JPS6265738A - Aqueous emulsion and cutting oil composed thereof - Google Patents

Abstract

PURPOSE:To obtain an aq. emulsion of an oil-in-water type which is useful as an excellent cutting oil by using a graft modified ethylene.alpha-olefin copolymer which is liquid or semi-solid at an ordinary temp. CONSTITUTION:The ethylene.alpha-olefin copolymer which had 30-70mol% ethylene content, in which alpha-olefin is alpha-olefin of 3-14C and which has 500-10,000 number average mol.wt. is brought into reaction with a graft monomer component in the presence of a radial generator by which the copolymer is graft-modified. An unsatd. carboxylic acid such as acrylic acid or maleic acid or the ethylene thereof is used as the graft modifying component and the graft modified ethylene.alpha-olefin copolymer contains about 1-20wt% modifying component. The aq. emulsion produced from the resulted graft modified ethylene.alpha-olefin copolymer by or without using a surface active agent obviates the generation of the deterioration and burn of the oil component even at a high temp. when used as the cutting oil.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to aqueous emulsions, and more particularly to aqueous emulsions useful as cutting fluids.

[Prior Art] Conventionally, it has been known to use an ethylene/α-olefin copolymer that is liquid at room temperature as a synthetic lubricating oil.

JP-A-51-112809 discloses that the propylene content is 37 to 30% by weight and the molecular weight distribution (MW/Mn) is 2.
A lubricating oil containing, as a viscosity index improver, an ethylene-propylene copolymer having an intrinsic viscosity of 0.4 to 145, measured as a toluene solution at 30° C., is described.

Japanese Patent Publication No. 47-42723 discloses a lubricating oil composition comprising a large proportion of lubricating oil and a small proportion of ethylene/α-olefin (03-01a) copolymer. The copolymer has an ethylene content of 70 to 91 mol%, a crystallinity of about 3 to 18%, and a Mw of about 4 or less.
/Mn and a viscosity average molecular weight of about 10,000 to 200,000, Japanese Patent Publication No. 47-21650 discloses that the kinematic viscosity at about 99°C is 1 to 30 centistokes and the viscosity index is 110. that's all,
Synthetic lubricating oils containing ethylene-propylene copolymers with pour points below 132° C. and containing 29 to 71 mole percent ethylene are described.

JP-A-48-65205 describes a lubricant containing a large proportion of lubricating oil and a small proportion of 1 to 25% of an ethylene-propylene copolymer for improving the viscosity index of crystallinity. ing.

In addition, JP-A-57-117595 discloses that the ethylene content is 30 to 70 mol%, the number average molecular weight is 300'-200
0. An ethylene/α-olefin copolymer synthetic lubricating oil having a Q value (Mw/Mn) of 3 or less and a statistical molecular weight distribution is described.

JP-A-59-227980 discloses (a) fats and oils;
A metalworking oil composition is described that contains as essential components a lubricating oil component selected from mineral oil and fatty acid ester, and (b) a water-soluble polymer compound containing a basic nitrogen atom or a cationic nitrogen atom. . The metal working oil composition is different from an aqueous emulsion in that the lubricating oil component (a) is emulsified.

In addition, Japanese Patent Application Laid-open No. 59-53599 discloses that 0°1 to 3
Multi-purpose emulsion mold for manufacturing heat-treated steel pipes containing 0% natural or synthetic wax, 0.1-50% rust inhibitor, 0.1-30% oiliness improver and 0.1-20% emulsifier. A composition is described.

However, as far as the present inventors know, an oil-in-water type aqueous emulsion using a graft-modified ethylene/α-olefin copolymer that is liquid or semi-solid at room temperature is not known.

[Problems to be Solved by the Invention] An object of the present invention is to provide an oil-in-water type aqueous emulsion using a graft-modified ethylene/α-olefin copolymer.

Another object of the present invention is to provide an aqueous emulsion using a graft-modified ethylene/α-olefin copolymer which itself has surfactant ability and can therefore be emulsified without the use of a separate surfactant. There is a particular thing.

Another object of the present invention is to provide a cutting oil comprising an oil-in-water type aqueous emulsion using a graft-modified ethylene/α-olefin copolymer.

Still another object of the present invention is to provide an excellent cutting machine that forms a strong oil film to reduce the amount of wear on drill teeth, bits, etc., has sufficient heat resistance, and can advantageously remove the amount of heat generated. The purpose is to provide oil.

Further objects and advantages of the present invention will become apparent from the following description.

[Means and effects for solving the problems] According to the present invention, the objects and advantages of the present invention are obtained by preparing an oil-in-water type graft-modified ethylene/α-olefin copolymer that is liquid or semi-solid at room temperature. Achieved by an aqueous emulsion.

Graft modified ethylene α- used in the present invention
Olefin copolymers are produced by graft modification of ethylene/α-olefin copolymers. Graft modification can be easily carried out, for example, by reacting an ethylene/α-olefin copolymer with a graft monomer component in the presence of a radical generator, such as a peroxide.

The graft-modified reaction product thus obtained is treated with an inorganic basic compound such as caustic soda, caustic potash or ammonia, a mono-, di- or tri-alkylamine such as -methylamine, -ethylamine, etc. prior to an aqueous emulsification treatment. Alternatively, the graft monomer component can be treated with an organic basic compound such as mono-, di-, or tri-ethanolamine or morpholine to produce a partially or fully neutralized form of the carboxylate group, as described below. By carrying out the emulsification treatment in the presence of the alkali described above, it is also possible to produce carboxylate groups in which part or all of the graft monomer components are neutralized. Therefore, it should be understood that the graft-modified ethylene/α-olefin copolymers of the present invention include those having carboxylate groups as described above.

The graft-modified ethylene/α-olefin copolymer preferably used in the present invention is, for example, about 1 to 20% by weight after conversion to the graft-modified component, more preferably about 3% by weight.
It has ~15% by weight of graft modification component.

The graft-modified components constituting the graft-modified ethylne/α-olefin copolymer of the aqueous dispersion of the present invention include, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and bisic acid. 2,2,1]bebuto-2-ene-5,6-dicarboxylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, bicyclo[2,2,1]hept-2-ene-5,
Unsaturated carboxylic acids or anhydrides thereof such as 6-dicarboxylic anhydride can be mentioned.

The graft modified ethylene/α-olefin copolymer is
That number average molecule! (Mn) is preferably 500 to 10,
000. It is particularly preferably in the range of 300 to 5.000, and its Q value (weight average molecular weight/number average molecular weight)
is preferably in the range of 3 or less, particularly preferably 2.8 or less, and the copolymer is liquid or semi-solid at room temperature. Combination is preferred.

The ethylene/α-olefin copolymer constituting the graft-modified ethylene/α-olefin copolymer preferably has an ethylene content of 30 to 70 mol%, more preferably 40 to 30 mol%.

Examples of the α-olefin as a copolymerization component include propylene, 1-puran, 1-pentene, 1-hexene, 1
- C 3 to 20 α-olefins such as octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 4-methyl-1-pentene are preferred, and -C is mentioned. I can do it. Among these, α-olefins having 3 to 14 carbon atoms are more preferred, and α-olefins having 8 to 14 carbon atoms are especially preferred. Two or more of these α-olefins can be used in combination.

The number average molecular weight of the ethylene/α-olefin copolymer is
Preferably it is 500-10,000.

The ethylene/α-olefin copolymer is preferably liquid at room temperature, and preferably has a Q value of 3 or less (weight average molecular weight/number average molecular weight, more preferably 2
．． It has a Q value of 8 or less.

Note that the ethylene content in the ethylene/α-olefin copolymer can be measured by l 3 C-NMR analysis. In addition, the number average molecular weight of the ethylene/α-olefin copolymer was determined by GPC (Gel P
chromat-ograph
) is measured by Furthermore, the Q value of the ethylene/α-olefin copolymer was determined using a standard material with known molecular weight (monodisperse polystyrene, Mw -500 to 840X10', 16
Measure the GPC counts using
A correlation diagram (calibration curve) is created, and using this correlation diagram, the molecular weight is determined and calculated from the GPC pattern of the copolymer whose Q value is to be determined.

The above-mentioned ethylene/α-olefin copolymer used in the present invention is produced by, for example, copolymerizing ethylene and α-olefin in a liquid phase using a catalyst formed from a soluble vanadium compound and an organoaluminum compound in the presence of hydrogen. Continuous copolymerization, at which time the vanadium compound concentration in the polymerization system is 0.3 mmol or more per liquid phase 11, and the vanadium compound supplied to the polymerization system has a concentration of 5 times or less than the vanadium compound concentration in the polymerization system. There is a method of diluting and supplying it to the polymerization medium so that

As a vanadium compound, VOCl3. VO(OC2
H5) C1e, VO<OCz Hs) 1.5C
l i, s , VCI s (7), the general formula VO (
OR) nX3-n or VXs (R is an aliphatic hydrocarbon group, X is a halogen, 0≦n≦3) can be used. In addition, as an organoaluminum compound, (Cp
Hs)zAl, (CzHs)2AlCI, (
C2Hs) 1. s, AI CI □, 6,
(1a o C4H9) x, 5AI Cl
General formula R" m AI X" 3-II
A compound represented by I (where R1 is an aliphatic hydrocarbon group, Xi is a halogen, 1≦m≦3) can be used.

Hydrocarbons such as pentane, hexane, heptane, kerosene, cyclohexane, toluene can be used as polymerization medium. The vanadium compound concentration in the liquid phase is 0.3 mmol/1 or more, preferably 0.5 to 20 mmol/1, and the organoaluminum compound concentration is AI/V (
The atomic ratio) may be in the range of 2 to 50, particularly 3 to 2o.

The copolymerization temperature is O to 100°C, especially 2o to 80°C.
℃, the polymerization pressure is O to 50 ko/crn2 (gauge conversion), especially O to 30 kg/cm2 ('7'-di conversion).
The polymerization conditions may be such that the average residence time is 5 to 300 minutes, particularly 10 to 250 minutes.

Since the graft-modified ethylene °α-olefin copolymer used in the present invention itself has surface-active ability, an aqueous emulsion can be obtained by using a surfactant separately.

Therefore, the aqueous emulsion of the present invention is prepared by preparing the graft-modified ethylene/α-olefin copolymer in the presence of water using a device such as a stirring emulsifier, a colloid mill, or an ultrasonic emulsifier. It can be produced by stirring under humid conditions of room temperature to 100°C.

Of course, surfactants can also be used in the aqueous emulsions of the invention. For example, if the degree of graft modification is small, or if ethylene or α-
When an olefin copolymer is used together with the Kraft-modified copolymer of the present invention, emulsification is easier and the resulting emulsion is more stable when a surfactant is used.

The surfactant used in the present invention may be any of nonionic surfactants, anionic surfactants, and cationic surfactants.

As the nonionic surfactant, for example, polyoxyethylene alkyl ether polyoxyethylene alkyl allyl ether, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene alkyl amine, etc. can be used. As the anionic surfactant, for example, fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkylphenyl ether disulfonates, and sulfate ester salts can be used.

Further, as a cationic surfactant, for example, a quaternary ammonium salt or the like can be used. Among these, nonionic surfactants are preferably used, especially HLB5~
1, especially 10 to 18 nonionic surfactants are more preferably used.

The aqueous emulsion of the present invention contains graft-modified ethylene.
Based on the total weight of the α-olefin copolymer and water, the amount of graft-modified ethylene/α-olefin copolymer is 10 to
It can be contained in a proportion of 90% by weight, more preferably 20 to 50% by weight. Water is 90~ based on the same standards
It can be contained in an amount of 10% by weight, more preferably 80 to 50% by weight.

In addition, when the aqueous emulsion of the present invention contains a surfactant, based on the same standard, the surfactant is
It can be contained in an amount of 3% to 2% by weight, preferably 3 to 2% by weight.

The aqueous emulsion of the present invention is an oil-in-water emulsion, and unless it is specially colored, it usually becomes translucent to milky white. The emulsion particle size is, for example, 0.0
The thickness is about 1 to 10 μm, more preferably about 0.05 to 3 μm.

The aqueous emulsion of the present invention may optionally contain a rust inhibitor,
Various additives can be added, such as preservatives, antifoaming agents, silicone oil, etc. These are usually used in amounts of several percent or less, for example, 2% or less.

The aqueous emulsion of the present invention can be used as, for example, a water-soluble cutting oil, a water-soluble plastic working oil, or a hot rolling oil.

The present invention will be described in detail below with reference to Examples.

Example 1 Ethylene containing 15Qmo1%, Mn=810, Q value -1,
For 100 parts of ethylene propylene copolymer No. 40,
As graft modification components, 14 parts of maleic anhydride and 3 parts
．． After mixing 3 parts by weight of di-tert-butyl peroxide and reacting at 130 degrees Celsius for 4 hours with stirring, 2
The mixture was stirred under vacuum for hours to obtain a pale yellow liquid ethylene-propylene copolymer grafted with maleic acid. The maleic acid content in this modified product was determined by infrared spectroscopy to be 10.1 wt%. In addition, 1yl after denaturation
The n and Q values did not change compared to before denaturation.

Next, 2N KO was added to 100 parts by weight of this modified product.
Mix 100 parts by weight of H water and heat at 80 degrees CC with a homomixer.
Emulsification was carried out under the conditions of 11,200 ORP. The resulting aqueous emulsion was measured using a Leeds-Northrup Micro Track particle size distribution analyzer, and the average particle size was 0.
It was a stable aqueous emulsion with a white color of 9 microns.

The performance of this aqueous emulsion was evaluated in drilling applications on a large radial drilling machine. The drill teeth used were threaded Laetrile F dovetails with a diameter of 32 mm and a tip angle of 117 degrees, and a 5US304 plate with a thickness of 120 mm was used.

While supplying cutting oil made by diluting this aqueous emulsion 30 times to a radial drilling machine, the drill rotation speed was 30 ORPM.
When cutting was performed at a feed rate of 0.5 RPV/min, the number of holes per drill was 300.

Example 2 100 parts by weight of an ethylene-propylene copolymer grafted with maleic acid obtained in the same manner as in Example 1 was kneaded with 18 parts of morpholine at 80 degrees Celsius. Then,
118 parts by weight of distilled water was added to this mixture, and the mixture was gently stirred at 80 degrees Celsius to obtain a pale yellow transparent microemulsion.

The average particle diameter of this aqueous emulsion was measured using a particle size distribution analyzer model Nycom P2O0 manufactured by Biatsuku Co., Ltd.
It was 0.07 micron.

The performance of this aqueous dispersion was evaluated in the same manner as in Example 1, and the number of holes per drill was 300.

Example 3 Ethylene content 4Qmo1%, Mn =900. Q value = 1
．． 100 parts by weight of ethylene/hexene-1 copolymer No. 65 was graft-modified with maleic acid in the same manner as in Example 1, and emulsified with KOH water of equal weight. The average particle size of the resulting aqueous emulsion was 1.1 microns.

The performance of this aqueous emulsion was evaluated in drilling applications on a large radial drilling machine. The drill teeth used were helix drills with a diameter of 32 mm and a tip angle of 117 degrees.
Komei conducted the test on a 5US304 plate with a thickness of 120 mm.

The performance of this aqueous emulsion was evaluated in the same manner as in Example 1, and the number of holes per drill was 250.

Example 4 Ethylene-containing 1i50mol1%, 1n-810, Q value = 1
．． 40 ethylene-propylene copolymer, 26 parts by weight of bicyclo[2
,2,1]hept-2-ene-5,6-dicarboxylic acid and 3.3 parts by weight of di-tert-butyl peroxide were mixed and reacted at 130°C for 4 hours with stirring 1; The mixture was stirred in a vacuum to obtain a pale yellow liquid ethylene-propylene copolymer bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid graft modified product.

The bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid graft content in this modified product was determined by infrared spectroscopy to be 20. It was Owt%. Furthermore, the Mn and Q values after denaturation did not change compared to before denaturation.

Next, 2N KO was added to 100 parts by weight of this modified product.
Mix 100 parts by weight of H water and heat at 80 degrees C with a homo mixer.
Emulsification was performed at 1200 ORPM. The resulting aqueous emulsion was measured using a Leeds-Northrup Micro Track particle size distribution analyzer, and the average particle size was 0.
It was an 8 micron milky white stable aqueous emulsion.

The performance of this aqueous emulsion was evaluated in the same manner as in Example 1, and the number of holes per drill was 250.

Comparative Example 1 To 100 parts by weight of mineral oil, 30 parts of stearic acid octyl ester as a surfactant was added, 1 part by weight of an antioxidant of 2.6 di-tert-butyl phenol was added, and oil:water was added. An aqueous emulsion was obtained by emulsifying at a ratio of 5o:50.

When this comparative amount was evaluated in the same manner as in Example 1, the number of holes per drill was 100, which revealed the superiority of the aqueous emulsion of the present invention.

[Effect of the invention J The aqueous emulsion of the present invention can be used as a cutting oil because the graft-modified ethylene/α-olefin copolymer used has excellent heat resistance stability and oxidation stability, and because it is an aqueous emulsion. In this case, oil deterioration and seizure will not occur even at the tips of bits and drills that are heated in high humidity. This is especially true for those that do not use surfactants. Conventional emulsified cutting oils use natural oils such as hand oil and mineral oil, which have poor high-temperature stability, as well as large amounts of unstable surfactants, so they deteriorate at high temperatures at the tips of bits and drills. The deteriorated components create a barrier that prevents fresh oil from being replenished to the tip, resulting in premature damage or seizure of the bite. The aqueous emulsion of the present invention solves all of the above-mentioned drawbacks.

Procedural amendment November 19, 1955

Claims (1)

[Scope of Claims] 1. An oil-in-water type aqueous emulsion of a graft-modified ethylene/α-olefin copolymer that is liquid or semi-solid at room temperature. 2. The ethylene/α-olefin copolymer constituting the graft-modified ethylene/α-olefin copolymer has an ethylene content of 30 to 70 mol% and a number average molecular weight of 50.
0 to 10,000, and is liquid at room temperature.
The aqueous emulsion according to claim 1, which is an olefin copolymer. 3. The graft modified ethylene/α-olefin copolymer is one of the graft components of the grafted product of ethylene/α-olefin copolymer and unsaturated carboxylic acid or its acid anhydride.
The aqueous emulsion according to claim 1, which is partially or completely neutralized with an alkali. 4. The aqueous emulsion according to claim 1, wherein the graft-modified ethylene/α-olefin copolymer has a maleated modified moiety of about 1 to 20% by weight based on maleic anhydride. 5. A cutting oil consisting of an oil-in-water type aqueous emulsion of a graft-modified ethylene/α-olefin copolymer that is liquid or semi-solid at room temperature.