. Production of anionic polyethers characterized by comprising a step of adding a polyether having a hydroxyl group to an epoxy group of an epoxidized fatty acid ester to obtain an intermediate product, and a step of saponifying the intermediate product Method. An aqueous lubricating composition comprising an anionic polyether obtained by adding water and a polyether having a hydroxyl group to the epoxy group of an epoxidized fatty acid ester and saponifying the resulting intermediate product.