CN1044714C - Application of unregular ethene improved with liquid oxidation - Google Patents
Application of unregular ethene improved with liquid oxidation Download PDFInfo
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- CN1044714C CN1044714C CN93120781A CN93120781A CN1044714C CN 1044714 C CN1044714 C CN 1044714C CN 93120781 A CN93120781 A CN 93120781A CN 93120781 A CN93120781 A CN 93120781A CN 1044714 C CN1044714 C CN 1044714C
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Abstract
The present invention relates to a liquid oxidized modified ethylene random copolymer which comprises 20 to 80% of ethylene, and 20 to 80% of alpha olefin by mol percentage. The present invention has number-average molecular weight of 200 to 10000 measured by a VPO method, and below 4 of molecular weight distribution measured by a gel permeation chromatography method. The oxygen content of the present invention is 1 to 20% by weight percentage, an acid value is from 1 to 50, and a saponification value is from 1 to 100. The present invention can be used as compounding agents. The performance of all additive agents can be fully performed by the present invention. Consequently, the performance of paint containing the compounding agents is excellent.
Description
The application is that original applying number is dividing an application of CN 93104658.0.Original application day be 880326, the denomination of invention of original application is " purposes of liquid oxidatively modified ethylenic random copolymer ".
The present invention relates to the purposes of liquid oxidatively modified ethylenic random copolymer.Particularly, the invention provides the Synergist S-421 95 that a kind of coating is used, promptly a kind of coating that contains the Synergist S-421 95 that constitutes by the liquid oxidation modification acetate random copolymers.The Synergist S-421 95 that constitutes with liquid oxidatively modified ethylenic random copolymer of the present invention can make the performance of each additive give full play to, thereby makes the coating that contains this Synergist S-421 95 have excellent performance.
For the lubricating oil such as releasing agent of gear grease, machine oil, lubricating grease, metalworking fluid, be used all additives according to its application target, improving its performance, and these additive major parts all are polar compounds.For making these additives reach the purpose at initial stage, best is that these additives are dissolved in above-mentioned those lubricant bases.But the affinity to base oil that these additives have is lower, in this case, usually do not have dissolved, most monodisperse status that only in base oil, are.Recently, lubricant base is just strided forward by the displaced direction of the ucon oil of representative with olefin polymer oil by the mineral oil in past, and these ucon oils have more obvious above-mentioned tendency, and the raising effect of most lubricants performances is not clearly.Therefore, in the purposes field of lubricating oil, be starved of and improve the deliquescent phase solvation of various lubricating oil additives in base oil.
In addition, in paint field, also be adapted to the additive of various purposes in cooperation, for example, for the filler anti-sedimentation agent, anti-drop down agent, the low temperature pliability is paid agent, always be in the past to adopt superfine SiO 2 powder, ultra tiny settleability lime carbonate, wilkinite and organobentonite class or the like.See according to application target, anyly it is hard to tell that all it can play a role fully.Therefore, in the purposes field of coating, people also wish to produce the coating Synergist S-421 95 of above-mentioned excellent property always consumingly.
Present inventors, recognize the problems referred to above that aspect lubricating oil Synergist S-421 95 in the past, exist, and intently studied the Synergist S-421 95 that to bring into play its performance better, found that the liquid oxidatively modified ethylenic with specific trait does not have a kind of new material that multipolymer comes to this, this liquid oxidatively modified ethylenic random copolymer just can achieve the above object, thereby has finished the present invention.
The object of the invention is, a kind of coating that contains the Synergist S-421 95 that is made of liquid oxidatively modified ethylenic random copolymer is provided.
The invention provides a kind of coating that contains the Synergist S-421 95 that constitutes by liquid oxidatively modified ethylenic random copolymer.Described liquid oxidatively ethylene atactic copolymer is characterised in that, it be a kind of be that 2～80 moles of % ethene and content are that the carbonatoms of 20～80 moles of % is that 3～20 alpha-olefin constitutes by content.Described liquid ethylene class random copolymers has following characteristic:
(ⅰ) number-average molecular weight of measuring with gas-phase permeation platen press (VPO) (Mn) be 200～10000,
(ⅱ) with gel infiltration strive molecular weight distribution (Mw/ Mn) that spectrometry measures be below 4,
(ⅲ) oxygen level is that 0.1～20 weight %, acid number are 0.1～50, its saponification value is 0.1～100.
In addition, the preparation method of the liquid oxidatively modified ethylenic random copolymer with following characteristics also can be provided, promptly this method is to be that 20～80 moles of % and alpha-olefin content are 20～80 moles of % with ethylene content, the number-average molecular weight of measuring with gas-phase permeation platen press (VPO) (Mn) is 200～10000, with the molecular weight distribution (Mw/ Mn) of gel permeation chromatography is liquid ethylene class random copolymers below 4, under 100～250 ℃ temperature, contact with gas that contains molecularity oxygen and/or gas ozoniferous, making its oxidation reach oxygen level was 0.1～20% (by weight).Simultaneously can also provide a kind of lubricating oil Synergist S-421 95 that constitutes by this liquid oxidatively modified ethylenic random copolymer as the purposes invention, and the coating Synergist S-421 95 that constitutes by this liquid oxidatively modified ethylenic random copolymer.
Liquid oxidatively modified ethylenic random copolymer of the present invention is by 20～80 moles of %, be preferably 30～70 moles of %, be preferably 40～60 moles of % ethene and 20～80 moles of %, be preferably 30～70 moles of %, be preferably the oxidation modification product of the liquid ethylene class random copolymers that the alpha-olefin of 40～60 moles of % constitutes.As the alpha-olefin that constitutes this liquid ethylene class random copolymers, but illustration is as follows: carbonatomss such as propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene are the alpha-olefin of 3-20.
The number-average molecular weight (Mn) of the liquid oxidatively modified ethylenic random copolymer of measuring with gas-phase permeation platen press (VPO) of the present invention is 200～10000, better be 300～8000, best be 500～5000, molecular weight distribution (Mw/ Mn) is below 4, preferably below 3.5, best below 3.The number-average molecular weight of this liquid oxidatively modified ethylenic random copolymer (Mn) all can reduce this material is used Synergist S-421 95 with Synergist S-421 95 or coating as lubricating oil performance less than 200 or greater than 10000 o'clock.In addition, the molecular weight distribution of this liquid oxidatively modified ethylenic random copolymer (Mw/ Mn) equally also can reduce the performance of this material as lubricating oil Synergist S-421 95 and coating material compounding agent greater than 4 o'clock.
The oxygen level of liquid oxidatively modified ethylenic random copolymer of the present invention is 0.1～20%, is preferably 0.5～15%, is preferably for 1～10% (by weight), and acid number is 0.1～50; Be preferably 0.2～40, be preferably 0.5～35, saponification value is 0.1～100, no matter the oxygen level of this liquid oxidatively modified ethylenic random copolymer is less than 0.1% (by weight), still acid number is less than 0.1, or its saponification value also all can reduce the performance of this material as lubricating oil Synergist S-421 95 or coating material compounding agent less than 0.1 o'clock.In addition, if the oxygen level of this liquid oxidatively modified ethylenic random copolymer is greater than 20% (by weight), acid number is greater than 50, or its saponification value also all can reduce its performance as lubricating oil Synergist S-421 95 or coating material compounding agent equally greater than 100 o'clock.
Liquid oxidatively modified ethylenic random copolymer of the present invention; be the molecular end of liquid oxidatively modified ethylenic random copolymer and the ethene composition and the propylene composition of copolymer chain inside; randomly oxidized product; as containing the oxygen functional group by oxidation is formed, but illustration is as follows: carboxyl, carbonyl oxygen base (ester bond), formyl radical, carbonyl, hydroxyl etc.And carboxyl-content is the 0.001-1 mole in per 1000 gram liquid oxidatively modified ethylenic random copolymers; be 0.01～0.8 mole preferably; the content of carbonyl oxygen base (ester bond) is 0.001～2 mole; the content range that always contains (full carbonyl) that better is 0.01～1.5 mole, formyl radical and carbonyl is 0.01～15 mole; be preferably 0.05～10 mole; the content range of hydroxyl is 0.01～15 mole, is preferably 0.05～10 mole.
Liquid oxidatively sex change ethylenic random copolymer of the present invention is to be 20～80 moles of % to ethylene content, and the content that is preferably 30～70 moles of %, the best and is 40～60 moles of % and alpha-olefin is more preferably 30～70 moles of %, the bests liquid ethylene class random copolymers that is 40～60 moles of % products of carrying out oxidation modification of 20～80 moles of %.In addition, the number-average molecular weight (Mn) that this liquid ethylene class random copolymers is measured with gas-phase permeation platen press (VPO) is 200～10000, better be 300～8000, best is 500～5000, this molecular weight distribution (Mw/ Mn) will be below 4, better will be below 3.5, best will be below 3.In addition, as the alpha-olefin composition that constitutes this liquid ethylene class random copolymers, can be that 3～20 alpha-olefin is as illustration with carbonatoms listed above equally.
The standard deviation value (δ) that the ethene composition of this liquid ethylene class random copolymers is formed is usually below 3, and is better below 2, best below 1.If the standard deviation value (δ) that the ethene composition of this liquid ethylene class random copolymers is formed is greater than 3, all can reduce the solvability of lubricating oil or coating etc.
In addition, the B value of this liquid ethylene class random copolymers of representing with formula I should be satisfied with the scope of formula II, that is,
1.0≤B≤1.5 (Ⅱ)
(in the formula: P
EThe molfraction, the P that contain the ethene composition in the expression multipolymer
oExpression contains molfraction, the P of alpha-olefin composition
OEThe molfraction of representing the alpha-olefin ethene chain link of complete two unit chain links.Above-mentioned B value is the index of the distribution of the various monomer components in the expression copolymer chain, and the B value is big more, and the chain link of expression block is few more, and the distribution of ethene and alpha-olefin is the same.
The desirable B value of this liquid ethylene class random copolymers is as described below
The content of ethene 50 moles of situations below the % is in the multipolymer:
1.0+0.2 * P
E≤ B≤1/ (1-P
E), better general expression is,
1.0+0.3 * P
E≤ B≤1/ (1-P
E), the general expression of optimal cases is,
1.0+0.4×P
E≤B≤1/(1-P
E)，
1.2-0.2 * P
E≤ B≤1/P
E, better general expression is:
1.3-0.3 * P
E≤ B≤1/P
E, best general expression is:
1.4-0.4×P
E≤B≤1/P
E
As long as open clear 57-123205 communique and special method of being willing to that clear 60-259835 patent application is provided according to the applicant the spy, suitably selective polymerization condition just can produce this liquid ethylene class random copolymers again.
Must adopt the gas and/or the gas ozoniferous that contain molecularity oxygen, and this liquid ethylene class random copolymers must be carried out oxidation in the inert hydrocarbon medium, just can obtain liquid oxidatively modified ethylenic random copolymer of the present invention.As the employed gas that contains molecularity oxygen, except that can enumerating oxygen, air, also can enumerate with inactive gass such as nitrogen, argon and carbonic acid gas is that the mixed gas etc. of proper concn is example with oxygen dilution in oxidation.In addition, as ozone gas, except that ozone and ozone and oxygen or Air mixing gas are arranged, the mixed gas that ozone and/or oxygen or air is diluted to proper concn with non-active gas such as nitrogen, argon, carbonic acid gas can illustratively be arranged also.Secondly, as gas ozoniferous, except that can example illustrating ozone and ozone and oxygen or the Air mixing gas, having shown in also can example, with ozone and/or oxygen or air with the suitable mixed gas that dilutes of rare gas elementes such as nitrogen, argon, carbonic acid gas.
Employed inert hydrocarbon when oxidizing reaction, but illustration is as follows: pentane, hexane, heptane, octane, decane, 12 carbon alkane, kerosene, gasoline, benzene,toluene,xylene etc.
The oxidation of this liquid ethylene class random copolymers is not normally having to implement under the situation of catalyzer.But under the situation that has radical initiator or oxide catalyst to exist, also can implement.As radical initiator, but particular instantiation is as follows: benzoyl peroxide, ditertiary butyl peroxide, tertbutyl peroxide, dicumyl peroxide, 2, organo-peroxide such as 5-dimethyl 2,5 a pair ofs (peroxide benzoate) hexin-3 grade.As oxide catalyst, what can specifically exemplify has: mineral compound such as Cobaltous diacetate, Manganous chloride tetrahydrate, copper, nickel oxide, Manganse Dioxide, cobalt naphthenate.
Temperature during this liquid ethylene class random copolymers oxidizing reaction is 100-250 ℃, and ideal is 120～230 ℃, and best is 130～200 ℃.The needed time of oxidizing reaction is 10 minutes～20 hours, and ideal is 30 minutes～10 hours.No matter this oxidizing reaction is all can carry out under the pressure condition of normal pressure or pressurization.Mixture after the oxidizing reaction is handled by ordinary method, just can be obtained liquid oxidatively modified ethylenic random copolymer of the present invention.
Liquid oxidatively modified ethylenic random copolymer of the present invention also can be used as the lubricating oil Synergist S-421 95 and uses.During as the lubricating oil Synergist S-421 95, all can use the mineral oil lubricant base, any ucon oil of olefin polymer or multipolymer wet goods olefines ucon oil, silicon class ucon oil, esters syntholube etc.This liquid oxidatively modified ethylenic random copolymer normally 0.5～300 part (by weight), is preferably 0.8～200 part (by weight), best 1～150 weight part for the cooperation ratio of the above-mentioned lubricant base of 100 parts (by weight).In this lubricating oil, except that can cooperating this liquid oxidatively modified ethylenic random copolymer, can also cooperate the well-known various additives that other can cooperate with lubricating oil.As additive for lubricant, can add mineral oil (neutral oil), low-molecular-weight alpha-olefinic polymer, silicon class ucon oil, esters syntholube, oxidation stabilizer, extreme pressure additive, rust-inhibiting additive, defoamer, extreme pressure compound etc. particularly.The cooperation ratio of these compositions will be selected for use in suitable scope.
The lubricating oil that cooperates this liquid oxidatively modified ethylenic random copolymer can be used in the purposes such as gear grease, machine oil, lubricating ester, metalworking fluid, releasing agent.
Liquid oxidatively modified ethylenic random copolymer of the present invention also can be used as coating material compounding agent and uses.Object lesson as the coating that can cooperate liquid oxidatively modified ethylenic random copolymer of the present invention has: for example, as varnish formation with aminoresin, urethane resin, dryness wet goods condensation polymer type coating resins such as the Synolac of resinous principle or its modified material, unsaturated polyester or its modified material, resol, Resins, epoxy or its modified material, urea resin, melmacs; And (addition) aggretion type coating resin such as propenyl resinoid, rubber-like coating resin etc.When being 100 weight parts for the varnish formation main component in the coating, the cooperation ratio of this liquid oxidatively modified ethylenic random copolymer, be generally 0.01～20 part, be 0.1～10 part (by weight) preferably, in the coating that has cooperated liquid oxidatively modified ethylenic random copolymer of the present invention, can also cooperate a certain amount of other known various additives, for example, pigment, solvent (under the situation of solvent based coating), dispersion agent (under the situation of emulsion paint) is coated with flat agent and weather stablizer etc.
Embodiment:
By the following examples the present invention is specifically described.
The measuring method and the evaluation method of the composition transitivity value of liquid oxidatively modified ethylenic random copolymer of the present invention and raw material liquid ethylenic random copolymer thereof are as follows.
(1) according to the carbon-13 magnetic resonance retrieval system (
13C-NMR) mensuration is obtained
The composition of ethene composition and alpha-olefin composition.
(2) measuring method of number-average molecular weight
With diphenylthanedione and 2,6,10,15,19,23-hexamethyl 24
Alkane in toluene solvant, according to a conventional method, is measured number average branch under 80 ℃ the condition with gas-phase permeation platen press (VPO) as the standard test specimen of known molecular amount
Son is put (Mn).
(3) mensuration of molecular weight distribution (Mw/ Mn) is with work in military, and ball is kind to be sent out
" gel permeation chromatography " (" グ Le パ-ミ エ-シ 3 Application Network ロ マ ト Network " テ of row
Off イ-) be standard, mode is carried out as described below.
(1) use the known molecular amount polystyrene standard (Japan ソ (strain) system,
Single Port リ ス チ レ Application that disperses) determining molecular weight M and GPC (Gel thereof
Permeation Chromatograph) counting is drawn molecule
Amount M and V
eThe graph of a relation of (elution volume (Elution Volum))
The shape calibration curve, the concentration that makes it this moment is 0.02 ω t%
(2) keep the GPC chromatographic adsorption analysis result of sample in mind according to the GPC measuring method,
By the method for above-mentioned (1), mark the number-average molecular weight Mn of polystyrene conversion
Put Mw with the weight average molecule, obtain Mw/ Mn value again.At this moment sample joins
The condition determination of system condition and GPC is as follows.
The preparation of sample:
(a) get a certain amount of sample and to make this sample be mixed with 0.1 ω t% concentration required
Neighbour's one benzene dichloride solvent of amount is put into Erlenmeyer flask together;
(b) Erlenmeyer flask is placed heated one hour under 140 ℃ the temperature after, with stainless
The strainer of steel (aperture is 0.5 μ m) filters, with this filtered liquid
Carrying out GPC measures.
GPC measures by following condition and implements:
(a) device:
(150C-ALC/GPC) that waters society makes
(b) chromatographic column (カ ラ system):
E.I.du pont de Nemours and company
(Zorba * く プ) that makes
(c) temperature:
140℃
(d) flow velocity:
1 ml/min
(4) ethene becomes the standard deviation value (δ) be grouped into
Adopt the different acetone/hexane mixed solvent of ratio of mixture, by following condition and side
Method also uses separating funnel to carry out solvent extraction, with the low-molecular-weight ethene of liquid state
Analog copolymer is divided into different three level parts forming.
The experimental technique of difference solvent extraction:
40 gram samples with accurate weighing are dissolved in 300 milliliters of hexane solvents, and put into separating funnel, under 25 ℃ condition, put into 500 milliliters of acetone, then (at this, the volume ratio of the mixed solvent of hexane/acetone is 3/5) after the vibration when leaving standstill, then be separated into two-layer.Its lower floor is called level part solution-1.In upper solution, append 400 milliliters of acetone then, can be separated into two-layerly when leaving standstill after the vibration again, lower floor is called a level part solution-2, the upper strata is called a level part solution-3.
Remove solvent in the at different levels parts of solution by distillation, just can obtain level part-1, level parts-2, level parts-3.
According to
13The ethene that the C-NMR analytical procedure is obtained at different levels parts is formed, and forms and parts by weight with at different levels parts ethene, is calculated as follows out the standard deviation (δ) that ethene is formed.The standard deviation value (δ) that ethene is formed is big more, and it is wide more to represent that then it forms distribution.
E in the following formula
iThe ethene of expression i level part is formed, and Wi represents the weight fraction of i level part, and E represents the average ethylene composition of multipolymer.
(5) B value:
The B value defined of this liquid low-molecular-weight ethylene analog copolymer is as follows:
P in the formula
EThe molfraction of ethene composition in the expression multipolymer, P
OThe molfraction of expression alpha-olefin composition, P
OEThe molfraction of representing the alpha-olefin ethene chain link of complete two unit chain links.The B value is the index of each monomer component distribution in the expression multipolymer, and the B value can (Macromolecules 10 based on GJRag, 773 (1977)), (Mocromolecules 15 for JCRandall, 353 (1982), JPolymer Science, polymer physicsEd., 11,275 (1973)) KKimura (poigmer, 25,441 (1984)) report is by obtaining the P of above-mentioned definition
E, P
OAnd P
OECan calculate.Above-mentioned B value is big more, and the chain link of block chain is just more little, and also expressing ethene is the same with the distribution of alpha-olefin.
Usually it is 120 ℃ measuring temperature, the mensuration frequency is 25.05MHz, spectral band width is 1500Hz, wave filter is wide to be 1500Hz, be 4.2 seconds pulse repetition time, and pulse height is 7 microseconds (μ sec), and cumulative number is under 2000-5000 time the condition, be determined at diameter and be in 10 millimeters the sample tube, be dissolved in about 200 milligrams multipolymer sample in 1 milliliter of hexachlorobutadiene equably
13The c-NMR spectral value.Then, by trying to achieve P from the sample spectrum that records
E, P
oAnd P
OECalculate the B value.
(6) acid number:
Measure by the total acid value measuring method of putting down in writing among the JISK 2501-1980.
(7) saponification value
Survey by the soap value test method of putting down in writing among the JISK 0070-1966
Fixed.
(8) oxygen level
Measure by the organic element analysis method.
(9) mensuration of hydroxyl
According to SSIGGIA work, " organic fixed according to functional group of translating exerted oneself in the mulberry field
Component analysis " the acetylizing method put down in writing measures.
(10) carboxyl-content, carboxylic oxygen base content and full carbonyl (carbonyl, formyl radical) content
Be calculated as follows.(ⅰ)
(carboxyl mole/1000 gram modified copolymers) (ⅱ)
(carbonyl oxygen base mole/1000 gram modified copolymers) be full carbonyl content=(full carbonyl mole/1000 gram modified copolymers) (ⅲ)
-((carboxyl-content+carbonyl oxygen base content) * 2+ hydroxy radical content)
Liquid oxidatively modified ethylenic random copolymer of the present invention also can use in other various uses except that cooperating the meter as above-mentioned lubricating oil Synergist S-421 95 and coating.For example: the dispersion agent that is used for the solid additives of lubricating oil, the processing aid of rubber or resin, the fiber process auxiliary agent, the properties-correcting agent of rubber or resin, softening agent, easer, the metal ion supplement, ion-exchanger, agricultural chemicals exhibition stick, the plasticity-of coating is paid agent, the priming paint modifying agent that coating is used and the modifying agent of caking agent etc.
Embodiment 1
In that being housed, air is blown into pipe, in the stirrer glass reactor of exhaust outlet and thermometer (operation capacity is 1.5 liters), the ethene of packing into consists of 49 moles of %, number-average molecular weight (Mn) is 1000, molecular weight distribution (Mw/ Mn) is 1.43, the standard deviation (δ) that ethene becomes to be grouped into is 0.1, the B value is that 1.2 viscosity (20 ℃) are the liquid ethylene of 1040CP--random copolymer of propylene 800 grams, stir with 1000 rev/mins rotating speed on one side, be warmed up to 200 ℃ on one side, then, dry air is blown into pipe with 100 liters/hour fast degree bubbling air, and the time of being blown into is 6 hours.Stop air and be blown into, mouthful be blown into nitrogen,, promptly make the oxidation modification multipolymer Yi Bian be cooled to room temperature Yi Bian change to be blown into by nitrogen thereafter.Prepared oxidation modification multipolymer, be have below shown in the yellow transparent liquid of physical properties.Number-average molecular weight (Mn) is 940, molecular weight distribution (Mw/ Mn) is 1.52, acid number is 3.7 milligrams of KOH/ grams, saponification value is 5.40 milligrams of KOH/ grams, oxygen level was 2.94% (by weight), viscosity (20 ℃) is 1640Cp, carboxyl-content is 0.066 mole/1000 gram modified copolymers, carbonyl oxygen base content is 0.030 mole/1000 gram modified copolymers, hydroxy radical content is 0.60 mole/1000 gram modified copolymers, and full carbonyl content is 1.50 moles/1000 gram modified copolymers.
Embodiment 2
Remove and adopt ethene to consist of 49 moles of %, number-average molecular weight (Mn) is 1240, molecular weight distribution (Mw/ Mn) is 1.74, it is 0.1 that ethene becomes to be grouped into standard deviation (δ), the B value is 1.2, and viscosity (20 ℃) is that liquid ethylene-random copolymer of propylene of 4670 CP is made raw material, and temperature of reaction is 130 ℃, it is outside 10 hours that air is blown into the time, and other operations are all carried out similarly to Example 1.The oxidation modification multipolymer that is obtained be have below shown in the yellow transparent body of characteristic.Its number-average molecular weight (Mn) is 1130, molecular weight distribution (Mw/ Mn) is 1.64, acid number is 15.3 milligrams of KOH/ grams, saponification value is 25.1 milligrams of KOH/ grams, oxygen level was 5.97% (by weight), viscosity (20 ℃) is 12400CP, carboxyl-content is 0.27 mole/1000 gram modified copolymers, carbonyl oxygen base content is 0.17 mole/1000 gram modified copolymers, hydroxy radical content is 0.62 mole/1000 gram modified copolymers, and full carbonyl content is 2.23 moles/1000 gram modified copolymers.
Evaluation Example 1
As follows, oxidation modification ethylenic random copolymer of the present invention is estimated with the performance of Synergist S-421 95 as lubricating oil.
(1) modulation of test portion
Get poly-χ-olefin oligomer-A (MObilSHF-1001 of Mobil ChemiCal society system) 65 weight parts and poly-alpha olefins oligopolymer B (the Synfluid GostpAO of ChevronCemical society system) 35 weight parts, in 300 milliliters beaker,, add commercially available gear grease composite additive (Texaco society system, TC9535 with behind the glass stick thorough mixing; S24.1%, P1.8%) 1 weight part and oxidation modification multipolymer 2 weight parts that obtained by embodiment 1, further stir, be modulated into the candidate oil (1) of estimating usefulness.Use the same method, do not add the oxidation modified copolymer and modulate, make the candidate oil (II) of estimating contrast usefulness.
(2) evaluation method
(ⅰ) intermiscibility
Get 100 milliliters of samples, put into diameter and be 40 millimeters Glass Containers, leave standstill a night after, use spectrophotometer, having measured wavelength is the absorptivity of 660nm.(cuvette (ヒ Le): glass, long 50 millimeters (nitre 50mm); Reference substance (symmetry): hexane) check the transparency.
" evaluation "
| Extinctivity | 0.05 below | 0.05～ 0.15 | 0.15～ 0.25 | 0.25～ 0.35 | 0.35 more than |
| Grading | 5 | 4 | 3 | 2 | 1 |
(ⅱ) add thermostability
To the Glass Containers of the sample behind the compatibility test be housed, put in the thermostatic bath of 80 ℃ of sons, places after one month and take out, at room temperature cool off a night, use and estimate transparent with above-mentioned (1) same method.
(ⅲ) resistance to emulsion
The method of pressing JIS K 2520 is checked the extinction time of emulsion layer.
" evaluation "
| Emulsion layer extinction time (branch) | Below 10 | 10～ 30 | 30～ 60 | 60～ 480 | More than 480 |
| Grading | 5 | 4 | 3 | 2 | 1 |
(3) evaluation result
Table 1
Evaluation Example 2
As follows, oxidation modification ethylenic random copolymer of the present invention is estimated with the performance of Synergist S-421 95 as coating.
(1) modulation of sample
With Resins, epoxy A (Mitsui petrochemical industry (strain) society system, エ ホ ミ ッ Network R-140) 85 weight parts and Resins, epoxy (the same, エ Port ミ Star Network R-09415 weight part and oxidation modification multipolymer 3 weight parts that obtained by embodiment 2, behind the thorough mixing, add ground silica (dragon lumber industry society system, Network リ ス ラ イ ト A-l more therein) 35 weight parts, fully stir again, obtain the epoxy coating (I) that uses for evaluation.With same method, prevent that with commercially available vegetables oil polymer class sedimentation agent from replacing the oxidation modification multipolymer again, make to estimating the epoxy coating (II) of contrast usefulness.
(2) evaluation method
(ⅰ) pigment rate of descent
At internal diameter 18mm, in the Glass Containers with cover of high 45mm, the sample of packing into, and make packing into of sample highly be 40mm, static placement was obtained the pigment rate of descent by following formula after one month.
In the formula, L
o: the packing height of pigment (40mm)
L: static placement is after 1 month, the top clear layer that occurs after the pigment sedimentation
Height (mm).
(ⅱ) flow
To the evaluation coating of 100 weight parts, add the modified polyamine class solidifying agent (Mitsui petrochemical industry (strain) society system, ユ ボ シ Star ヶ Q-636) of 28 weight parts, and be coated on the sheet glass after mixing fully, then its vertical fixing is left standstill curing.When observing the sagging situation, obtain the highest applied thickness that the sagging phenomenon does not take place.(ⅲ) evaluation result
Table 2
Liquid oxidatively modified ethylenic random copolymer of the present invention is as the lubricating oil Synergist S-421 95, and coating all has good effect with Synergist S-421 95 and resin modifying agent.
Below accompanying drawing is made a brief description
Fig. 1 is the infrared absorption spectrum figure of the liquid oxidatively modified ethylenic random copolymer of embodiment 1.
Fig. 2 is the infrared absorption spectrum figure of the liquid oxidatively modified ethylenic random copolymer of embodiment 2.
Claims (1)
1. coating that contains the Synergist S-421 95 that constitutes by liquid oxidatively modified ethylenic random copolymer, in the described liquid oxidatively modified ethylenic random copolymer, the ethene containing ratio is 20-80 mole %, and carbonatoms is that the containing ratio of the alpha-olefin of 3-20 is 20～80 moles of %
Described liquid oxidatively modified ethylenic random copolymer has following characteristic:
(1) the number-average molecular weight Mn that measures with the gas-phase permeation platen press is 200～10000,
Molecular weight distribution Mw/ Mn with gel permeation chromatography is below 4,
(2) oxygen level is that 0.1-20 weight %, acid number are 0.1～50, saponification value is 0.1～100.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93120781A CN1044714C (en) | 1993-12-06 | 1993-12-06 | Application of unregular ethene improved with liquid oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93120781A CN1044714C (en) | 1993-12-06 | 1993-12-06 | Application of unregular ethene improved with liquid oxidation |
Related Parent Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88102774A Division CN1024351C (en) | 1987-03-26 | 1988-03-26 | Liquid oxidatively modified ethylenic random copolymer, process of making and use |
| CN93104658A Division CN1025436C (en) | 1987-03-26 | 1993-04-20 | The use of liquid oxy-modified ethene random copolymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1089973A CN1089973A (en) | 1994-07-27 |
| CN1044714C true CN1044714C (en) | 1999-08-18 |
Family
ID=4993430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93120781A Expired - Lifetime CN1044714C (en) | 1993-12-06 | 1993-12-06 | Application of unregular ethene improved with liquid oxidation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1044714C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998058024A1 (en) | 1997-06-19 | 1998-12-23 | Mitsui Chemicals, Inc. | Molding resin composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3692877A (en) * | 1969-12-25 | 1972-09-19 | Sanyo Chemical Ind Ltd | Emulsifiable oxidized polyolefins |
| US4156061A (en) * | 1974-03-06 | 1979-05-22 | Exxon Research & Engineering Co. | Epoxidized terpolymer or derivatives thereof, and oil and fuel compositions containing same |
-
1993
- 1993-12-06 CN CN93120781A patent/CN1044714C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3692877A (en) * | 1969-12-25 | 1972-09-19 | Sanyo Chemical Ind Ltd | Emulsifiable oxidized polyolefins |
| US4156061A (en) * | 1974-03-06 | 1979-05-22 | Exxon Research & Engineering Co. | Epoxidized terpolymer or derivatives thereof, and oil and fuel compositions containing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1089973A (en) | 1994-07-27 |
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