CN1035331C - Ashless butyl diimide dispersant and its prepn process - Google Patents
Ashless butyl diimide dispersant and its prepn process Download PDFInfo
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- 239000002270 dispersing agent Substances 0.000 title claims abstract description 26
- -1 butyl diimide Chemical compound 0.000 title description 15
- 229910000071 diazene Inorganic materials 0.000 title description 10
- 238000000034 method Methods 0.000 title description 10
- 229920002367 Polyisobutene Polymers 0.000 claims abstract description 28
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 23
- 229920000768 polyamine Polymers 0.000 claims abstract description 21
- 150000004291 polyenes Chemical class 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 238000006467 substitution reaction Methods 0.000 claims abstract description 14
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012467 final product Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims abstract 8
- 229960002317 succinimide Drugs 0.000 claims abstract 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 20
- 239000001384 succinic acid Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012429 reaction media Substances 0.000 claims description 6
- 239000013067 intermediate product Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- 238000004132 cross linking Methods 0.000 claims 1
- 239000011976 maleic acid Substances 0.000 claims 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 52
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 26
- 239000004215 Carbon black (E152) Substances 0.000 abstract 2
- 229930195733 hydrocarbon Natural products 0.000 abstract 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract 2
- 150000001408 amides Chemical class 0.000 abstract 1
- 150000001728 carbonyl compounds Chemical class 0.000 abstract 1
- 150000003949 imides Chemical class 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 20
- 239000000543 intermediate Substances 0.000 description 18
- 238000000354 decomposition reaction Methods 0.000 description 14
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 11
- 150000008065 acid anhydrides Chemical class 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000007127 saponification reaction Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000002199 base oil Substances 0.000 description 5
- 239000010687 lubricating oil Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 229920001083 polybutene Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 150000007520 diprotic acids Chemical group 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000010710 diesel engine oil Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010711 gasoline engine oil Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Lubricants (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
本发明是关于丁二酰亚胺无灰分散剂及其制备方法。本发明所说的无灰分散剂主要特征是：聚异丁烯分子上丁二酸(酐)的取代度为1.3～2.0、最终产物的羰基数与多烯多胺的摩尔比为4～7∶1。该无灰分散剂的制备方法是：将具有相同或两种不同分子量的烃基酰化剂与多烯多胺进行反应制得烃基酰胺和酰亚胺的混合物，再与1～3种具有交联作用的、含羰基化合物的后反应试剂反应即得，后反应试剂采取分步加入方式。The invention relates to a succinimide ashless dispersant and a preparation method thereof. The main features of the ashless dispersant in the present invention are: the degree of substitution of succinic acid (anhydride) on the polyisobutylene molecule is 1.3-2.0, and the molar ratio of the carbonyl number of the final product to the polyene polyamine is 4-7:1. The preparation method of the ashless dispersant is: react the hydrocarbon-based acylating agent with the same or two different molecular weights with polyene polyamines to prepare a mixture of hydrocarbon-based amides and imides, and then cross-link with 1 to 3 kinds of The post-reaction reagents containing carbonyl compounds can be obtained by reaction, and the post-reaction reagents are added step by step.
本发明所说的无灰分散剂不仅具有较高的氮含量和良好的低温分散性，而且热氧化稳定性好，热分解温度高。The ashless dispersant of the present invention not only has relatively high nitrogen content and good low-temperature dispersibility, but also has good thermal oxidation stability and high thermal decomposition temperature.
Description
The invention belongs to the lubricating oil additive field, exactly is about Ashless butyl diimide dispersant and preparation method thereof.
The succimide dispersion agent just begins a large amount of uses the sixties, it is the at present most widely used general and maximum a kind of dispersion agent of usage quantity, its preparation method is: earlier by about about 1000 polyisobutene of molecular weight and maleic anhydride reaction, make the polyisobutenyl maleic anhydride, and then with the reaction of the polyamines polyene of different ratios, make single, double and poly isobutenyl succimide.Mono butonediimide has the good low-temperature dispersiveness, is used in the following diesel engine oil of gasoline engine oil and APICC level (Huang Wenxuan etc. " lubricating oil and fuel dope handbook " P, 25) more.USP5062980 discloses a kind of multistage trapezoid succimide lubricant additive, and the used afterreaction reagent of this patent is polyprotonic acid (as hexanodioic acid and alcohol acid, as oxyacetic acid).USP4234435 discloses a kind of lubricating oil additive, this additive is by polybutene diacid (acid anhydride) and polyamines polyene or polyol reaction, and then make with one or more afterreaction reagent reacts, said afterreaction reagent comprises epoxy compounds, episulfide compounds or boric acid and terephthalic acid, the substitution value that this patent has been mentioned Succinic Acid (acid anhydride) on the polybutene molecule is at least 1.3, but the adding mode of not mentioned afterreaction reagent is not controlled the carbonyl number of final product and the mol ratio of polyamines polyene yet.
Though above-mentioned each piece prior art has been used the afterreaction technology to some extent, improved the dispersive ability and the anti-rubber swelling ability of succimide type dispersion agent, do not mention and improve the thermo-oxidative stability problem.More do not mention and to satisfy low temperature dispersity and thermo-oxidative stability problem simultaneously.Usually have only and satisfy high nitrogen content and just have good low temperature dispersity, as mono butonediimide, its nitrogen content height, low temperature dispersity is better, but thermo-oxidative stability is relatively poor, and many succimides, have good thermo-oxidative stability, but its nitrogen content is low, low temperature dispersity is also undesirable.
The purpose of this invention is to provide and a kind ofly not only have higher nitrogen content and good low temperature dispersity, and have the improved Ashless butyl diimide dispersant of good thermo-oxidative stability.
Another object of the present invention provides a kind of preparation method of improved Ashless butyl diimide dispersant.
The present invention realizes by following proposal: the alkyl acylating agent and the polyamines polyene reaction that will have identical or two kinds of different molecular weights make hydrocarbyl amide and imido mixture; make ashless dispersant of the present invention with 1～3 kind of afterreaction reagent react again with carbonyl containing compound of crosslinked action; the substitution value that the mode that afterreaction reagent adopts substep to add, gained Ashless butyl diimide dispersant have a Succinic Acid on the polyisobutene molecule (acid anhydride) is 1.3～2.0, the mol ratio of the carbonyl number of the finished product and polyamines polyene is characteristics such as 4～7: 1.
Molecular weight by changing polyisobutene, can obtain two kinds of different ashless dispersant products.
First kind of ashless dispersant, its principal character is:
(1) the polyisobutene number-average molecular weight M in the polyisobutene acylating agent
n=1500～2500, molecular weight distribution M
w/ M
n=2.0～7.0, M wherein
wBe weight-average molecular weight;
(2) number that the substitution value of Succinic Acid (acid anhydride) is 1.3～2.0 on the polyisobutene molecule, substitution value is represented Succinic Acid (acid anhydride) on each polyisobutene molecule;
(3) mol ratio of the carbonyl number of final product and polyamines polyene is 4～7: 1;
(4) wave number of the ft-ir characteristic absorption peak of this dispersion agent is 1643cm
-1
Second kind of ashless dispersant, its principal character is:
(1) polyisobutene of two kinds of different molecular weights is arranged in the polyisobutene acylating agent,
M
n1＝1500～2500，M
w1/M
n1＝2.0～7.0，
M
n2＝50-1000，M
w2/M
n2＝2.0～3.0；
M
N1, M
W1, and M
N2, M
W2Number-average molecular weight and the weight-average molecular weight of representing two kinds of polyisobutene respectively;
(2) substitution value of Succinic Acid (acid anhydride) is 1.3～2.0 on the polyisobutene molecule;
(3) mol ratio of the carbonyl number of the finished product and polyamines polyene is 4～7: 1;
(4) wave number of the ft-ir characteristic absorption peak of this dispersion agent is 1643cm
-1
The preparation method's of the said ashless dispersant of the present invention principal feature is that afterreaction reagent is taked substep adding mode, and its preparation process is as follows:
(1) will have alkyl acylating agents identical or two kinds of different molecular weights
(I), in the presence of reaction medium, at N
2Gas shiled
Down, respectively with polyamines polyene H
2N (CH
2)
n[NH (CH
2)
n]
m(II) 100～250 ℃ preferably 100～200 ℃ the reaction 2～10 hours, generate intermediate product (hydrocarbyl amide and imido mixture), the carbonyl number in the acylating agent and the mol ratio of polyamines polyene are 3.6～5.5: 1, the weight ratio of I and reaction medium is 0.5～1.5: 1, R is a polyisobutene in the I formula, X=1.3～2.0, is substitution value; N=2,3 in the II formula; M=1～4;
Said reaction medium is selected from a kind of in toluene, dimethylbenzene, the mineral oil, and when using the alkyl acylating agent of different molecular weight, two kinds of acylating agents must react with polyamines polyene respectively.
(2) the afterreaction reagent (III) of the intermediate product that step (1) is made and 1～3 kind of carbonyl containing compound with crosslinked action is at 100～250 ℃, preferably 130～200 ℃, under nitrogen protection, reacted 4～8 hours, afterreaction reagent is taked substep adding mode, the add-on of afterreaction reagent is controlled at that the mol ratio of carbonyl number and polyamines polyene is 4～7: 1 in the final product, III is selected from diprotic acid, hydrocarbyl substituted dicarboxylic acid or alkyl to replace one of polyprotonic acid or its mixture, and said diprotic acid is Succinic Acid (acid anhydride) or toxilic acid (acid anhydride); Said hydrocarbyl substituted dicarboxylic acid is polyisobutenyl Succinic Acid (acid anhydride), the number-average molecular weight M of polyisobutene
n=500～1000; Said alkyl replaces polyprotonic acid and has following structure:
In IV, the V formula, R
1Be polybutene, its number-average molecular weight M
n=500～1000, Y=1.3～2.0 are substitution value.
Because the said acylating agent of the present invention is the polyisobutene Succinic Acid (acid anhydride) with high substitution value; thereby the intermediates that step (1) makes are different from the intermediates that use general acylating agent to make; show that mainly intermediates of the present invention have higher dispersive ability and tackifying ability; again owing to adopt substep to add the mode of afterreaction reagent with crosslinked action; thereby further improved the dispersive ability of product, tackifying ability and thermo-oxidative stability.
The ashless dispersant that the present invention makes is a kind of hydrocarbyl amide and imido mixture of alkyl with multi-ladder structure, its flowability is very good, this also is because afterreaction reagent is to adopt due to the substep adding mode, once add afterreaction reagent, be unfavorable for the formation of hierarchic structure, but a kind of reticulated structure, it is mobile poor.
The Ashless butyl diimide dispersant that the present invention makes is compared with conventional Ashless butyl diimide dispersant.Not only have higher nitrogen content and good low temperature dispersity, and thermo-oxidative stability is good, the heat decomposition temperature height.
The following examples will the invention will be further described.
The analytical procedure of every index and method of calculation in the example of the present invention:
1. saponification value analytical procedure: SY2604-77.
2. analysis of nitrogen content method: SH/T0224.
3. molecular weight analyse method (M
n, M
w, and M
w/ M
n): SH/T0108-92.
4. lubricating oil additive initial decomposition temperature: test (DSC method) with difference formula scanning calorimeter.
5. spot test: by the dispersive ability of spot test explanation lubricating oil additive.Make dispersed substance with carbon black, launch on filter paper at 50 ℃, measure the ratio of diffusion circle and scraper ring then, ratio is bigger, the low temperature dispersive ability is described better.
M
n-polyisobutene number-average molecular weight.
Example 1 adds 60 gram polyisobutylene butanedioic anhydrides (according to the described method preparation of USP4234435, polyisobutenyl number-average molecular weight M in there-necked flask
n=1500, M
w/ M
n=7.0; 106 milligrams of KOH/ grams of saponification value; X=1.6) and 60 the gram 150SN base oils (Dalian Petrochemical Industry Company); being heated to 100 ℃ stirs; add 5.45 gram tetraethylene pentamine (Japanese import packing; Shanghai reagent company supply station), under nitrogen protection, is warming up to 170 ℃ of reactions 5 hours, makes intermediates A
1, the carbonyl number of these intermediates and tetraethylene pentamine mol ratio are 4: 1.
Get 80 gram A
1With 0.4 gram maleic anhydride (technical pure.Jing He chemical plant, Tianjin) react in 150 ℃ under nitrogen protection, maleic anhydride divided in 3 hours and adds for three times, and add maleic anhydride is 1/3 of total amount at every turn, and total coreaction 6 hours makes product P A of the present invention
1, in this product, the mol ratio of carbonyl number and tetraethylene pentamine is 4.5: 1, its initial decomposition temperature and low temperature dispersity can see Table 1.
Example 2
In there-necked flask, add 70 gram polyisobutenyl succinic anhydride (M
n=2300, M
w/ M
n=2.8, saponification value=61 milligram KOH/ restrains, and X=1.3) with 70 grams, 150 SN base oils, under agitation is heated to 130 ℃, adds 2.7 gram tetraethylene pentamine then and be warming up to 170 ℃ of reactions 5 hours under nitrogen protection, gets intermediates A
2, the carbonyl number of these intermediates and tetraethylene pentamine mol ratio are 5.3: 1.Get 110 gram A
2React in 150 ℃ under nitrogen protection with 0.7 gram maleic anhydride, maleic anhydride divides and adds for three times, and coreaction 6 hours makes product P A of the present invention
2, the carbonyl number of this product and the mol ratio of tetraethylene pentamine are 6.8: 1, its initial decomposition temperature and low temperature dispersity can see Table 1.
Example 3
Prepare intermediates A according to USP 4234435 described methods
3
In there-necked flask, add 161 gram polyisobutylene butanedioic anhydride (M
n=2000, M
w/ M
n=2.0, saponification value=83 milligram KOH/ gram, X=1.6) and 161 grams, 150 SN base oils, postheating to 150 ℃ stirs, and adds 10.2 gram tetraethylene pentamine again, is warming up to 170 ℃ of reactions 5 hours under nitrogen protection, intermediates A
3., its carbonyl number and tetraethylene pentamine mol ratio are 4.4: 1.Get 116 gram A
3React in 150 ℃ under nitrogen protection with 1.10 gram maleic anhydrides, maleic anhydride divided in 3 hours and adds for three times, and always coreaction is 6 hours, makes product P A of the present invention
3, the carbonyl number of this product and the mol ratio of tetraethylene pentamine are 5.3: 1, its initial decomposition temperature and low temperature dispersity can see Table 1.
Comparative example 1
Prepare contrast product PA according to USP 4234435 described methods
4
Get 116 gram A
3With 6.4 the gram terephthalic acids (commercially available, chemical pure) be blended in be heated under the nitrogen protection 150-160 ℃ the reaction 3 hours, make contrast product PA
4, its initial decomposition temperature and low temperature dispersity can see Table 1.
Example 4
In there-necked flask, with 60 gram polyisobutylene butanedioic anhydride (M
n=1000, saponification value=139.5 milligram KOH/ gram X=1.4) mixes stirring with 60 grams, 150 SN base oils, is heated to 140 ℃, adds 7.0 gram tetraethylene pentamine subsequently, is warming up to 170 ℃ and reacted 5 hours under nitrogen protection, makes intermediates B
1, its carbonyl number and tetraethylene pentamine mol ratio are 4: 1.
In there-necked flask, add 6300 gram polyisobutenyl succinic anhydride (M
n=2000, M
w/ M
n=2.0, saponification value=101 milligram KOH/ restrains, and X=2.0) with 6300 gram 150SN base oils, under agitation mixes, and is heated to 150 ℃, adds 589.4 gram tetraethylene pentamine subsequently, is warming up to 170 ℃ of reactions 5 hours under nitrogen protection, gets intermediates A
4, its carbonyl number and tetraethylene pentamine mol ratio are 3.6: 1.
With intermediates B
1, A
4Respectively getting 50 grams mixes; and be heated to 150 ℃, and under nitrogen protection, in 3 hours, divide then to add three kinds of afterreaction reagent three times, add maleic anhydride 0.6 gram for the first time; (Jinzhou Petrochemical Co. produces, M to add for the second time 6.6 gram polyisobutylene butanedioic anhydrides
n=1000, X=1), add the many Succinic anhydried (M of 5.6 gram polyisobutene for the third time
n=1000, saponification value=147 milligram KOH/ gram X=1.5), reacts on 150 ℃ and carries out, and coreaction 6 hours makes product P A of the present invention
5, the carbonyl number of this product and tetraethylene pentamine mol ratio are 5.3: 1, its initial decomposition temperature and low temperature dispersity can see Table 1.
As can be seen from Table 1:
(1) ashless dispersant of the present invention is compared with conventional Ashless butyl diimide dispersant, not only have higher nitrogen content and good low temperature dispersity energy, and thermo-oxidative stability is fine, and the heat decomposition temperature height is as ashless dispersant PA of the present invention
1, PA
2, PA
3, PA
5, not only its initial decomposition temperature all be higher than 290 ℃ but also low temperature dispersity can be good, nitrogen content is also higher.And commercially available succimide L
61, though the dispersed and higher nitrogen content of good low-temperature is arranged, this product thermo-oxidative stability is poor, and initial decomposition temperature has only 282 ℃, commercially available succimide product L
62Though, have good thermo-oxidative stability, its initial decomposition temperature reaches 294 ℃, low temperature dispersity also can, its nitrogen content is low, has only 0.85%.
(2) alkyl acylating agent and the polyamines polyene reaction by two kinds of different molecular weights makes intermediates (A
4+ B
1), the dispersion agent PA of the present invention that makes with three kinds of afterreaction reagent reacts again
5Though, the low temperature dispersity of this product and nitrogen content and product A in the middle of it
4Difference is little, but its initial decomposition temperature improves 10 ℃ nearly.
(3) kind of afterreaction reagent and adding mode thereof are also extremely important, as dispersion agent PA of the present invention
3With contrast product PA
4Though all be to use same intermediates A
3(preparing), but PA of the present invention according to USP 4234435 described methods
3Used afterreaction reagent is maleic anhydride, and is to adopt substep adding mode, Zhi Bei PA thus
3Though low temperature dispersity and intermediates A
3It is little to compare difference, but its thermo-oxidative stability obviously improves, and initial decomposition temperature is brought up to 290 ℃ by 288 ℃.Nitrogen content also increases, and brings up to 1.18% by 1.08%.And according to the PA of the described method of USP4234435 preparation
4, its thermo-oxidative stability, low temperature dispersity and nitrogen content and intermediates A
3Compare, do not have notable difference.
In order further to determine the textural difference of ashless dispersant of the present invention and conventional Ashless butyl diimide dispersant, use the U.S. MaGna-750 of NicoLet company type infrared spectrometer to sample P A of the present invention
3, intermediates A
3And commercially available prod L
62Carried out examination of infrared spectrum, test result is seen Fig. 1-3.
Fig. 1 is PA of the present invention
3Infrared spectrogram, Fig. 2 is intermediates A
3Infrared spectrogram, Fig. 3 is commercially available prod L
62Infrared spectrogram.
Can be found out by Fig. 1-3: product P A of the present invention3At 1643cm-1There is the characteristic absorption peak of the last one position, intermediate products A3There is not this characteristic absorption peak, commercially available prod L62Characteristic absorption peak be bimodal, 1643 and 1604cm-1The position.
Table 1
| Example number | Sample number into spectrum | Initial decomposition temperature (℃) | Spot | Nitrogen content (%) |
| 1 | PA 1 | 290 | 53 | 1.54 |
| 2 | PA 2 | 290 | 50 | 1.05 |
| 3 | PA 3 | 290 | 52 | 1.18 |
| Comparative example 1 | PA 4 | 288 | 50 | 1.06 |
| 4 | PA 5 | 292 | 49 | 1.58 |
| A 3 | 288 | 52 | 1.08 | |
| A 4 | 283 | 51 | 1.59 | |
| Commercially available L61 | 282 | 52 | 1.05 | |
| Commercially available L62 | 294 | 49 | 0.85 |
Claims (7)
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|---|---|---|---|
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|---|---|---|---|
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| CN1035331C true CN1035331C (en) | 1997-07-02 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103666645B (en) * | 2012-09-26 | 2017-05-24 | 中国石油化工股份有限公司 | Ashless dispersing agent, preparation method thereof and lubricating oil composite |
| CN104927983B (en) * | 2014-03-20 | 2017-12-22 | 中国石油化工股份有限公司 | Emulsion cutting fluid composite |
| CN105985827B (en) * | 2015-02-27 | 2018-09-04 | 中国石油天然气股份有限公司 | Preparation method and application of ashless dispersant with soot dispersing performance |
| CN105985460B (en) * | 2015-02-27 | 2018-10-16 | 中国石油天然气股份有限公司 | Preparation method and application of high molecular weight ashless dispersant |
| CN111100301A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Novel lubricating oil dispersing agent, preparation method and application |
| CN113402638B (en) * | 2020-03-16 | 2022-09-27 | 中国石油化工股份有限公司 | Boron modified ashless dispersant, preparation method and application thereof |
| CN111690081A (en) * | 2020-06-23 | 2020-09-22 | 新乡市瑞丰新材料股份有限公司 | Preparation method of boronized high-molecular-weight ashless dispersant |
| CN111690143B (en) * | 2020-06-23 | 2022-08-05 | 新乡市瑞丰新材料股份有限公司 | Preparation method of high molecular weight high-nitrogen ashless dispersant |
| CN111676080A (en) * | 2020-06-23 | 2020-09-18 | 新乡市瑞丰新材料股份有限公司 | Preparation method of novel efficient soot dispersant |
| CN114058422B (en) * | 2020-08-04 | 2022-08-05 | 中国石油天然气股份有限公司 | Mannich ashless dispersant and preparation method thereof |
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| US4234435A (en) * | 1979-02-23 | 1980-11-18 | The Lubrizol Corporation | Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation |
| US5356550A (en) * | 1988-10-18 | 1994-10-18 | Bp Chemicals (Additives) Limited | Lubricating oil additives |
| US5062980A (en) * | 1989-10-30 | 1991-11-05 | Texaco Inc. | Polymeric step ladder polysuccinimide compositions suitable for lubricating oil dispersants and fuel additives |
| US5308523A (en) * | 1990-09-24 | 1994-05-03 | Texaco Inc. | VI improver, dispersant, and antioxidant additive and lubricating oil composition |
Also Published As
| Publication number | Publication date |
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| CN1126752A (en) | 1996-07-17 |
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