CN1161344A - Dispersant additives - Google Patents
Dispersant additives Download PDFInfo
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- CN1161344A CN1161344A CN 96121407 CN96121407A CN1161344A CN 1161344 A CN1161344 A CN 1161344A CN 96121407 CN96121407 CN 96121407 CN 96121407 A CN96121407 A CN 96121407A CN 1161344 A CN1161344 A CN 1161344A
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Abstract
The reaction product is disclosed, lubricant compositions including the reaction product, fuel compositions including the reaction product and additive concentrates including the reaction product are used as dispersant.
Description
The present invention relates to polyolefinic reaction product, its preparation method, the lubricating oil composition that contains this reaction product, fuel composition and multifunctional additive for lubricating oils and as the purposes of dispersant additives.
Be surprisingly found out that some nitrogenous polyolefine reaction product has low turbidity and good dispersiveness, and show good consistency for sealing member and bearing.
According to the present invention, provide the reaction product of following material:
(i) a kind of oligomer, its number-average molecular weight is not higher than 7500 and formed by one or both or multiple different monomers, this monomer or each monomer are that a kind of ethylenically unsaturated compounds and described oligomer or every kind of described monomer can be randomly by partial esterization or full esterifications, its each monomer can not contain ether moiety, neither cyclopentadienyl, described oligomer can be randomly with the low molecular weight amine reaction and
(ii) a kind of ethene belongs to unsaturated carboxylic reagent polymerase chain alkenyl derivative (iii), when oligomer be wherein a kind of monomer when being the monomeric oligomer altogether of two kinds of normal olefine this derivative have at least 1600 number-average molecular weight, and
(iv) a kind ofly contain at least two-NH
2And/or-polyamines of NH base, or and
(v) reagent (ii) and pre-formation product (iv), wherein the alefinically unsaturated compounds of oligomer at least a have a kind of can with the functional group of amine reaction, oligomeric reaction product is randomly further reacted with low molecular weight amine.
Oligomer (i) preferably has and is not higher than 5000 number-average molecular weight, more preferably no higher than 4000.
Preferably a kind of molecular weight of low molecular weight amine is 17～300 amine, for example oleyl amine or benzylamine, especially preferably aniline; Or by the suitable polyamines of top (iv) middle definition.
Ethene belongs to unsaturated carboxylic reagent and (iii) contains altogether at least 3 carbon atoms, preferably altogether 3-50, more preferably 3-30, and further preferred 4-20, further preferred 4-10 carbon atom.
It can be the 6th page of EP-B-0285609 that ethene belongs to unsaturated carboxylic reagent, the 6th page of the capable or EP-B-0287569 of 15-48, the alpha-beta ethylenically unsaturated carboxylic acids reagent of the capable definition of 11-39, for example vinylformic acid (C
3), methacrylic acid (C
4), styracin (C
9), Ba Dousuan (C
4), 2-phenylacrylic acid (C
9), toxilic acid (C
4), fumaric acid (C
4), propene dicarboxylic acid (C
5), methylfumaric acid (C
5), methylene-succinic acid (methene succinic acid) (C
5), citraconic acid (methyl-maleic acid) (C
5) and their functional derivatives, for example acid anhydrides is (as, maleic anhydride (C
4), glutaconic anhydride (C
5), itaconic anhydride (C
5), citraconic anhydride (C
5)), ester (as, methyl acrylate) C
4)), acid amides, imide, salt, carboxylic acid halides and nitrile.
Best, ethene belongs to unsaturated carboxylic reagent and (iii) is selected from single ethene and belongs to unsaturated C
4-C
10Dicarboxylic acid and acid anhydrides, wherein maleic anhydride most preferably.
Ethene belongs to unsaturated carboxylic reagent polymerase chain alkenyl derivative (iii) (ii) can be by method preparation known in the art.For example, (iii) be maleic anhydride if ethene belongs to unsaturated carboxylic reagent, then its polymerase chain alkenyl derivative can make polyolefine mix with the maleic anhydride of specified amount and make chlorine pass mixture and prepare by for example method of GB-A-949981 introduction.In addition, the method that this derivative also can be introduced according to GB-A-1483729 under proper temperature, makes the maleic anhydride of polyolefine and specified amount carry out thermal response and prepares.EP-A-0542380 has introduced a kind of special preferred method for preparing this derivative, comprises making polyolefine and maleic anhydride in the presence of the sulfonic acid of 150-260 ℃ and a kind of addition polymerization amount of suppression, and the mol ratio that is higher than 1: 1 with maleic anhydride and polyolefine is reacted.The mol ratio that ethene belongs to unsaturated carboxylic acid part and polyalkenyl part in the derivative that forms is preferably 1: 1～and 5: 1, more preferably 1: 1～1.3: 1, particularly 1: 1～1.2: 1.
The polyolefine that is used to prepare the polyolefin derivative thing can be for example at least a C
2-10The homopolymer of monoolefine or multipolymer.Best, polyolefine is at least a C
2-5The polymkeric substance of monoolefine, for example ethylene-propylene copolymer.Monoolefine is C preferably
3-4Alkene, particularly propylene or iso-butylene, and the preferred polyolefine that obtains thus comprises polyisobutene and atactic or isotaxy or syndiotactic propylene oligomer.Polyisobutene, that for example sell with trade(brand)name " GLISSOPAL " and by the polyisobutene of British Petroleum Company p.l.c. with trade(brand)name " ULTRAVIS ", " HYVIS " and " NAPVIS " sale by BASF, as " HYVIS75 ", " HYVIS120 ", " HYVIS200 " and " HAPVIS120 " polyisobutene is particularly preferred for the present invention.
Polyolefinic number-average molecular weight (Mn) is preferably 300-7000, more preferably 500-5000, further preferred 700-3000.
Polyamines (iv) contains at least two-NH
2And/or-the NH base, have at least one reactive hydrogen respectively on this class group.The example that is used for polyamines of the present invention is the 16th page at EP-B-0287569 ,～the 19 page of 21 row, the material that 53 styles of writing are introduced in this.
Best, polyamines is following formula: compound (I)
H
2N-(CHR
1)
x-CH
2-[A-CH
2-(CHR
1)
x]
y-NH
2(I) wherein A be-NH or-O-, each R
1Independent represent hydrogen atom or methyl, x is 1-3, and when A be-during NH, y is 1-10, or when A be-during O-, y is 1-200.
In following formula (I), preferably when A be-during NH, x is 1, each R
1Represent hydrogen atom, and y is 1-8; Or when A be-during O-, x is 1, each R
1Represent methylidene and y are 1-50.
Reagent (v) be reagent (ii) and pre-formation product (iv), and can be according to the conventional art preparation in present technique field.For example, if reagent (ii) is the polymerase chain alkenyl derivative of maleic anhydride and polyamines when being the ethylidene polyamines, the method for introducing according to EP-A-0587250 for example is in 100-250 ℃ and a kind of hydrocarbon solvent, with polymerase chain alkenyl derivative and polyamines 1-4: 1 mol ratio makes them one react easily.In the product mole coupling ratio of polymerase chain alkenyl derivative and amine be preferably 1: 1～3: 1, more preferably 1: 1～2.5: 1.
But ethylenically unsaturated compounds can be selected from any compound of oligomerization, for example alpha-olefin and alpha-beta-beta-unsaturated carbonyl compounds.Specially suitable compound comprises vinylbenzene, maleic anhydride and vinylformic acid.
Described ethene belongs to the reaction that forms oligomer between the unsaturated monomer can be undertaken by radical cation or negatively charged ion oligomerizing.Described oligomer is selected from the material of the functional group with the reaction of a kind of and amine, more preferably with the vinylbenzene of maleic anhydride copolymerization, with acrylic acid copolymer vinylbenzene, polyacrylic acid and with the alpha-olefin of maleic anhydride copolymerization.
No matter reaction product of the present invention is to be made by the oligomer (i) of partial esterization or full esterification by wherein oligomer or its one or more monomers, still by not having oligomer (i) through this esterification to make, all shows good dispersiveness.Find that many reaction product (particularly ester) have very low turbidity (haze) level, therefore reduced the needs of further processing (for example filtering).Such esterification of these oligomers or monomer whose can be by preferably under a kind of catalyzer of tosic acid (PTSA) and so on and pure as C
1-20Aliphatic series or aromatic alcohol react and carry out.
But, there are common oligomer of commercially available (1) this class ethylenically unsaturated compounds and the partial ester form that (2) are total to oligomer (1).(1) example is an altogether oligomer (SMA) of vinylbenzene/maleic anhydride, for example by ELf-Atochem with trade(brand)name " SMA1000A ", the material of " SMA2000A " and " SMA3000A " sale.(2) example is the half ester of described " SMA3000A " and iso-octyl alcohol, is sold with trade(brand)name " SMA3840A " by Elf-Atochem.Find, by this commercially available SMA of use partial ester or full esterified form, the SMA of for example commercially available partial ester form, or by using the polyacrylic acid of esterification, as the polyacrylic acid n-pentyl ester, can prepare dispersion agent with low turbidity water flat (pressing ASTM D1003 measures).
To produce full esterification oligomer (that is, diester), preferably use C for esterification SMA
1-20Aliphatic series or aromatic alcohol, more preferably C
5-8Branched aliphatic alcohol, particularly primary isoamyl alcohol (it is branched-chain alcoho, mainly is the mixture of the pure and mild 2-methylbutane of 3-methylbutane-1--1-alcohol) or isooctyl alcohol, especially excessive use.C is preferably used in polyacrylic esterification
1-20Aliphatic series or aromatic alcohol, for example straight-chain fatty alcohol, particularly Pentyl alcohol.Described esterification technique preferably 0-250 ℃, more preferably 70-190 ℃ and 0.5-10 normal atmosphere (50-1000kPa), more preferably under the normal atmosphere, in the presence of a solvent, more preferably be selected from alcohol, aromatic hydrocarbons such as toluene, dimethylbenzene and and ether such as tetrahydrofuran (THF) and 1, the solvent of 4-diox and their mixture exists down, and in the presence of a catalyzer, more preferably be selected from acid as sulfuric acid and PTSA, carry out under the catalyzer existence of Lewis acid as aluminum chloride and alkali such as pyridine and 4-(N, N-dimethylamino) pyridine.At solvent is reactive, for example under the condition of alcohol as isooctyl alcohol, with the reaction of oligomer (i) can with polyamines (iv) or with (reaction is v) carried out simultaneously.
The present invention further provides a kind of preparation method of reaction product as defined above, this method comprises: make
(i) a kind of oligomer, wherein the number-average molecular weight of this oligomer is not higher than 7500 and the oligomer that formed by a kind of monomer or two or more different monomers, this monomer or each monomer are that ethylenically unsaturated compounds and described oligomer or every kind of described monomer are arbitrarily selectively by partial esterization or full esterification, its each monomer does not contain ether moiety, do not contain cyclopentadienyl yet, described oligomer selectively reacts with low molecular weight amine arbitrarily, with
The polymerase chain alkenyl derivative that (ii) a kind of ethene belongs to unsaturated carboxylic reagent (iii), when oligomer is wherein a kind of monomer when being the monomeric oligomer altogether of two kinds of normal olefine, the number-average molecular weight of this derivative is at least 1600, and
(iv) a kind ofly contain at least two-NH
2And/or-polyamines of NH base, or with
(v) reagent (ii) and pre-formation product (iv) reacts, wherein at least a ethylenically unsaturated compounds of oligomer have a kind of can with the functional group of amine reaction, this oligomeric reaction product is randomly further reacted with low molecular amine.
(i), (ii) and (iv) or (i) and (reaction v) is preferably in a suitable solvent and exists down, is heating up (promptly, be higher than under the envrionment temperature (20 ℃) for example 25-200 ℃, especially at 160-200 ℃, often under refluxad, if necessary, boosting down, as 2-100 * 10
5Pa carries out easily.The example of solvent comprises hydrocarbon solvent, as hexane, hexanaphthene, toluene, dimethylbenzene; Also have synthetic and mineral oil, for example " HVI-60 "; Ether solvents, as tetrahydrofuran (THF) and 1, the 4-diox; Nitrile is as acetonitrile; Alcohol is as 1-amylalcohol (amylalcohol) and 2-methyl-2-propyl alcohol (trimethyl carbinol); And chlorocarbon, as 1.This technology can be carried out in the presence of the solvent not having, but as noted above, also can carry out easily in the presence of solvent.For example use dean stark trap can remove any water or excessive alcohol.
In the method for the invention, weight ratio (ii): (iv) be preferably 100: 1-5: 1, more preferably 33: 1-13: 1, weight ratio (iv): (i) be preferably 1: 20-20: 1, more preferably 1: 5-5: 1.
Reaction product of the present invention can be used as the lubricating oil dispersant additive.Therefore, the invention provides a kind of lubricating oil composition, it comprises of the present invention a kind of reaction product (actives) of lubricating oil with a small amount of (being lower than 50%w), preferred 0.1-20%w, the particularly 0.5-10%w of a kind of main amount (being higher than 50%w), and this weight percentage is based on the composition gross weight.
Proper lubrication oil is natural, mineral or synthetic lubricating oil.
Natural lubricating oil comprises animal and plant oil, for example Viscotrol C.Mineral oil comprises the lubricating oil fraction that is obtained by crude oil, coal or shale, and described fraction may be carried out some and be handled as clay acid, solvent or hydrotreatment.Ucon oil comprises synthetic polymer, modification alkylene oxide polymer and the ester lubricant of hydrocarbon, and they are known in the art.These lubricating oil preferably are used for the crankcase oil of spark ignition and compression-ignition engine, but also comprise hydraulic lubricant, metal working fluid and automatic transmission liquid.
Best, the lubricating base oil component of the present composition is the mixture of a kind of mineral lubricating oils or mineral lubricating oils, for example by the material of Royal Duth/Shell Group member company, or by the synthetic hydrocarbon base oil of Royal Datch/Shell Group of Companies member company with the trade mark " XHVI " (trade(brand)name) sale with the trade mark " HVI " sale.
The lubrication base oil viscosity that exists in the present composition can change in wide region, generally is in 100 ℃ of 3-350mm
2/ s.
Lubricating oil composition of the present invention can contain various other additive known in the art, viscosity index improver for example, for example diene (as, isoprene or divinyl) linear or star polymer, or this diolefine and the cinnamic multipolymer that replaces arbitrarily.These multipolymers are suitably segmented copolymer and preferably are hydrogenated to a certain degree with saturated most of alkene unsaturated link(age).Other suitable additive comprises dispersion agent V.I. improving agent, for example based on the material of segmented copolymer or polymethacrylate, extreme pressure/wear preventive additive such as zinc dithiophosphate or sodium, ashless dispersant is as the succinimide of polyolefine replacement, the material of introducing at GB-A-2231873 for example, antioxidant, rust-proofing additive, friction modifiers or metallic washing composition, as phenates, sulfonate, alkylsalicylate or naphthenate, all these washing composition can be overbasic.
Reaction product of the present invention also can be used as the dispersant additives in the fuel.Therefore, the present invention further provides a kind of fuel composition, it comprises a kind of fuel of main amount (being higher than 50%w) and a small amount of (being lower than 50%w), preferred 0.001-2%w, the more preferably reaction product a kind of of the present invention (actives) of 0.001-0.5%w, particularly 0.002-0.2%w, and weight percentage is based on the composition gross weight.
Suitable fuel comprises gasoline and diesel oil fuel.These basic fuel can comprise the saturated alkene or the mixture of aromatic hydrocarbons.They can be by straight-run spirit, the synthetic aromatic hydrocarbons mixture that makes, thermocatalysis cracked hydrocarbon feed, the petroleum fractions of hydrocracking or the hydrocarbon of catalytic reforming.
Fuel composition of the present invention can contain other additive known in the art, and for example lead compound is as antiknock dope; Antiknock dope except lead compound, for example methyl cyclopentadienyl-manganese tricarbonyl or neighbour-azido-phenyl; Be total to antiknock dope, as benzoyl acetone; Go clouding agent (dehazer) (as, ethoxylated glycerol, as conduct " SURDYNE " (trade(brand)name) M155 (ex Shell Chemicals, the material that UK sells) or alkoxylated phenol formaldehyde polymers, as conduct " NALCO " (trade(brand)name) 7D07 (ex Nalco), " TOLAD " (trade(brand)name) 2683 (ex Petrolite) or " SURDYNE " (trade(brand)name) D265, M153, M154 or M156 (ex Shell Chemicals, UK) commercially available material; Defoamer (as, polyether-modified is polysiloxane-based, and they are as " TEGOPREN " (trade(brand)name) 5851, Q25907 (ex Dow Corning).Or " RHODORSIL " (trade(brand)name) (ex Rhone Poulenc) sold); Ignition improver (as, nitric acid 2-ethylhexyl, cyclohexyl nitrate, the 2nd row among peroxide di-t-butyl and the US-A-4208190,27 row-Di, 3 row, disclosed material in 21 row); Funcitonal rust-proof agent (as, Rhein Chemie, Mannheim, the material that Germany sells with " RC 4801 "), or the polyol ester of succinic acid derivative, this succinic acid derivative has C at least one of its alpha-carbon atom
20-500Replace or unsubstituted aliphatic hydrocarbyl (for example, the pentaerythritol diester of the succsinic acid of polyisobutene replacement); Regeneration spices (reodorants); Wear preventive additive; Antioxidant (as, phenols, as 2,6 di t butyl phenol or phenylenediamine, as N, N '-two sec-butyls-Ursol D); Metal passivator; Lubricant (as, with EC831 (ex Paramins) or the commercially available product of " HITEC " (trade(brand)name) 580 (ex Ethyl Corporation)); Or transport fluid, as polyether, as C
12-C
15The propylene glycol (" SAP 949 " are sold by Royal Dutch/Shell group member company) that alkyl replaces, " HVI " or " XHVI (trade(brand)name) base oil is by C
2-C
6The polyolefine that monomer obtains, as have the polyisobutene of 20-175, a particularly 35-150 carbon atom, or be 2 * 10 in 100 ℃ of viscosity
-6-2 * 10
-5m
2The poly-alpha olefins of/s (2-20 centistoke) is for by at least a C
8-18'alpha '-olefin monomers deutero-C
18-80 hydrogenation oligomers.
Lubricating oil of the present invention and fuel composition can prepare by reaction product of the present invention is added in lubricating oil or the fuel.Traditionally, multifunctional additive for lubricating oils and lubricating oil or fuel mix.This enriched material generally includes the additive of a kind of inertia transport fluid and one or more conc forms.Therefore, the present invention also provides a kind of multifunctional additive for lubricating oils, and it comprises of the present invention a kind of reaction product (actives) of a kind of inertia transport fluid and 10-80%w, and weight percentage is based on the enriched material gross weight.
The example of inertia transport fluid comprises the mixture of hydrocarbon and hydrocarbon and alcohol or ether, for example methyl alcohol, ethanol, propyl alcohol, butoxy ethanol or methyl tert-butyl ether.For example, transport fluid can be an aromatic solvent, as the mixture of toluene, dimethylbenzene, its mixture or toluene or dimethylbenzene and alcohol.In addition, transport fluid can be the mixture of mineral base oil or mineral base oil, for example by Royal Dutch/ShellGroup with the trade mark " HVI " (as, " HVI60 " base oil) product of Chu Shouing, or the synthetic hydrocarbon base oil of selling with the trade mark " XHVI " (trade(brand)name) by the member company of Royal Dutch/Shell Group of Companies.
The present invention also provides the purposes of reaction product of the present invention as dispersant additives.
Further understand the present invention from following illustrative embodiment.In these embodiments, number-average molecular weight (Mn) for the atactic oligomeric acrylamide body portion regulation in the part of the polyisobutene in polyisobutenyl succinic anhydride/succinimide and the atactic oligomeric acrylamide body base succinyl oxide/succinimide is according to the modern gel chromatography of using polystyrene standard, W.W.Yau for example, J.J.Kirkland and D.D.Bly, " Modern Size Exclusion LiquidChromatography ", John Wiley and Sons, New York, the method for introducing in 21979 is measured.
The mensuration of active matter content is told the torpescence thing from required actives and is carried out by using ether to make eluent on alumina column; Acid number is measured according to ASTM D664; Total basicnumber is measured according to ASTM D2896.
In an embodiment, use hereinafter to be referred as:
PIBSA: polyisobutenyl succinic anhydride, wherein the Mn of polyisobutene base section (pressing GPC measures) is at embodiment 1-21,37-52, be 2200 ± 200 in 55 and 56, in embodiment 22-36,53, being 1000 ± 200 in 54 and 57, is according to the preparation of the method for EP-A-0542380.
APOSA: atactic oligomeric acrylamide body base succinyl oxide, wherein the Mn of atactic oligomeric acrylamide body portion (measuring according to GPC) is 2200 ± 200 in embodiment 58-60, being 835 ± 100 in embodiment 61, is according to the preparation of the method for EP-A-0490454.
TETA: Triethylenetetramine (TETA)
TEPA: tetren
PEHA: penten
S75: contain the polyamine mixture of tetren, penten and senior ethylidene polyamines (weight ratio is 1: 2: 1), sell by Delamine B.V.Netherlands.
Embodiment 1
In 150 ℃, " SMA 3000A " and isooctyl alcohol (" SMA 3840A " ex.Elf-Atochem) (1.5g) are dissolved in " SHELLSOLA " (trade(brand)name) (are rich in arylide (99% arylide), high boiling point (B.Pt.166-180 ℃) solvent (ex.ShellNederland Chemie B.V.)) reaction product (coupling is 1.5 ± 0.1 than (PIBSA mole number/polyamines mole number)) (50g, 40.9% actives) that is added to PIBSA and S75 of monoesters (150ml) is dissolved in " SHELLSOLA " solution that is stirring (50ml).Temperature of reaction per hour raises about 15 ℃, and any alcohol of removing " SHELLSOLA ", water and discharge by dean stark trap.Can change heating rate.In case temperature reaches 200 ℃, will react on this temperature maintenance 1 hour.Excessive solvent is removed in decompression.
Embodiment 2-41
Employing is similar to the method that the foregoing description 1 is introduced, the further reaction product of preparation the present invention, the i.e. product of embodiment 2-41.The coupling ratio that is used for embodiment 21 is 1.2 ± 0.1, and the coupling ratio that is used for embodiment 37 and 38 is 1.0 ± 0.1.
The kind of agents useful for same and consumption and under known case the total basicnumber of gained polymeric amide derivative and the details of nitrogen content be listed in the table below 1, wherein the percentage ratio of reactant B is not considered the percentage ratio of actives among the A with respect to the gross weight of reactant A:
Table 1
| Reactant | Product | |||||
| Embodiment number | A actives % | ????％B | Actives % | Total basicnumber (mg KOH/g) | Nitrogen content (%w) | |
| ????1 | The monoesters of A=PIBSA+S75 B=SMA 3000A and iso-octyl alcohol | ????40.9 | ????3.0 | ????42.8 | ????21.6 | ????0.95 |
| ????2 | The diester of A=PIBSA+S75 B=SMA 3000A and isoamyl alcohol | ????40.9 | ????2.5 | ????41 | ????22.6 | ????0.93 |
| ????3 | The diester of A=PIBSA+S75 B=SMA 3000A and isoamyl alcohol | ????40.9 | ????4.7 | ????42 | ????22.0 | ????0.95 |
| ????4 | The diester of A=PIBSA+S75 B=SMA 3000A and isoamyl alcohol | ????40.9 | ????10.0 | ????43 | ????20.6 | ????0.89 |
| ????5 | The diester of A=PIBSA+S75 B=SMA 3000A and isoamyl alcohol | ????40.9 | ????5.0 | ????42 | ????22.8 | ????0.91 |
Table 1 (continuing)
| ????6 | The monoesters of A=PIBSA+S75 B=SMA 3000A and iso-octyl alcohol | ????40.9 | ????1.0 | ????43.1 | ????23.2 | ????0.95 |
| ????7 | The monoesters of A=PIBSA+S75 B=SMA 3000A and iso-octyl alcohol | ????40.9 | ????2.0 | ????44.6 | ????21.2 | ????0.92 |
| ????8 | The monoesters of A=PIBSA+S75 B=SMA 3000A and iso-octyl alcohol | ????40.9 | ????4.0 | ????43.2 | ????20.8 | ????0.97 |
| ????9 | The monoesters of A=PIBSA+S75 B=SMA 3000A and iso-octyl alcohol | ????40.9 | ????5.0 | ????45.4 | ????19.2 | ????0.91 |
| ????10 | The monoesters of A=PIBSA+S75 B=SMA 3000A and iso-octyl alcohol | ????40.9 | ????6.0 | ????46.5 | ????18.2 | ????0.90 |
| ????11 | The monoesters of A1=PIBSA A2=S75 B=SMA 3000A and iso-octyl alcohol | ????60 | ????6.0 | ????60.2 | ????NM | ????NM |
| ????12 | The monoesters of A=PIBSA+S75 B=SMA 3000A and iso-octyl alcohol | ????40.9 | ????7.0 | ????45.1 | ????18.0 | ????0.92 |
Table 1 (continuing)
| ????13 | The monoesters of A=PIBSA+S75 B=SMA 1000A and iso-octyl alcohol | ????40.9 | ????2.0 | ????41.6 | ????18.9 | ????0.95 |
| ????14 | The monoesters of A=PIBSA+S75 B=SMA 1000A and iso-octyl alcohol | ????40.9 | ????4.0 | ????42.8 | ????19.3 | ????0.98 |
| ????15 | The monoesters of A=PIBSA+S75 B=SMA 1000A and iso-octyl alcohol | ????40.9 | ????5.0 | ????43.6 | ????16.9 | ????0.96 |
| ????16 | The monoesters of A=PIBSA+S75 B=SMA 1000A and iso-octyl alcohol | ????40.9 | ????6.0 | ????43.7 | ????17.3 | ????0.96 |
| ????17 | The monoesters of A=PIBSA+S75 B=SMA 1000A and iso-octyl alcohol | ????40.9 | ????8.0 | ????44.7 | ????16.7 | ????0.95 |
| ????18 | The monoesters of A=PIBSA+S75 B=SMA 1000A and iso-octyl alcohol | ????40.9 | ????10.0 | ????45.9 | ????16.3 | ????0.94 |
| ????19 | The monoesters of A=PIBSA+S75 B=SMA 1000A and iso-octyl alcohol | ????40.9 | ????20.0 | ????47.6 | ????14.1 | ????0.89 |
Table 1 (continuing)
| ????20 | The monoesters of A=PIBSA+S75 B=SMA 1000A and iso-octyl alcohol | ????40.9 | ????30.0 | ????51.7 | ????12.1 | ????0.89 |
| ????21 | The monoesters of A=PIBSA+S75 B=SMA 3000A and iso-octyl alcohol | ????42.1 | ????4.0 | ????40.0 | ????28.0 | ????1.2 |
| ????22 | The monoesters of A=PIBSA+TEPA B=SMA 3000A and iso-octyl alcohol | ????46.8 | ????2.5 | ????47.8 | ????44.7 | ????1.93 |
| ????23 | The monoesters of A=PIBSA+TEPA B=SMA 3000A and iso-octyl alcohol | ????60.0 | ????3.0 | ????61 | ????55.5 | ????2.43 |
| ????24 | The monoesters of A=PIBSA+TEPA B=SMA 3000A and iso-octyl alcohol | ????46.8 | ????3.0 | ????48.2 | ????44.0 | ????1.91 |
| ????25 | The monoesters of A=PIBSA+TEPA B=SMA 3000A and iso-octyl alcohol | ????60.0 | ????4.0 | ????61 | ????56.7 | ????2.43 |
| ????26 | The monoesters of A=PIBSA+TEPA B=SMA 3000A and iso-octyl alcohol | ????46.8 | ????4.0 | ????48.6 | ????45.0 | ????1.92 |
Table 1 (continuing)
| ????27 | The monoesters of A=PIBSA+TEPA B=SMA 3000A and iso-octyl alcohol | ????46.8 | ????5.0 | ????48.8 | ????43.4 | ????1.87 |
| ????28 | The monoesters of A=PIBSA+TEPA B=SMA 3000A and iso-octyl alcohol | ????46.8 | ????6.0 | ????49.3 | ????40.9 | ????1.88 |
| ????29 | The monoesters of A=PIBSA+TEPA B=SMA 3000A and iso-octyl alcohol | ????46.8 | ????7.0 | ????49.2 | ????41.0 | ????1.89 |
| ????30 | The monoesters of A=PIBSA+TEPA B=SMA 3000A and iso-octyl alcohol | ????46.9 | ????8.0 | ????48.7 | ????38.4 | ????1.79 |
| ????31 | The monoesters of A=PIBSA+TEPA B=SMA 3000A and iso-octyl alcohol | ????46.8 | ????10.0 | ????47.4 | ????37.0 | ????1.76 |
| ????32 | The monoesters of A=PIBSA+TEPA B=SMA 3000A and iso-octyl alcohol | ????46.8 | ????15.0 | ????48.8 | ????34.4 | ????1.76 |
| ????33 | The monoesters of A=PIBSA+TEPA B=SMA 1000A and iso-octyl alcohol | ????46.8 | ????5.0 | ????49.5 | ????38.4 | ????1.84 |
Table 1 (continuing)
| ????34 | The monoesters of A=PIBSA+TEPA B=SMA 1000A and iso-octyl alcohol | ????46.8 | ????10.0 | ????49.6 | ????31.3 | ????1.73 |
| ????35 | The monoesters of A=PIBSA+TEPA B=SMA 1000A and iso-octyl alcohol | ????46.8 | ????15.0 | ????43.2 | ????28.9 | ????1.73 |
| ????36 | The monoesters of A=PIBSA+TEPA B=SMA 1000A and iso-octyl alcohol | ????46.8 | ????20.0 | ????47.3 | ????25.2 | ????1.58 |
| ????37 | The monoesters of A=PIBSA+S75 B=SMA 3000A and iso-octyl alcohol | ????60 | ????4.0 | ????60.1 | ????54.2 | ????2.02 |
| ????38 | The monoesters of A=PIBSA+TEPA B=SMA 3000A and iso-octyl alcohol | ????42.6 | ????4.0 | ????43.7 | ????29.3 | ????1.14 |
| ????39 | A=PIBSA+S75 B=polyacrylic acid n-pentyl ester | ????40.9 | ????3.0 | ????43.0 | ????20.1 | ????0.95 |
| ????40 | A=PIBSA+S75 B=polyacrylic acid n-pentyl ester | ????40.9 | ????5.0 | ????43.6 | ????16.7 | ????0.94 |
| ????41 | A=PIBSA+S75 B=polyacrylic acid n-pentyl ester (carrying out aftertreatment) with aniline | ????40.9 | ????3.0 | ????NM | ????24.9 | ????1.1 |
In the embodiment of above embodiment and back:
(a) " SMA 3000A " is vinylbenzene/maleic anhydride oligomer (Mn 2350), wherein vinylbenzene: the mol ratio of maleic anhydride is 3 (ex Elf-Atochem)
(b) " SMA 1000A " is vinylbenzene/maleic anhydride oligomer (Mn 962), wherein vinylbenzene: the mol ratio of maleic anhydride is 1 (ex Elf-Atochem)
(c) embodiment 1,6-12,21-32, reactant B is " SMA3840A " in 37 and 38, a kind of lower molecular weight (Mn 3120) oligomer, wherein vinylbenzene: the mol ratio of maleic anhydride is 3, and wherein maleic anhydride generates monoesters (ex Elf-Atochem) with the reaction of iso-octyl alcohol
(d) reactant B is to use lower molecular weight (about 1000) polyacrylic acid of Pentyl alcohol esterification among the embodiment 39-41
(e) embodiment 1-10,12-20, reactant A has 1.5 ± 0.1 coupling than (PIBSA mole number/polyamines mole number) among 22-36 and the 39-41
(f) reactant A has 1.2 ± 0.1 coupling than (PIBSA mole number/polyamines mole number) among the embodiment 21
(g) reactant A has 1.0 ± 0.1 coupling than (PIBSA mole number/polyamines mole number) among the embodiment 37 and 38
(h) embodiment 22-36, reactant A is in 53,54 and 57 " SAP 230TP ", a kind of list/double amber imide ashless dispersant (ex.Shell Additives International Ltd.)
(i) reactant A is among the embodiment 43-47 and 56 " SAP 285 ", a kind of high molecular double amber imide ashless dispersant (ex.Shell Additive International Ltd.)
(j) " NM "=undetermined
Embodiment 42
Under 140 ℃ and nitrogen, " the SMA 3000A " that will be dissolved in (50ml) (100 ℃) (1.65g) is added in the solution that " the SHELLSOL A " of the reaction product (coupling is 1.5 ± 0.1 than (PIBSA mole number/polyamines mole number)) (50g, 40.9% actives) of PIBSA and S75 (50ml) stir.Improve temperature of reaction, remove " SHELLSOLA " and water gradually, last 4 hours by dean stark trap.In case temperature reaches 200 ℃, will react under this temperature and keep 15 hours.Excessive solvent (120 ℃, 5mmHg, 2 hours) is removed in decompression, obtains the transparent liquid of burgundy (51g).
The total basicnumber and the nitrogen content of the kind of agents useful for same and consumption and gained polyimide derivative are listed in the table below 2, and wherein the percentage ratio of reactant B is not considered the percentage ratio of actives among the A with respect to the gross weight of reactant A:
Table 2
| Reactant | Product | |||||
| Embodiment number | A actives % | ????％B | Actives % | Total basicnumber (mg KOH/g) | Nitrogen content (%w) | |
| ????42 | ????A＝PIBSA+S75 ????B＝SMA?3000A | ????40.9 | ????3.0 | ????39.6 | ???16.3 | ??0.8 |
Embodiment 43
Under 140 ℃ of nitrogen, with " SMA 3000A " and iso-octyl alcohol (" SMA 3840A; ex.Elf-Atochem) (4.0g) monoesters of being dissolved in dimethylbenzene is added in the solution that the dimethylbenzene (100ml) of PIBSA and S75 reaction product (coupling is 2.0 ± 0.2 than (PIBSA mole number/polyamines mole number)) (100g, 42.0% actives) stirs.Improve temperature of reaction, remove removal xylene, water and any alcohol gradually by Dean Rodney Stark couch water trap.In case temperature reaches 200 ℃, will react on and keep under this temperature 1 hour.Excessive solvent (110 ℃, 5mmHg, 2 hours) is removed in decompression, obtains the transparent liquid of burgundy (100g).
Embodiment 44-47
Employing is similar to the method that the foregoing description 43 is introduced, the further reaction product of preparation the present invention.
The total basicnumber of the kind of used reagent and consumption and gained polyimide derivative and the details of nitrogen content are listed in the table below 3, and wherein the percentage ratio of reactant B is not considered actives percentage ratio among the A with respect to the gross weight of reactant A:
Table 3
| Reactant | Product | |||||
| Embodiment number | A actives % | ????％B | Actives % | Total basicnumber (mg KOH/g) | Nitrogen content (%w) | |
| ????43 | The monoesters of A=PIBSA+S75 B=SMA 3000A and iso-octyl alcohol | ????42.0 | ????4.0 | ????44.1 | ????13.3 | ?????0.7 |
| ????44 | The diester of A=PIBSA+S75 B=SMA 3000A and isoamyl alcohol | ????42.0 | ????1.0 | ????44.0 | ????14.8 | ?????0.72 |
| ????45 | The diester of A=PIBSA+S75 B=SMA 3000A and isoamyl alcohol | ????42.0 | ????2.0 | ????43.3 | ????14.4 | ?????0.71 |
| ????46 | The diester of A=PIBSA+S75 B=SMA 3000A and isoamyl alcohol | ????42.0 | ????3.0 | ????46.1 | ????13.7 | ?????0.68 |
| ????47 | The diester of A=PIBSA+S75 B=SMA 3000A and isoamyl alcohol | ????42.0 | ????5.0 | ????44.4 | ????12.9 | ?????0.69 |
Embodiment 48
Under 140 ℃ and nitrogen, will be dissolved in " SHELLSOL A " (10ml) with the C maleic anhydride copolymerization
10-20(" PX-100 " (Mn 2400) ex.Akzo NobelGmbH (2.5) are added in the solution that " the SHELLSOL A " of PIBSA and S75 reaction product (coupling is 1.5 ± 0.1 than (PIBSA mole number/polyamines mole number)) (50g, 40.9% actives) (50ml) stir linear alpha-olefin.Improve temperature of reaction, remove " SHELLSOL A " and water gradually, last 4 hours by dean stark trap.In case temperature reaches 200 ℃, will react on and keep under this temperature 15 hours.Excessive solvent (120 ℃, 5mmHg, 2 hours) is removed in decompression, obtains the transparent liquid of burgundy (51g).
Embodiment 49-52
Employing is similar to the method that the foregoing description 48 is introduced, the further reaction product of preparation the present invention.
The total basicnumber of the kind of used reagent and consumption and gained polyimide derivative and the details of nitrogen content are listed in the table below 4, and wherein the percentage ratio of reactant B is not considered actives percentage ratio among the A with respect to the gross weight of reactant A:
Table 4
| Reactant | Product | |||||
| Embodiment number | A actives % | ????％B | Actives % | Total basicnumber (mg KOH/g) | Nitrogen content (%w) | |
| ????48 | The C of A=PIBSA+S75 B=and maleic anhydride copolymerization 10-20Linear alpha-olefin | ????40.9 | ????5.0 | ????44.5 | ????17.4 | ????0.97 |
| ????49 | The C of A=PIBSA+S75 B=and maleic anhydride copolymerization 10-20Linear alpha-olefin | ????40.9 | ????2.0 | ????42.0 | ????24.0 | ????0.97 |
| ????50 | The C of A=PIBSA+S75 B=and maleic anhydride copolymerization 10-20Linear alpha-olefin | ????40.9 | ????4.0 | ????43.0 | ????19.6 | ????0.96 |
| ????51 | The C of A=PIBSA+S75 B=and maleic anhydride copolymerization 10-20Linear alpha-olefin | ????40.9 | ????6.0 | ????45.0 | ????19.6 | ????0.93 |
| ????52 | The C of A=PIBSA+S75 B=and maleic anhydride copolymerization 10-20Linear alpha-olefin | ????40.9 | ????8.0 | ????45.5 | ????19.5 | ????0.93 |
Embodiment 53
Under 140 ℃ and nitrogen, polyacrylic Pentyl alcohol ester (" GOODRITE 752 ") (Mn 1000) the ex Coodrich Chemicals (6.3g) that will be dissolved in dimethylbenzene (63ml) are added in the solution that the dimethylbenzene (63ml) of PIBSA and TEPA reaction product (coupling is 1.5 ± 0.1 than (PIBSA mole number/polyamines mole number)) (63g, 45.0% actives) stirs.Improve temperature of reaction, remove removal xylene and water gradually, last 4 hours by dean stark trap.In case temperature reaches 200 ℃, will react on and keep under this temperature 15 hours.Excessive solvent (120 ℃, 5mmHg, 2 hours) is removed in decompression, obtains the transparent liquid of burgundy (65g).
Embodiment 54
Employing is similar to the method that the foregoing description 53 is introduced, the further reaction product of preparation the present invention.
The total basicnumber of the kind of used reagent and consumption and gained polyimide derivative and the details of nitrogen content are listed in the table below 5, and wherein the percentage ratio of reactant B is not considered actives percentage ratio among the A with respect to the gross weight of reactant A:
Table 5
| Reactant | Product | |||||
| Embodiment number | A actives % | ????％B | Actives % | Total basicnumber (mg KOH/g) | Nitrogen content (%w) | |
| ????53 | The polyacrylic Pentyl alcohol ester of A=PIBSA+TEPA B= | ????45.0 | ????10.0 | ????49.9 | ????30.8 | ?????1.84 |
| ????54 | The polyacrylic Pentyl alcohol ester of A=PIBSA+TEPA B= | ????45.0 | ????5.0 | ????47.8 | ????40.0 | ?????1.91 |
Embodiment 55
In room temperature, the reaction product (coupling is 1.5 ± 0.1 than (PIBSA mole number/polyamines mole number)) that styrene/acrylic acid co-polymer (" MOREI 300 " are ex.Morton International Limited (Mn1300)) (7g) is added to PIBSA and S75 (100g) and the different third oxygen titanium (IV) " SHELLSOL A " (0.15g) (150g) in the solution.Introduce nitrogen and clean, and temperature is raised to 120 ℃ to dissolve " MOREZ 300 " with 1 hour time.Improve temperature then, remove " SHELLSOL A " and water gradually, last 4 hours by dean stark trap.In case temperature reaches 200 ℃, will be reflected at and keep under this temperature 24 hours.Product is dissolved in the toluene and filters.Excessive solvent (120 ℃, 5mmHg, 2 hours) is removed in decompression, obtains burgundy liquid (100g).
Embodiment 56-57
Employing is similar to the method that the foregoing description 56 is introduced, the further reaction product of preparation the present invention.
The kind of used reagent and consumption and under known case the total basicnumber of gained polyimide derivative and the details of nitrogen content be listed in the table below 6, wherein the percentage ratio of reactant B is not considered actives percentage ratio among the A with respect to the gross weight of reactant A:
Table 6
| Reactant | Product | |||||
| Embodiment number | A actives % | ????％B | Actives % | Total basicnumber (mg KOH/g) | Nitrogen content (%w) | |
| ????55 | A=PIBSA+S75 B=styrene/acrylic acid co-polymer | ????40.9 | ????7.0 | ????43.2 | ????14.0 | ?????0.91 |
| ????56 | A=PIBSA+S75 B=styrene/acrylic acid co-polymer | ????40.9 | ????4.0 | ????43.4 | ????11.0 | ?????0.67 |
| ????57 | A=PIBSA+S75 B=styrene/acrylic acid co-polymer | ????45.0 | ????11.0 | ????47.4 | ????30.0 | ?????NM |
Embodiment 58
Under 140 ℃ and nitrogen, will be dissolved in " SHELLSOL A " " SMA3000A " and monoesters (" SMA 3840 A " ex.Elf-Atochem) of iso-octyl alcohol in (20ml) and (2g) be added to APOSA and S75 reaction product (coupling than) APOSA mole number/polyamines mole number (being 1.5 ± 0.1) (50g) in the solution of " SHELLSOL A " stirring in (130ml).Improve temperature of reaction, remove " SHELLSOL A ", water and any alcohol gradually by dean stark trap.In case temperature reaches 200 ℃, will react on and keep under this temperature 1 hour.Excessive solvent (120 ℃, 5mmHg, 2 hours) is removed in decompression, obtains the transparent liquid of burgundy (500g).
Embodiment 59-61
Employing is similar to the method that the foregoing description 58 is introduced, the further reaction product of preparation the present invention.The coupling ratio that is used for embodiment 59 is 2.0 ± 0.2.
The total basicnumber of the kind of used reagent and consumption and gained polyimide derivative and the details of nitrogen content are listed in the table below 7, and wherein the percentage ratio of reactant B is not considered actives percentage ratio among the A with respect to the gross weight of reactant A:
Table 7
| Reactant | Product | |||||
| Embodiment number | A actives % | ????％B | Actives % | Total basicnumber (mg KOH/g) | Nitrogen content (%w) | |
| ????58 | The monoesters of A=APOSA+S75 B=SMA 3000A and iso-octyl alcohol | ????47.9 | ????4.0 | ????48.5 | ????18.4 | ????0.93 |
| ????59 | The monoesters of A=APOSA+PEHA B=SMA 3000A and iso-octyl alcohol | ????42.0 | ????2.0 | ????46.2 | ????14.9 | ????0.8 |
| ????60 | The monoesters of A=APOSA+PEHA B=SMA 3000A and iso-octyl alcohol | ????42.0 | ????4.0 | ????45.6 | ????22.9 | ????1.09 |
| ????61 | The monoesters of A=APOSA+TEPA B=SMA 3000A and iso-octyl alcohol | ????42.0 | ????5.0 | ????55.1 | ????37.7 | ????1.82 |
Embodiment 62
Turbidity (haze) test
" turbidity " is the percentage ratio that is departed from the transmitted light of incoming beam when passing sample by forward scattering.Concerning this method, have only on average to be higher than 2.5 ° of BEAM SQUINTs and to be considered to muddy.
In 100 ℃, dispersion agent is dissolved in (mass ratio is 1: 9) in " HVI 60 " oil.Utilize the pivot ball turbidimetric apparatus, the turbidity of solvent is proofreaied and correct the turbidity of measuring solution.Turbidimeter is by ASTM D1003 regulation, and digital indicator reads 0.1%.
These tests the results are shown in table 8:
Table 8
| Embodiment number | Turbidity (%) | Embodiment number | Turbidity (%) |
| ????1 | ????5.0 | ????29 | ????2.2 |
| ????2 | ????9.6 | ????30 | ????5.0 |
| ????3 | ????8.8 | ????31 | ????1.0 |
| ????4 | ????6.2 | ????32 | ????0.4 |
| ????5 | ????7.1 | ????33 | ????2.8 |
| ????6 | ????7.9 | ????34 | ????2.0 |
| ????7 | ????5.2 | ????35 | ????1.8 |
| ????8 | ????6.0 | ????36 | ????4.3 |
| ????9 | ????10.3 | ????39 | ????6.5 |
| ????10 | ????7.0 | ????40 | ????4.0 |
| ????12 | ????14.7 | ????48 | ????5.4 |
| ????13 | ????3.4 | ????49 | ????5.2 |
| ????14 | ????4.8 | ????50 | ????6.8 |
| ????15 | ????4.5 | ????51 | ????5.5 |
| ????16 | ????4.6 | ????52 | ????6.9 |
| ????17 | ????5.1 | ????53 | ????3.3 |
| ????18 | ????6.5 | ????54 | ????2.4 |
| ????19 | ????6.7 | ????55 | ????1.0 |
| ????20 | ????9.3 | ????56 | ????1.0 |
| ????21 | ????11.0 | ????57 | ????3.0 |
| ????22 | ????＜1.0 | ????58 | ????3.7 |
| ????24 | ????＜1.0 | ????59 | ????2.4 |
| ????26 | ????＜1.0 | ????60 | ????4.6 |
| ????27 | ????1.3 | ????61 | ????1.6 |
| ????28 | ????＜1.0 |
From the numeral of table 8 as can be seen, reaction product of the present invention has low-level turbidity.
Embodiment 63
Carbon black dispersion test (CBDT)
(British?Rail?Publication?BR?669：1984)
Modification obtains containing the oil that concentration is the derivative of 1%w actives by the oligomer reaction product of mixing embodiment to contain the sample of SAE15W40 Middle East lubricating oil of commodity packaging of zinc dialkyl dithiophosphate, high alkalinity alkyl sodium salicylate and VI improving agent.Then, join the 3%w carbon black in each oil and utilize the Ubbelohde viscometer determining in 60 ℃ of kinematic viscosity (percentage ratio) increment rate.Low result shows functional.The gained absolute value depends on used sooty active surface area, therefore, uses identical carbon black sample and measures relatively series.Test with " Flamruss " (trade(brand)name) carbon black.
These test-results are shown in table 9:
Table 9
| Embodiment number | ???CBDT(％) | Embodiment number | ???CBDT(％) |
| ????1 | ????15.3 | ????24 | ????15.3 |
| ????2 | ????14 | ????26 | ????16.2 |
| ????3 | ????18 | ????27 | ????14.7 |
| ????4 | ????23 | ????28 | ????18.4 |
| ????5 | ????13.7 | ????29 | ????15.2 |
| ????6 | ????15.9 | ????30 | ????15.3 |
| ????7 | ????15.9 | ????31 | ????14.8 |
| ????8 | ????15.5 | ????32 | ????15.3 |
| ????9 | ????18.3 | ????37 | ????14.8 |
| ????10 | ????19.5 | ????38 | ????15.3 |
| ????11 | ????20.3 | ????40 | ????17.6 |
| ????12 | ????17.2 | ????41 | ????18.1 |
| ????22 | ????15.7 | ????42 | ????16.7 |
Embodiment 64
Rheological test
(using controlled strain rate rheometer (Couette geometry))
The carbon black (Cabot Vulcan XC72R) of oven dry utilizes the heated and stirred unit in 100 ℃ of balances, makes the sample dispersion agent suitably fully in the test oil of preparation suitable concentration arranged.Under the shearing rate of a certain scope, use Couette geometry to measure the equilibrated sample.Carry out initial manually shearing rate scan to determine that rheometer suitable sensitivity location and pretreatment sample are to eliminate any shearing course.Afterwards, make sample temperature compensation at least 10 minutes before mensuration.With regard to carbon black dispersion test (CBDT), show as " SAP 230TP " and " SAP285 " low viscosity increase that than parent dispersion agent dispersiveness is improved than those succinimides.
These test-results are shown in table 10, and the numeral in the bracket is corresponding parent dispersion agent.
Table 10
| Embodiment number | Rheological (1s -1) | Embodiment number | Rheological (1s -1) |
| ??1 | ??1????(5) | ??32 | ??0.5??(3) |
| ??6 | ??1.5??(5) | ??33 | ??1????(3) |
| ??7 | ??2????(5) | ??34 | ??0.5??(3) |
| ??8 | ??0.5??(5) | ??35 | ??0.5??(3) |
| ??9 | ??0.5??(5) | ??36 | ??0.5??(3) |
| ??10 | ??0.5??(5) | ??39 | ??1.2??(3) |
| ??12 | ??0.5??(5) | ??40 | ??1????(3) |
| ??13 | ??4????(5) | ??42 | ??3????(5) |
| ??14 | ??2????(5) | ??43 | ??5????(8) |
| ??15 | ??4????(5) | ??44 | ??6????(8) |
| ??16 | ??2????(5) | ??45 | ??4????(8) |
| ??17 | ??3????(5) | ??46 | ??5????(8) |
| ??18 | ??3????(5) | ??47 | ??5????(8) |
| ??19 | ??4????(5) | ??48 | ??2????(4) |
| ??20 | ??4????(5) | ??49 | ??2????(4) |
| ??22 | ??2????(3) | ??50 | ??2????(4) |
| ??24 | ??1.5??(3) | ??51 | ??2????(4) |
| ??26 | ??1????(3) | ??52 | ??3????(4) |
| ??27 | ??0.5??(3) | ??53 | ??1????(3) |
| ??28 | ??0.5??(3) | ??54 | ??1????(3) |
| ??29 | ??0.5??(3) | ??55 | ??0.5??(3) |
| ??30 | ??0.5??(3) | ??56 | ??1????(3) |
| ??31 | ??0.5??(3) | ??57 | ??0.5??(2) |
Embodiment 65
Corrosion test
(with reference to the APICG-4 test) shows and reduced corrosion compound of the present invention according to the crooked corrosion test of the L-10 that adjusts without strictness.Under identical dispersion agent treatment rate, the result is as follows:
Table 11
The lead (ppm) that sample leaches
“SAP?230TP”???????18
Embodiment 27 5
Embodiment 66
The fluoroelastomer seal test
Compound of the present invention is less to fluoroelastomer sealing member aggressiveness, and this can obtain the proof of MercedesBenz elastomeric seal test.When the prescription that the sealing fluoroelastomer is contained embodiment 47 was handled, its tensile strength only reduced by 16%, and the degree that it can be stretched before fracture only is 15%, under identical dispersion agent treatment rate, contains the similar prescription of " SAP 285 ", reduces higher.
Table 12
Sample tensile strength tension set
“SAP285”??????????-31％????????-30％
Embodiment 47-16%-15%
Claims (10)
1. the reaction product of following material:
(i) a kind of oligopolymer, its number-average molecular weight is not higher than 7500 and formed by one or both or multiple different monomers, this monomer or each monomer are that a kind of ethylenically unsaturated compounds and described oligomer or every kind of described monomer can be randomly by partial esterization or full esterifications, its each monomer does not contain ether moiety, neither cyclopentadienyl, described oligomer can be randomly with the low molecular weight amine reaction and
(ii) a kind of ethene belongs to unsaturated carboxylic reagent polymerase chain alkenyl derivative (iii), when oligomer be wherein a kind of monomer when being the monomeric oligomer altogether of two kinds of normal olefine this derivative have at least 1600 number-average molecular weight, and
(iv) a kind ofly contain two-NH at least
2And/or-polyamines of NH base, or and
(v) reagent (ii) and pre-formation product (iv), wherein the alefinically unsaturated compounds of oligomer at least a have a kind of can with the functional group of amine reaction, oligomeric reaction product is randomly further reacted with low molecular weight amine.
2. according to the reaction product of claim 1, wherein low molecular weight amine is an aniline.
3. according to the reaction product of claim 1 or 2, therein ethylene belongs to unsaturated carboxylic reagent and is selected from single ethene and belongs to unsaturated C
4-10Dicarboxylic acid and acid anhydrides.
4. according to the reaction product of claim 1,2 or 3, wherein to be derived from be at least a C to polymerase chain alkenyl derivative
2-5The polyolefine of monoolefine polymer.
5. according to each reaction product of aforementioned claim, wherein polyamines is following general formula compound
H
2N-(CHR
1)
x-CH
2-[A-CH
2-(CHR
1)
x]
Y-NH
2(I) wherein A be-NH or-O-, each R
1Represent hydrogen atom or methyl independently, x is 1-3, and when A be-during NH y be 1-10 or when A be-y is 1-200 during O-.
6. method for preparing according to the reaction product of claim 1, this method comprises: make
(i) a kind of oligomer, wherein the number-average molecular weight of this oligomer is not higher than 7500 and the oligomer that formed by a kind of monomer or two or more different monomers, this monomer or each monomer are that ethylenically unsaturated compounds and described oligomer or every kind of described monomer are arbitrarily selectively by partial esterization or full esterification, its each monomer does not contain ether moiety, neither cyclopentadienyl, described oligomer selectively reacts with low molecular weight amine arbitrarily, with
The polymerase chain alkenyl derivative that (ii) a kind of ethene belongs to unsaturated carboxylic reagent (iii), when oligomer is wherein a kind of monomer when being the monomeric oligomer altogether of two kinds of normal olefine, the number-average molecular weight of this derivative is at least 1600, and
(ii) a kind ofly contain at least two-NH
2And/or-polyamines of NH base, or with
(v) reagent (ii) and pre-formation product (ii) reacts, wherein at least a ethylenically unsaturated compounds of oligomer have a kind of can with the functional group of amine reaction, this oligomeric reaction product is randomly further reacted with low molecular weight amine.
7. lubricating oil composition comprises the lubricating oil of main amount and a spot of a kind of according to each reaction product of claim 1-5.
8. fuel composition comprises the fuel of main amount and a spot of a kind of according to each reaction product of claim 1-5.
9. multifunctional additive for lubricating oils comprises a kind of inertia transport fluid and in total enriched material, and 10-80%'s is a kind of according to each reaction product of claim 1-5.
According to each reaction product of claim 1-5 as the purposes of dispersant additives.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96121407 CN1161344A (en) | 1995-11-13 | 1996-11-11 | Dispersant additives |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP95308088.4 | 1995-11-13 | ||
| CN 96121407 CN1161344A (en) | 1995-11-13 | 1996-11-11 | Dispersant additives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1161344A true CN1161344A (en) | 1997-10-08 |
Family
ID=5126866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96121407 Pending CN1161344A (en) | 1995-11-13 | 1996-11-11 | Dispersant additives |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1161344A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1856539B (en) * | 2003-09-23 | 2011-08-03 | 索维公司 | Polymer composition |
-
1996
- 1996-11-11 CN CN 96121407 patent/CN1161344A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1856539B (en) * | 2003-09-23 | 2011-08-03 | 索维公司 | Polymer composition |
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