CA2205643A1 - Low chlorine polyalkylene substituted carboxylic acylating agent compositions and compounds derived therefrom - Google Patents

Abstract

Polyalkylene substituted carboxylic acylating agents which contain chlorine are synthesized by chlorine induced condensation of polyalkylenes and ~-.beta.
unsaturated carboxylic groups are treated with sulfur to reduce chlorine content of the carboxylic acylating agent.

Description

CA 0220~643 1997-0~-16 Case No. 2759 LOW CHLORINE POLYALKYLENE SUB~ lll U l~ CARBOXYLIC
ACYLATING AGENT COMPOSITIONS AND COMPOUNDS DERIVED
TIIEREFROM

FIELD OF INVENIION
This invention relates to the synthesis and use of low chloAne content polyalkylene subsfftuted carboxylic acylating agent compositions. The primary use of the compositions are to forrn reaction products with alcohols, polyamines, metals and the like, which products when used in minor amounts in lubricating fluids impart L~proved dispersing and viscosity properties to such fluids.
BACKGROIJND OF 1~ INVENTION
It is by now well-known that carboxylic acylating agents produced by polyalkylene reactions with carboxylic-cont~inil-g compounds when further reacted with (a) an amine having at least one H-Nc group; (b) an alcohol; (c) reactive metal or reactive metal compound and (d) a combination of any two or more of (a)-(c), the components of (d) being reacted sim~lt~neously or sequentially produce compositions having dispersing, fluidity or detergency properties or combinations thereof depending on the nature of the composition. In depth ~ cussion of these compositions, their properties and modes of prepa~aLion and post treatments are discussed in detail in U.S. Patents 4,234,435; 5,041,622; and 5,230,714 which are herein incorporated by reference in their elltirety, including references cited therein, for disclosure and examples and enablement related to this invention.
In the patents mentioned herein-above and references given therein, disclosure is made of reacting polyalkylenes with carboxylic-cont~ining groups in the presence of chlorine to obtain substituted acylating agents. For such reactions conducted in the presence of bromine and/or chlorine, halogen is incorporated into the substituted acylating agent. A method of producing a chlorine free substituted acylating agent is to use a high vinylidene polyalkylene to react with maleic anhydride under thermal . conditions without chlprine. High vinylidene -CA 0220~643 1997-0~-16 polybutylenes and substituted acylating agents deAved therefiom are described inU.S. Patents 4,152,499; 4,605,808; and 5,071,919 which are herein incorporated by reference. However, high vinylidene polyalkylenes are more expensive than polyalkylene such as polyisobutylene derived from acid catalyzed polymerization 5 of a C~-r~ffln~te of a cat cracker or ethylene plant butane/butene stream, so there is a conffn-led interest in using a chlorine-col~lAinill~ process to react polyalkylenes with maleic anhydrides to form polyalkylene substituted acylating compositions.

SI~MMARY OF Th~ rNVENTION
Polyalkylenes derived from C2-Cl6 olefins are reacted with unsaturated carboxylic acids or de-i~dlives thereof in the présence of chlorine to form chlorine-co..t~il-ill~ substituted carboxylic acylating agents. The chlorine-col-L~illingsubsfituted acylating agents are further reacted with el~ment~l sulfur at elevated tempe~al~rcs whereby the chlorine content in the substituted acylating agent is reduced.
A further aspect of this invention is that new compositions of matter, including polyalkylene phthalic anhydrides are formed. The substituted phthalic anhydrides having reduced chlorine content are thermally stable components of the sulfur treated substituted acylating agent.
Reaction products from sulfur treated substituted acylating agents contain sulfur and have an increased kin~m~tic viscosity at 100~C when compared to substituted acylating agents prior to sul~'u~i~alion.
DETAILED DESCRIPTION OF THE lNVENTION
In the present invention, a polyalkylene derived from a C2-Cl6 polyolefin is reacted in the presence of chlorine with a a-~ unsaturated mono or dicarboxylic acid or derivatives such as maleic anhydride or acrylic acids or esters to form chlorine-cont~ in~ polyalkylene substituted "carboxylic" acylating agents. Said di-carboxylic acylating agents are also known as succinic acylating agents. In general, this well known reaction is depicted in Formula I below for maleic anhydride.

CA 0220~643 1997-0~-16 O O
[~ ~Cl] R
o b Forrnula I
In the invention disclosed herein, R is preferably Mn 1~0-10,000 polyalkylene. R is more preferably low vinylidene polyisobutylenes which are commercially available.
S In the reaction labeled Formula I above maleic anhydride is depicted as the carboxylic agent to condense with the polyalkylene to give a substit~lted succinic compound.
It should be understood in the scope of this invention that maleic anhydride compounds are represe~ t~e of those compounds as such, but also represent a 10 class of acidic compounds depicted by Formula II

O O
X - C - CH= CH- C - X Formula II
which react with polyalkylenes under the influçnce of chlorine.
In Formula II what is required is that X and X' are the same or different 15 provided at least one of X and X' is such that the substituted acylating agent can function as carboxylic acylating agents. That is, at least one of X and X' must be such that the substituted acylating agent can ei~le~iîy alcohols, form amides oramine salts with amines or ammonia, form metal salts with reactive metals or basically reacting metal compounds, and otherwise function as a conventional 20 carboxylic acid acylating agents. Transesterification and transamidation reactions are considered, for purposes of this invention, as conventional acylating reactions.
Thus, X and/or X is usually --OH, --O, --hydrocarbyl, --Cl, and together X and X' can be--O so as to form the anhydride. The specific identity of any X or X' group which is not one of the above is not critical so long as its 25 presence does not prevent the rem~ininE group from entering into acylation reactions. Preferably, however, X and X are each such that both carboxyl functions ofthe succinic group (i.e., both O O
--C--X and--C--X ) can enter into acylation reactions. The prefel~ed compounds as depicted by Forrnula II are maleic acid, maleic anhydride and ~ ures thereof. However, in the claims appended hereto, maleic acid and anhydride represel1t these chemicals as 5 such, but also all other applicable compounds which have been described hereinabove in connection with Formula II.
It must also be understood that the maleic term used above for compounds depicted by Formula II and which are described above also is used herein to ll describe compounds of Figure II in which one X--C group is replaced by a 10 hydrogen or hydrocarbyl group. Such compounds are a-,~ unsaturated monocarboxylic acids or ester such as acrylic acid. For a definition of hydrocarbyl, see U.S. Patent 5,354,485 which is incorporated herein by referencefor disclosure of hydrocarbyl groups.
The reaction depicted in Formula I shows chlorine as being a part of the 15 reaction. As is well known in the art, the polyalkylene substituent may be chlorinated before being reacted with the maleic anhydride. The alkylation reaction may also be run by mixing the polyalkylene and maleic component and adding chloAne to the mixture. The important point is that the prefelled method for forming the substituted acylating agent from a-~ unsaturated acids and 20 anhydrides and polyalkylenes with low vinylidene content is to use chlorine in the reaction whereby some chlorine is retained in the substituted acylating agent.
Methods of prepaling the chlorine-cont~ining substituted succinic acylating agents also identified herein as chlorine cont~ining substituted carboxylic acylating agents are given in U.S. Patent 5,489,390 which is hereby incorporated herein by25 reference in its enlirely. As pointed out in the '390 patent, several methods may be used to prepare the chlorinated succinic acylating agent.
The methods involve the two-step process as described in U.S. Patent 3,219,666. In this patent, which is incorporated herein by reference the CA 0220~643 1997-0~-16 polyalkylene is first reacted with chlorine and the chlorinated polyalkylene is reacted with maleic anhydride.
Another method of producing the s-lccinic acylating agent is described in U.S. Patent 3,912,764 which is herein incorporated by reference. In this method,S the polyalkylene is condensed with maleic anhydride under thermal conditions to produce "direct alkylation". Following direct alkylation chlorine is added to the reaction llfi~lure to promote reaction of unreacted maleic anhydride.
U.S. Patent 3,231,587, which is incorproated herein by reference described the "one step" process for making succinic acylating agents. In this process, the 10 polyalkylene and maleic anhydride are mixed then cont~cted with chlorine.
The novel class of substitllted sucçinic acylating agents of this invention are those which can be characterized by the presence within their structure of two groups or moieties. The first group or moiety is refelred to herein, for convenience, as the "substitue-nt group(s)" and is derived from a polyalkylene. The 15 polyalkylene from which the substituted groups are derived is characterized by a Mn (number average molecular weight) value of from 140 to about 10,000 and a Mw/Mn value of about 1.5 to about 4. More preferably, the polyalkylene may be a Mn 1000-2000 polyisobutylene.
The second group or moiety is referred to herein as the "succinic group(s)"
20 or "carboxylic groups", both of which names are used herein. The succinic groups are those groups characterized by the structure in Formulas I and II and have been diccucsed herein above.
The substit~lted succinic acylating agents are characterized by the presence within their structure of at least 1.0 succinic groups (that is, groups corresponding 25 to Formulas I and II) for each equivalent weight of substituent groups. For purposes of this invention, the number of equivalent weights of substituent groups is deemed to be the number corresponding to the quotient obtained by dividing the Mn value of the polyalkylene from which the substituent is derived into the total weight of the substituent groups present in the substituted succinic acylating 30 agents. Thus, if a substituted succinic acylating agent is characterized by a total weight of substituent group of 40,000 and the Mn value for the polyalkene from CA 0220~643 1997-05-16 which the substit~lçnt groups are derived is 2000, then that substituted succinic acylating agent is characterized by a total of 20 (40,000/2000=20) equivalent weights of subsfituçnt groups. Therefore,:that particular succinic acylating agent must also be characterized by the presence within its structure of at least 20 5 succinic groups to meet one of the requirements of the novel succinic acylating agents of this invention.
The chlorine content of the substituted acylating agents of this invention will normally run to less than one percent by weight based on the weight of the acylating agent but the value can range as high as 2-3 weight percent and as low as 10 0.5 weight percent or less depending on the specific reaction conditions. Lowchlorine is prertlled in products in which said acylating agents or compounds derived thererrol-l are included.
In one aspect of the invention described herein, the reaction products of a polyalkylene with maleic anhydride is treated with sulfur at elevated temperatures 15 to reduce the chlorine content of the substituted acylating agent. In this manner, the chlorine content of the reaction products shown in For nula I can be reducedby at least 50% or even up to 75% or even more depending on the given reaction products and the process used to reduce chlorine.
Formula I symbolizes the well-known reaction of a polyalkylene and maleic 20 anhydride in the presence of chlorine to form a substituted acylating agent with a given chlorine content. However, by use of carbon 13C nuclear magnetic resonance spectroscopy, a more accurate depiction of the reaction products is formed.
By use of 13C N~, it has been found that the chlorine cont~ining 25 processes for condensing a polyalkylene with maleic anhydride results in products as shown below in Formula III as well as the "normal" reaction product substituted acylating agents shown in Pormula I.

CA 0220~643 1997-0~-16 O ~ ~
R1~lo R~ l' Forrnula lll R~ ,0 R1 =CH3, H
~ o R = polyalkylene Polyalkylene substituted tetrahydrophthalic anhydrides and Polyalkylene subst~ ted rlicuccinic carboxylic acylating agents The chlorine cont~ining substituted tetrahydrophthalic anhydrides and substituted disuccinic acylating agent from Formula III form significant amounts of the reaction products. The di~uccinic carboxylic acylating agent is a tetracarboxylic acid or anhydride. It is thought that these products are formed by Diels-Alder con-lenc~tion of a "diene" derived from the polyalkylene substituent15 and an "ene" derived from the maleic anhydride substituent The reaction products, of course, contain chlorine. In the chlorine-cont~il-ing reaction products, from Formula m, the substituted tetrahydrophthalic acylating agent maybe present in an amount of up to 65 tetrahydrophthalic cont~ining units per 100 s~lbstituent groups.; That is, of the polyalkylene groups being con~çn~ed with 20 maleic anhydride to form a polyalkylene substitllted maleic anhydAde, up to 65 per 100 polyalkylene groups may contain the tetrahydrophthalic substituent group.
The disuccinic component of the reaction mi~l.lre may contain up to 30 groups per 100 polyalkylene groups in the reaction products. The disuccan reaction product has at least two groups derived from the ac-~ unsaturated moiety per polyalkylene 25 group.

CA 0220~643 1997-0~-16 NMR Experiments 13C Nuclear Magnetic Resonance (N~) spectra were recorded on either Bruker AMX 500 (125.6 MHz) or Bruker ARX 300 (75.4 MHz) instruments.
Samples were dissolved in deuterated chloroform (CDCl3) with typical 5 concenllalions of 1.5-2.0 g/5mL. Spectra were referenced to internal tetramethylsilane (TMS) at 0.0 ppm.
lH N~ spectra were recorded on either Bruker AMX 500 (500 Mhz) or Bruker ARX 300 (300 Mhz) insl~ nts Samples were dissolved in CDCI3 with typical concentiations of 1.5-2.0 g/SmL. Spectra were referenced to internal TMS10 atO.Oppm.
Figure 1 demonstrates spectral characteristics of reaction products formed by reacting sulfur with the reaction products of Formulas I and III. Trace 1(A) shows the l3C N~ spectra for the carboxy region for the reaction products of a Mn 1000 polyisobutylene with maleic anhydride in the presence of chlorine. The 15 trace for the products from reacting sulfur with the products of l(A) at 210~C is shown in l(B). The tracing at 210~C, 1(13), shows nearly complete conversion of the tetrahydrophthalic component to the arom~ti7ed phthalic component.
Conversion at 190~C was not complete. While any amount of sulfur may be employed to dechlorinate and dehydrogenate the tetrahydrophthalic compound to 20 form its aro.n~l;,ed counterpart, it has been found that at least two equivalents or more of sulfur per equivalent of tetrahydrophthalic component give the highest conversion of tetrahydro component to the aromatic component with liberation of two equivalents of H2S. This is the prererred sulfur usage for arom~ti~tion.
The time used in the reactions shown in FIGURE 1 was 4.5 hours but up to 25 12 hours or longer may be prere.red. The sulfurization of the substituted tetrahydrophthalic component of the reaction products leads to the phthalic compound through dehydrogenation. The disuccinic component of the reaction products is largely unaffected. Thus in calcul~ting sulfur charge for the dehydrogenation reaction, only the amount of the substituted tetrahydrophthalic 30 component of the reaction products should be considered.

CA 0220~643 1997-0~-16 The highest polyalkylene substituted phthalic anhydride yields which were obtained resulted from sulfurization of a succan prepared by the Two-Step reaction of Mn 1000 polyisobutylene. This finding can be rationalized by the observation that the Two-Step Process yields greater amounts of 5 tetrahydrophathalic anhydrides than our One-Step Process. The Two-SteptSulfurization sequence is described below.
Two-Step Reaction of Mn 1000 Polyisobutylene A l~fi~lure of Mn 1000 polyisobutylene in 20% (m/m) cyclohexane is reacted with 1.1 equivalents of chlorine at 65~C. The cyclohexane is removed by 10 rli~till~tion and the resulting polyisobutylene chloride is reacted with 1.1 equivalents of maleic anhydride at 200~C for 24 hrs. Excess/unreacted maleic anhydride is removed by vacuum sllippil1g.
Product Analyticals:

% Unreacted 12.6 % Unreacted malan 0.155 AgNO3 % chlorine 0.297 Sulfurization of the Two-Step Product The product from above is reacted with 1 sulfur/CO (or 2 sulfur/anhydride) at 210~C for 6 hours. 13C NMR indicates that 72% ofthe product carbonyl groups are attributable to substituted phthalic anhydride groups as compared to about 50% for sulfur treatment of products from the one-step reaction of polyisobutylene with maleic anhydride described later herein in Example 1.
Product Analyticals:
SAP 96. 8 AgNO3 % chlorine 0.032 % sulfur 0.97 In addition to the formation of the phthalic moiety during the reaction of sulfur with reaction products formed by the chlorine catalyzed condensation of polyalkylenes with maleic anhydrides, products of increased viscosity are also CA 0220~643 1997-0~-16 obtained. This, of course, is in addition to a lowering of the chlorine content caused by sulfur tre~tm~nt of the chlorine col-t~il-in~ substituted acylating agents.
Sulfur tre~tm~nt causes sulfur to be incorporated into the sulfurized substituted acylating agents in the amount as high as 2-3 weight percent. It is thought that5 sulfur coupling or crosslinking may be the cause of the viscosity value increase.
While it has been found as part of this invention that sulfur at elevated te"lpe-alures reduces the chloAne content of the substituted acylating agent reaction products, it has also been found that given treatm~nts of the reaction products in conjunction with sulfur can reduce the chloAne content even further.10 These tre~tments include reacting the chlorinated reaction products with iodine pAor to reacting with sulfur. Iodine treatment of chloAne co~ ning substituted acylating agents in combination with Lewis acid to reduce chloAne is descAbed inU.S. Patent 5,489,390 which is herein incorporated by reference. The treatments of the instant invention to reduce chlorine also include reacting the chlorinated 15 reaction products with a Lewis acid or mineral acid and sulfur in any order. Also included are reactions in which the chlorinated reaction products are treated with iodine and then with the Ir,ixl~re of sulfur and a Lewis acid or mineral a~;id. The prefe"ed Lewis acid for use in the scope of this invention is zinc acetate. A wide vaAety of Lewis acids are useful in the process of the present invention. Various 20 compounds of zinc, magnesium, calcium, iron, copper, boron, ~lll...il-ll..~, tin and tit~nillm are useful Lewis acids. Examples of zinc compounds useful as well as Lewis acids in the process of the present invention includes zinc ~cet~te, zinc oleate, zinc bromide, zinc chloAde, zinc iodide, zinc oxide and zinc sulfate.
Examples of iron compounds include ferrous acet~te, ferric ~cet~te, ferrous 25 bromide, ferric bromide, ferrous chloride, ferric chloride, ferrous iodide and ferric iodide. Examples of magnesium compounds include m~gnesium iodide and magnesium sulfate. Calcium compounds such as calcium iodide and calcium sulfate are useful. Examples of copper compounds include cuprous oxide, curprous chloAde cupAc ~cet~te, cupAc bromide, cupric chloAde, cupAc iodide, 30 cupAc oxide, cupAc sulfate and cupAc sulfide. Examples of boron compounds include boron tAfluoride, boron tAchloride, boron tribromide, tAmethylborane, CA 0220~643 1997-0~-16 triethylborane, trimethylborate, triethylborate, triisopropylborate and tributylborate. Examples of ahlmin-lm compounds include trialkyl~ minl-m compounds such trimethylal~-mim-m, triethyl~ min~m and triisobutyl~lllminllm al~ alko-xides such as ~ i.. -..l isopropoxides, ~ll-...il~...~. sec-butoxides and S al.l.ni~ -- t-butoxides; ~ .. , halides such as al.. il-.. -. fluorides, ~Illmim~m chlorides and ~ll..,.in~..l, bromides; and all....i.-~,... oxide. Examples of tin compounds include the stannous and stannic forms of tin acet~te, tin bromide, tin chtoride, tin iodide and tin sulfate. Examples of ~ compounds include lit~ni~.. (IV) chloAde, I;t~nil..n (IV) isopropoxide, lit~ - (IV) isobutoxide and 10 ~;L~nilJ-t~ (IV) ethoxide and ~ ni~.", oxides. Any of the above Lewis acids may be converted to other Lewis acids under the procéss conditions. For example, zinc oxide may be con~e"ed to zinc chloride by reaction with chlorine or hydrogen chloAde preselll in the organochlorine compound, or the zinc oxide may be converted to zinc iodide by reaction with the source of iodine added to the 15 reaction n~xl~l-e. Lewis acids may also be formed in situ by adding to the reaction ~l~xlures~ metals such as m~gnesillm~ al~ zinc, etc. Other examples of Lewis acids which may be utilized include tetraethylenetetracarbo-xylate and tetracyanoethylene.
Mineral acids, other than hydriodic acid and hydrobromic acid which may 20 be utilized in the present invention include strong mineral acids such as sulfuric acid, nitAc acid, phosphoric acid, pyrophosphorus acid, etc. The acid also may be a strong organic acid such as organic acids having a pKa of less than about 2.
Examples of such acids include aliphatic and aromatic sulfonic acids such as methane sulfonic acid, trifluoromethyl sulfonic acid, benzene sulfonic acid, various 25 p-alkylbenzene sulfonic acids, p-toluene sulfonic acid, and naphthalene sulfonic acid; carboxylic acids such as cyclopropane-1,1-dicarboxylic acid, nitroacetic acid, dichloroacetic acid, maleic acid, oxalic acid, picric acid, trichloroacetic acid, trifluoroacetic acid, trihydrGxybenzoic acid; phenolic compounds such as trinitrophenol; and phosphonic acids such as phenyl phosphonic acid, methyl 30 phosphonic acid and trifluoromethyl phosphonic acid.

CA 0220~643 1997-0~-16 The various combination of reactions which will lead to a low chlorine substituted acylating agent under this invention are combinations of I. Sulfur treatm~nt of (A). chlorine cont~ining polyalkylene substituted carboxylic acylating agent;
(13). (A) treated with iodine;
(C). (A) treated with iodine and Lewis acid;
(D). (A) treated with iodine and mineral acids;
II. Sulfur and Lewis acid treatment of (A). chlorine containing polyalkylene substituted carboxylic acylating agent;
(B). (A) treated with iodine;
(C). (A) treated with iodine and Lewis acid;
(1)). (A) treated with iodine and mineral acid.
While elemental sulfur is the prefe~ed chemical to effect removal of chlorine from chlorine cont~ining substituted acylating agents, other types of sulfur cont~ining chemicals may be used. For instance, organic sulfur donors may be used. Thiuram disulfides are represented by tetramethylthiuram disulfide. Also dipentamethylene-thiulal" tetra and he~ulfides can be used to reduce chlorine.
20 Also of use are 2-(4-morpholinodithio) benzothiazole and 4,41 dithiobismorpholine. It will be recognized that sulfur as well as organic sulfurdonors mentioned above are vulc~ni7.ing agents used in the rubber industry but which are also useful in the present invention. Vulcani7ing agents are o~en usedwith accelerators and such accelerators may be useful to this invention also. For a 25 review of vulc~ni7.ing agents and accelerators, see Kirk-Othmer, Encyclopedia of Chemical Technolo~y, 3rd Ed. 1982 pp. 337 and forward which is incorporated herein by reference.
Table 1 gives analytical data for a chlorine cont~ining substituted acylating agent and for the acylating agent following various chemical treatments. The 30 acylating agent is prepared by reacting polyisobutylenes of Mn 1000 and Mn 2000 with maleic anhydride and chlorine in the "one step" process.

CA 0220~643 1997-0~-16 Example 1. Synthesis of substituted acylating agents and reaction with sulfilr (A) 1000 grams of a commercially available Mn 1000 polyisobutylene (1 mole) is mixed with 108 grams maleic anhydride (1.10 mole) and the mi,~lure heated to about 110~C with stirring. To the stirred ,nixl.ll~ over 6.5 hours is S added 100 grams chlorine (1.4 moles) gas under the surface of the reaction l~f~lure. The tcmpe.~lùrc is controlled between 110~C and 190~C. Nitrogen may be blown through the reaction ~fi~lur~ to remove excess chlorine and maleic anhydride.
(B) 1000 grams of a commercially available Mn 2000 polyisbutylene (O.Smole) is reacted with 108 grams maleic (1.1 mole) anhydride and 1.4 mole chlorine gas as above. The di~erence between preparations l(A) and lQ3) is that l(B) has a higher degree of s~lccin~tion than 1(A).
(C) The products of 1(A) and 1(B) above are heated at 210~C with sulfi~r under a nitrogen purge. Sulfilr in the reaction ~ lur~s is based on two 15 equivalents of sulfilr per equivalent of anhydride for chlorine reduction and dehydrogenation to form the phthalic component.
Table 1. Analytical Data for Treatment of Products from E~amples 1(A) and 1~) Item 1 2 3 4 Prep Number l(A) l(A) l(A) l(A) T~mell~ no sulfur 2 S/anhydride 2 Process -- 210~C, 4.5h 190~C, 4.5h S/anhydride210~C, 4.5h D445 100 Kin Vis (cSt)1280 1123 250 1900 D1522 ~/- Sulfur ns ns : .22 1.34 AgNO3 ~/O Cl 0.82 0.362 0.338 0.226 Item 5 6 7 8 Prep Number l(A) l(A) l(A) l(B) Tlea~,.le.. ~ 2 2.5 S/anhydride 2 S/anhydride 0.17 Process S/anhydride 210~C, 6h 205~C, 6h S/anhydride 210~C, 1500 g 210~C, 7.25h 6 hrs.
D445_100 Kin Vis 1750 1633 1700 --(cSt) D1522 % Sulfur 1.51 1.88 1.8 --AgNO3 % Cl 0.208 ~ 0.193 0.256 0.205 The notations used in the tables are as follows:
Prep Number - Product from Example l 5 S/anhydAde - equivalents of sulfur/equivalent of anhydride component D445 - 100~C kinematic viscosity based on cSt value D1552 - % sulfur in sample on a weight percent basis AgNO3 Cl % - % chlorine in sample on a weight percent basis 10 XRF Cl % - % chlorine in sample on a weight percent basis XRF I % - % iodine in sample on a weight percent basis The inrollllalion to be focused on in the Table 1 is that a greater than 50%
reduction of chlorine can be achieved in the chlorine-contA~ products with the greatest reduction in chlorine coming in Items 6, 5 and 4 respectively. These items 15 were treated with 0.10-2.S equivalents of sulfur per equivalent of anhydride component at 205~C - 210~C for 4.5-7.25 hours. However, depending on the chlorine content of the acylating agent and the amount of chlorine reduction sought, the sulfur content of the reaction mi~Lure may be widely varied.
Comparing item 6 with item 5, it can be seen that an increase in sulfur/anhydride 20 leads to lower Cl content of the reslllt~nt products. The sulfur content of the treated products ranged from about 1.3-3.2 weight percent based on the weight ofthe products with Item 3 being very high.
The 100~C kinematic viscosity of the substituted acylating agents ereated with sulfur at over 200~C with two equivalents of sulfur per equivalent of 25 anhydride shows a marked increase over the non-sulfurized starting materials.Dispersants made from these sulfurized substitutecl acylating agents should thus have viscosity improving as well as dispersant properties.
In addition to the reduction of chlorine content of polyalkylene substituted acylating agents by sulfur, other methods may be used to further reduce the 30 chlorine content. Such methods were summ~rized hereinabove using sulfur or CA 0220~643 1997-0~-16 sulfur and Lewis acid combined to treat various substituted acylating agents. The reaction products of Example 1. above may also be treated with iodine prior to tre~t...~ with sulfur, or F.Y~mple 1. products may be treated with sulfur and a Lewis acid cimlllt~neoll~ly~ or iodine treated products of Example 1. above may be 5 treated with sulfur and a Lewis acid siml~lt~neously or an iodine Lewis acid l~e~..f~l may be made prior to sulfur. The prefelled Lewis acid is zinc ar~
acetate ~2H20. The results of some of these treatments is given in Table 2.
Fx~mrle 2. Lewis acid, iodine and sulfur treatments of chlorine-cont~ ing substitute~ acylating agents.
(A.) Substituted chlorine-co.-l~ining acylating agents from Example 1.
were treated with sulfur as in Example 1.(C) and inclllded in the sulfur tre~tm~nt was 0.02 weight percent, based on the weight percent of the products from FY~mple 1., of zinc ~ acetate ~2H20.
~B.) Substituted chlorine-cont~ining acylating agents from Example 1.
were treated with iodine to reduce chlorine. In the iodine reaction, 1000 grams of the products of Example 1. were heated to 150~C and 2-5 grams iodine added.
The reaction l~ixl~lre is heated at about 150~C for two hours. After two hours, the temperature is raised to 205~C and the reaction ~lixl~re is nitrogen stripped under agitation until the halogen content is 1000 ppm or less (approxi",ately 24 hours).
The nitrogen flow is 40 SCFM.
(C.) The reaction products from 2(~3) above were treated with 0.02 weight percent zinc (II) acetate ~2H20 and sulfur for time periods of 3.5-6 hours at 205-210~C.
Table 2. Anal~rtical Data for Sulfurization of the Products of E~ample 1. in the Presence of zinc (II) acetate ~2E~0.
Item 1 2 3 Prep Numberl(A) l(A) l(A) Treatment 2 S/anhydride 2 S/anhydride Process 210~C, 4.5 h 210~C, 6 h 0 02% Zn(OAc)2 0.02% Zn(OAc)2 -Item (Cont'd) 1 2 3 TAN 60.1 55.57 54.35 D445 100~C 1280 1475.37 1441.78 Kinematic Visc (cSt) D1552 % S ns 1.34 1.37 A~N03 % Cl 0.82 0.139 0.132 The results presçntecl in Table 2 demonstrate a Lewis acid in conjunction with sulfilr reduce the chlorine content of the subst~ ted acylating agents evenfilrther than the Ire~nf ~t with sulfi~r alone as can be seen by a comparison ofItems 2 and 3 in Table 2 with Items 4 and 7 of Table 1. In another treatment to reduce chlorine, the reaction products from Examples l(A) and l(B) were first treated with 0.2-0.5 weight percent iodine to displace chlorine, and the iodine treated reaction products were then treated as in various ways with sulfilr and zinc acetate and combinations thereof.
Table 3. below gives analytical data for sulfilr treatment of the chlorine-reduced substit~lted acylating agent from Example 2.(B) where chlorine reductionis effected by iodine treatment.
Table 3. Analytical Data for Sulfurization of Iodine Treated Products of Example 2.(B).
Item 1 2 3 Prep # 2(B) 2(B) 2(B) T~aLIllent Process 1.8 S/anhydride 1.8 S/anhydride 210~C, 6 H 210~C, 6 H
--.AN 56.59 54.;6 55.17 ~~O Sulfur ns 0.9~ .02 ~445 100~C 463.7 11,5 002 Kinrm~t c Visc cSt XRF % - 0.0372 not det'd 0.0007 Ag~O3.~/O Cl 0.05 0.034 0.022 % lalogenred'n 61 74 .

CA 0220~643 1997-0~-16 As described hereinabove, it was found that sulfur tre~tm~nt of the reaction products of a polyalkylene with an a-,~ unsaturated compound in the presence of chlorine resulted in the dehydrogenation of polyalkylene substit~lted tetrahydrophthalic to give the substituted phthalic acylating agent. We have found 5 that a dehydrogenation reaction also occurs by reacting iodine with the tetrahydrophthalic compounds. The reaction conditions are given above in Table 3. The initial reaction products of the chlorine catalyzed polyalkylene - con-lçn~tion reaction with maleic anhydride result in products with little or no phthalic content. Following tre~tment with I2, up to 19 percent of the carbonyl 10 peaks in the 13C N~ are attributed to phthalic anhydride rings.
Table 4. gives analytical data for reduction of chlorine in an iodine treated chlorine-col-tAining substituted acylating agents by various treatments with zinc (II) acetate ~2H20, and sulfur combinations and sequences.
Table 4. AnalYtical Data for Treated With Combinations of Iodine~
Zn(OAc) 2H~O, and Sulfur.
Item 1 2 3 4 Prep # 1~) 1~) 1~) 1~) Initial I2, 6 h I2, 3.5 h I2, 3.5 h I2, Zn(II), 3.5 tre~tm~nt h Secondary none 0.2 S/CO, 3 h 0.2 S/CO, 0.2 S/CO, 3 h lle~ Zn(II), 3 h D445 100~C 4950 5400 4904 4520 Kin~m~tic Visc. cSt A~NO % CI 0.156 0.137 0.171 0.071 Cl 0.1585 0.1326 0.1128 0.0684 XRF P~o I 0.0243 0.0165 0.0238 0.0242 XRF lalogen 0.1828 0.1491 0.1366 0.0926 Examples shown in Table 4. start with an iodine-treated chlorine-cont~ining substituted acylating agent from Examples l(A) and l(B) which were treated with 20 iodine, zinc (II) acetate ~2H20 and sulfur in various combinations. The data demonstrates that a chlorine (halogen) reduction results.
In the examples and text above, several methods of analysis for various parameters are given. D445 and D1522 are ASTM standard tests for 100~C

CA 0220~643 1997-0~-16 kinematic viscosity in centistroke units and weight percent sulfur in a sample respectively. Tests identified as AgNO3 and XRF are for chlorine and chlorine and iodine respcclively. In test AgNO3 for chlorine, a sensitivity limit of about 200 ppm chlorine prevails. In this test, the chlorine-cont~ining sample is combusted5 with a Parr oxygen bomb. Following combustion, the residue is worked up with water which is diluted with an equal volume of isopropyl alcohol and one drop concentrated HNO3 and cooled to about 5~C. The cooled solution is titrated with N/100 AgNO3 standardized solution against a chloride specific electrode.
Test XRF is a wavelength dispersive x-ray fluorescçnce analysis for chlorine in the range of 0-0.75 mass percent and iodine in the range of 0-0.5 mass percent. In this test, a sample is placed in the x-ray beam and the intensity of the appropriate fluorescence lines of chlorine and iodine are measured. The concenll~ion of the elements are deterrnined from a calibration curve. An x-ray spectrometer such as an ARL-Eisons WDXRF 8410 equipped for soft x-ray detection is used in this test. The spectrometer must also include GEIII and LiF200 analyzing crystals for use in analyzing chlorine and iodine respectively.
Further in the tables above, TAN refers to total acid number and SAP to saponification number. These are values whose determinations are well known to those in the lubricant arts.
By the reaction of sulfur with the substituted succinic acylating agents or tetrahydrophthalic components the more thermally stable substituted phthalic component results. The therrnal stability of the sulfur treated material is exhibited by thermoglavhna~ic analysis (TGA) For TGA 10-20 mg. of samples were heated under N2 to about 700~C at a heat rate of 10~C/minute.
Under identical experimental conditions, the sulfur treated substituted acylating reaction products lost significantly less weight, over a wide temperature range, than the untreated reaction products. The significance of this result is that de.iva~ives ofthe substit~lted phthalic acylating agents, such as dispersants, esters, metal and amine salts and so on will also show greater thermal stability than those derived from the corresponding tetrahydro counter parts. This will result in more thermally stable lubricating and function fluids by virtue of the incorporation of CA 0220~643 1997-0~-16 more thermally stable components therein. It is reasoned that thermal stability for the sulrul;~ed acylating agents and derivatives thereof is greater because the phthalic co,..ponents are less susceptible to retro Diels-Alder reactions than their tetrahydro analogues.
As has been illustrated and described above, substit~lted carboxylic acylating agents with reduced chlorine content may be made through sulfurizationof chlorine-cont~ining acylating agent prepared by reaction of chlorine, polyalkylene component, and maleic acid and/or anhydride component.
In addition, the chlorine-col-t~ining sulrulizalion products contain new compositions of matter defined herein above as chlorine-co~ ining substituted phthalic co",polents, and chlorine-co~ inil~ bicylic or ~icucçinic components and, if sulrùu~alion is not carried to completion, chlorine-col-t~ ing substituted tetrahydrophthalic components.
The major use of the low chlorine substituted acylating agent reaction products of this invention is to react said products with other compounds to form new materials. Such materials are added to lubricating fluids to improve the desired qualities and properties of the lubricating fluids. As used herein, the term lubricating fluids comprises fluids for use as lubricants and greases and fluidswhich are functional and fluids which are both. Examples of lubricating fluids are engine oils, gear lubricants, manual tr~n.cmicsion fluids and the like.
A functional fluid is a term which encompasses a variety of fluids including but not limited to tractor fluids, automatic tr~ncmiccion fluids, manual tr~n.cmi.ccion fluids, hydraulic fluids, power steering fluids, fluids related to power train components and fluids which have the ability to act in various di~erent capacities.
The materials may also be used as additives to fuel compositions.
As used hereinafter, the term lubricating composition encompasses fluids for lubrication, greases, and fluids with functional properties as well as fuels. Also as used hereil a~ler, the low chlorine substituted carboxylic acylating agents which have been formed by sulfurizing the chlorine-cont~ining substituted carboxylic acylating agents formed by reacting a polyalkylene and maleic anhydride in the presence of chlorine will be identified as acylating agents.

CA 0220~643 1997-0~-16 The acylating agents of this invention have utility, in and of themselves, as additives for lubricant and fuel compositions in the same manner as the known high molecular weight carboxylic acid acylating agents of the prior art. For example,the acylating agents of this invention which are s~lcçinic acids, s~lccinic acidanhydrides, and lower alkyl esters of succinic acids can be used as fuel additives to reduce deposit formations when used in concenlra~ions of about 50 to about 1000 ppm in hydrocarbon-based fuels boiling subst~nti~lly in the range of 100~ to 750~
F. U.S. Pat. No. 3,346,354 is c,~,rcssly incorporated herein by reference for instructions for using the known high molecular weight carboxylic acid acylating10 agents since those instructions are applicable to the acylating agents of this invention. Similarly, U.S. Pat. No. 3,288,714 is e~pressly incorporated herein by reference for its teaÇl-ings of how to use known high molecular weight carboxylic acid acylating agents which are succinic anhydrides as additives in lubricant compositions where they function as dispersant/detergents since these teachings 15 are applicable to the acylating agents of this invention.
For the same reason, U.S. Pat. No. 3,714,042 is expressly incorporated herein by reference for its teaçtling.~ with respect to how to use the acylatingagents of this invention to treat overbased complexes. Thus, the acylating agents of this invention cont~ining succinic acid groups, succinic anhydride groups, and 20 succinic ester groups can be used to treat basic metal sulfonate complexes, sulfonatecarboxylate complexes, and carboxylate complexes in the same manner and according to the same procedure as described in U.S. Pat. No. 3,714,042 by replacing the high molecular weight carboxylic acid acylating agents discussed therein with the acylating agents of this invention on an equivalent weight basis.
Because the acylating agents of this invention have utility in and of themselves, beyond that of being intermediates for preparing other novel compositions, lubricant compositions and concentrates cont~ining the acylating agents, as mentioned hereinbefore and described more fully hereafter con~titllte a part of this invention.
The major compounds with which the low chlorine substit~lted acylating agents of this invention are reacted are those prese~ted in U.S. Patents 4,234,435, -5,041,622 and 5,230,714 which are incorporated herein by reference in their entirely.
The principle use of the acylating agents of this invention is as interme~i~tes in processes for preparing carboxylic derivative compositions 5 comprising reacting one or more acylating agents with a reactant selected from the group concicting of (a) amine characterized by the presence within its structure of at least one HN< group, (b) alcohol, (c) reactive metal or reactive metal compound, and (d) a combination of two or more of (a) through (c), the components of (d) being reacted with said acylating agents simult~neously or 10 sequentially in any order. Reaction conditions for condensing the chlorine cont~ substitl1ted acylating agents of this invention with compounds of (a)-(d) above are given in U.S. Patent 4,234,435 which has been incorporated herein by reference.
The amine, (that is, (a) above) characterized by the presence within its 15 structure of at least one HN< group can be a monoamine or polyamine compound.For purposes of this invention, hydrazine and substituted hydrazines cont~ining up to three substit~lçnts are includçd as amines suitable for prepaling carboxylic delivalive compositions. Mixtures of two or more amines can be used in the reaction with one or more acylating agents of this invention. Preferably, the amine 20 contains at least one primary amino group (i.e.,--~IH2) and more preferably the amine is a polyamine, especially a polya,lline conl~il-ing at least two HN< groups, either or both of which are primary or secondary amines The polyamines not only result in carboxylic acid dc~i~àli~e compositions which are usually more effective as dispersant/detergent additives, relative to derivative compositions derived from 25 monoamines, but these prerelled polyamines result in carboxylic derivative compositions which exhibit more pronounced viscosity improving properties.
Alcohols which can be used as (b) include the monohydric and polyhydric alcohols. Again, the polyhydric alcohols are prefelled since they usually result in carboxylic delivalive compositions which are more effective dispersant/detergents 30 relative to carboxylic derivative compositions derived from monohydric alcohols.
Further, the carboxylic acid derivative compositions derived from polyhydric -CA 0220~643 1997-0~-16 alcohols exhibit very pronounced viscosity improving properties and are especially prerelled react~ntc Reactive metals and reactive metal compounds useful as (c) are those which are known to form salts and complexes when reacted with carboxylic acid and S carboxylic acid acylating agents.
Detailed disclosure of the reactions of (a), (b), (c) and (d) above with various acylating agents as well as the compounds defined under (a), (b) and (c)above are given in U.S. patents 4,234,435, 5,041,622 and 5,230,714.
Of the carboxylic derivative compositions described hereinabove, those 10 prepared from novel acylating agents and the alkylene polyamines especially polyethylene pol~alllines, and/or polyhydric alcohols, especially the polyhydricalkanols, are especially pr~lled. As previously stated, miAl~lres of polyamines and/or polyhydric alcohols are contemplated. Normally, all the carboxyl functions on the acylating agents of this invention will either be esterified or involved in 15 formation of an amine salt, amide, imide or imidazoline in this prefelled group of carboxylic derivative compositions.
In order to achieve the requisite degree of viscosity improving capabilities in the carboxylic deli~alive compositions of this invention, it has been found necess~ry to react the acylating agents of this invention with polyfunctional 20 react~nt~. For example, polyamines having two or more primary and/or secondary amino groups, polyhydric alcohols, amino alcohols in which there are one or moreplilllalr and/or secondary amino groups and one or more hydroxy groups, and polyvalent metal or polyvalent metal compounds. It is believed that the polyfunctional react~nts serve to provide "bridges" or crosslinking in the 25 carboxylic derivative compositions and this, in turn, is somehow responsible for the viscosity improving properties. However, the mech~nicm by which viscosity improving properties is obtained is not understood and applicants do not intend to be bound by this theory. Since the carboxylic derivative compositions derived, in whole or in part, from polyhydric alcohols appear to be particularly effective in 30 pe~ ing a reduction of the amount of viscosity improver in lubricating compositions, the polyfunctronality of react~nts (a), (b) and (c) may not fully CA 0220~643 1997-0~-16 explain the viscosity hnprovillg properties of the carboxylic derivative compositions.
Obviously, however, it is not necessA~y that all of the amine, alcohol, reactive metal, or reactive metal compound reacted with the acylating agents be 5 polyfunctional. Thus, combinations of mono- and polyfunctional amines, alcohols, reactive metals and reactive metal compounds can be used; for example, monoamine with a polyhydric alcohol, a monohydric alcohol with polyamine, an amino alcohol with a reactive metal compound in which the metal is monovalent, and the like.
While the pa~ elers have not been fully detçrmined as yet, it is believed that acylating agents of this invention should be reacted with amines, alcohols,reactive metals, reactive metal compounds, or ~ ures of these which contain sufflcient polyfunctional re~ct~nt, (e.g. polyamine, polyhydric alcohol) so that at least about 25% of the total number of carboxyl groups (from the succinic groups15 or from the groups derived from the maleic reactant) are reacted with a polyfunctional reactant. Better results, insofar as the viscosity improving facilities of the carboxylic delivalive compositions is concerned, appear to be obtained when at least 50% of the carboxyl groups are involved in reaction with such polyfunctional react~nt~. In most in~t~nces, the best viscosity improving 20 propellies seem to be achieved when the acylating agents of this invention are reacted with a sufflcient amount of polyall~ine and/or polyhydric alcohol (or amino alcohol) to react with at least about 75% of the carboxyl group. It should be understood that the foregoing percentages are "theoretical" in the sense that it is not required that the stated percentage of carboxyl functions actually react with 25 polyfunctional react~nt Rather these percentages are used to characterize theamounts of polyfunctional react~nts desirably "available" to react with the acylating agents in order to achieve the desired viscosity i.,.proving properties.
Another aspect of this invention involves the post-treatment of the carboxylic de~ live compositions as described in U.S. Patent 4,234,435.
30 Experiment~l conditions and examples of post-treatment are as described in U.S.
Patent 4,234,435. Acylated nitrogen, and l.ydro~y compositions, prepared by CA 0220~643 1997-0~-16 reacting the acylating agents of this invention with amines and alcohols as described above are post-treated by cont~cfing the acylated compositions thus formed (e.g., the carboxylic derivative compositions) with one or more post-treating agents selected from the group co~icting of boron oxide, boron oxide 5 hydrate, boron halides, boron acids, esters of boron acids, carbon disulfide, sulfur, sulfur chlorides, alkenyl cyanides, carboxylic acid acylating agents, aldehydes,ketones, urea, thiourea, ~l~ni~ine~ dicyanodiamide, hydrocarbyl phosphates, hydrocarbyl phosphites, hydrocarbyl thiophosphates, hydrocarbyl thiophosphites, phosphorus sulfides, phosphorus oxides, phosphoric acid, hydrocarbyl 10 thiocyanates, hydrocarbyl isocyanates, hydrocarbyl isothiocyanates, epoxides,episulfides, formaldehyde or formaldehyde-producing compounds plus phenols, and sulfur plus phenols. The same post-treating agents are used with carboxylic delivdlive compositions prepared from the acylating agents of this invention and a combination of amines and alcohols as described above. However, when the 15 carboxylic de~ivalive compositions ofthis invention are derived from alcohols and the acylating agents, that is, when they are acidic or neutral esters, the post-treating agents are usually selected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron acids, esters of boron acids, sulfur, sulfur chlorides, phosphorus sulfides, phosphorus oxides, carboxylic acid acylating 20 agents, epoxides, and episulfides.
Since post-treating processes involving the use of these post-treating agents is known insofar as application to reaction products of high molecular weight carboxylic acid acylating agents of the prior art and amines and/or~lcohols, detailed descriptions of these processes herein is unnecess~ry. In order to apply 25 the prior art processes to the carboxylic derivative compositions of this invention, all that is necessary is that reaction conditions, ratio of reactants, and the like as described in the prior art, be applied to the novel carboxylic derivative compositions of this invention. The following U.S. patents are expressly incorporated herein by reference for their disclosure of post-treating processes and 30 post-treating agents applicable to the carboxylic derivative compositions of this invention: U.S. Pat. Nos.

CA 0220~643 1997-0~-16 - 3,087,936; 3,200,107; 3,252,908; 3,254,025; 3,256,185; 3,278,550; 3,281,357;
3,281,428; 3,282,955; 3,284,409; 3,284,410; 3,306,908; 3,325,567; 3,338,832;
3,344,069; 3,346,493; 3,366,569; 3,367,943; 3,373,111; 3,403,102; 3,428,561;
3,502,677; 3,513,093; 3,515,669; 3,519,564; 3,533,945; 3,541,012; 3,558,743;
3,579,450; 3,632,511; 3,708,522; 3,759,830; 3,859,318; 3,865,813; 4,034,038;
4,136,043; 4,140,643; 4,234,435; 4,491,527; 4,695,390; 4,780,011; 4,857,214;
5,256,324; (use of acidified clays in post-treating carboxylic derivative compositions derived from the acylating agents of this invention and amines);
3,184,411; 3,185,645; 3,185,704; 3,245,908; 3,245,909; 3,245,910; 3,280,034;
3,312,619; 3,367,943; 3,369,021; 3,390,086; 3,415,750; 3,458,530; 3,470,098;
3,551,466; 3,558,743; 3,573,205; 3,639,242; 3,652,616; 3,692,681; 3,708,522;
- 3,718,663; 3,749,695; 3,859,318; 3,865,740; 3,865,813; 3,954,639; UK Pat. No.
1,085,903; ~JK Pat. No. 1,162,436. The processes of these incorporated patents, as applied to the carboxylic de,iv~live compositions of this invention, and the post-treated carboxylic derivative compositions thus produced constitute a further aspect of this invention.
As préviously indicated, the acylating agents, the carboxylic derivative compositions, and the post-treated carboxylic derivative compositions of this invention are useful as additives in lubricating oils. From the foregoing 20 description, it is seen that the acylating agents, the carboxylic derivative compositions, and the post-treated carboxylic derivative compositions, especially the latter two, function primarily as dispersant/detergents and Viscosity improvers.

The lubricant compositions of this invention include lubricating oils and greases although, for the most part they will be lubricating oils. The lubricating oil compositions of this invention are based on natural and synthetic lubricating oils and ll~ib~lures thereof. These lubricants include cr~nkca~e lubricating oils for5 spark-ignited and conlpr~ss;on-ignited internal combustion engines, such as automobile and truck Pngines, marine and railroad diesel çngines and the like.
Automatic tr~n~micsion fluids, transaxle lubricants, gear lubricants, metal-working lubricants, hydraulic fluids and other lubricating oii and grease compositions can also benefit from the incorporation therein of the acylating agents and carboxylic 10 delivali~e compositions of the present invention.
The lubricant and functional fluid compositions of the present invention are based on diverse oils of lubricating viscosity, including natural and synthetic lubricating oils and llfi~ures thereo~ The lubricating compositions may be lubricating oils and greases useful in industAal applications and in automotive 15 engines, tr~n~mi.ssions and axles. These lubricating compositions are effective in a variety of applications in~ ldin~ cr~nkc~ce lubricating oils for spark-ignited and comprcss;on-ignited internal combustion engines, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and low-load diesel Pngin~S and the like. Also, automatic tr~n~micsion fluids, transaxle lubricants,20 gear lubricants, metalwolking lubricants, hydraulic fluids, and other lubricating oil and grease compositions can benefit from the incorporation of the compositions of this invention.
The lubricants and functional fluid compositions of this invention employ an oil of lubricating viscosity which is generally present in a major amount (i.e. an 25 amount greater than about 50% by weight). Generally, the oil of lubricating viscosity is present in an amount of greater than about 80% by weight of the composition.
The natural oils useful in making the inventive lubricants and functional fluids include animal oils and vegetable oils (e.g., lard oil, castor oil) as well as 30 mineral lubricating oils such as liquid petroleum oils and solvent treated oracid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed par-CA 0220~643 1997-0~-16 aff~nicnaphthenic types which may be further refined by hydrocracking and L~drol~l-iching processes and are dewaxed. Oils of lubricating viscosity derivedfrom coal or shale are also useful. Synthetic lubricating oils include hydrocarbon oils and halo-substit~lted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, poly~rop~lenes, propylene-isobut-ylene copolymers, chlorinated polybutylenes, etc.); poly~l-hexenes), poly-(l-octenes), poly(l-decçnes), etc. and ~ L~lres thereof; alkyl-b~n7~nes (e.g., dodecylbenzenes, tetradecylbçn7enes, dinonylbe~7~nes di-(2-ethylhexyl)-benz-enes, etc.); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls, çtc.);
10 alkylated diphenyl ethers and alkylated diphenyl sulfidçs and the derivatives, analogs and homologs thereof and the like.
Alkylene oxide polymers and interpolymers and del;~dli~es thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another class of known synthetic lubricating oils that can be used.
15 These are exemplified by the oils prepared through polymerization of ethyleneoxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having an average molecularweight of about 1000, diphenyl ether of polyethylene glycol having a molecular weight of about 500-1000, diethyl ether of polypropylene glycol~naving a 20 molecular weight of about 1000-1500, etc.) or mono- and polycarboxylic estersthereof, for example, the acetic acid esters, mixed C3.8 fatty acid esters, or the Cl3Oxo acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating oils that can be used comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl 25 succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.) Specific examples of these 30 esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl ~7el~te, diisodecyl ~7~1~te, dioctyl ph~h~l~te, didecyl CA 0220~643 1997-0~-16 phth~l~te, dieicosyl sebac~te, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylh~Y~noic acid and the like.
Esters useful as synthetic oils also include those made from C~ to Cl2 5 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, tAmethylol propane, pentaerythritol, dipentaerythAtol, tApentaerythAtol, etc.
Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils comprise another useful class of synthetic lubAcants (e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-eth-10 ylhexyl)silicate, tetra-(4-methyl-hexyl)silicate, tetra-(p-tert-butylphenyl) silicate, hexyl-(4-methyl-2pentoxy)disiloxane, poly(methyl) siloxanes, poly-(methyl-phenyl)siloxanes, etc.). Other synthetic lubAcating oils include liquid esters of phosphorus-cont~inil-g acids (e.g., tAcresyl phosphate, tAoctyl phospha~, diethyl ester of decane phosphonic acid, etc.), polymeAc tetrahydrofurans and the like.
Unrefined, refined and re-refined oils, either natural or synthetic (as well as mixl~lres of two or more of any of these) of the type disclosed hereinabove can be used in the lubAcants of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further puAfication treatment.
For example, a shale oil obtained directly from retorting operations, a petroleum 20 oil obtained directly from pAmary rli~till~tion or ester oil obtained directly from an esteAfication process and used without further tre~tm~t would be an unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such puAfication techniques are known to those skilled in the art such as solvent 25 extraction, secondary ~ till~tion~ acid or base extraction, filtration, percolation, etc. Re-refined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such re-refined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives and oil 30 breakdown products.

- - -CA 0220~643 1997-0~-16 In one embodiment, the oil of lubricating viscosity is a poly-alpha-olefin (PAO). Typically, the poly-alpha-olefins are derived from monomers having from about 4 to about 30, or from about 4 to about 20, or from about 6 to about 16 carbon atoms. Examples of useful PAOs include those derived from 1-decene.
5 These PAOs may have a viscosity from about 2 to about 150.
In use, the various chlorine cont~ining substituted carboxylic acylating agents, carboxylic delivalive compositions and post-treated carboxylic derivative compositions are contained as additives in a composition comprising a majority of lubricating oil, functional fluid or fuel. As is well-known in the art, the 10 compositions of this invention are included with several other components in an oil of lubricating viscosity and/or function fluid. The components of this inventionwhen included in a oil of lubricating viscosity provide superior wear propertieswhen used in a (Ford) Sequence V~ Engine Test, ASTM D5302-92. Wear values for Sequence VE tests in mils are given below for a series of oil compositions and 15 for an oil composition having a low chlorine content substituted carboxylic acylating agent derivative prepared by reacting the low chlorine cont~ining acylating agent with amine bottoms to form the substituted acylating agent delivdlive.
Table 5. Wear Values in Mils for Sequence VE Test 1. 2.
Wear Max 1.03 0.40 Ave. 0.8 0.23 The value given in column 1. is for the composition without the 25 composition of this invention. The values in column 1. were selected as the best values available from three base line tests. One can determine that the composition of column 2. is superior to the best values of the base line composition. The only difference between the composition used for columns 1. and 2. is that the succinimide dispersant of the composition of column 2. is that as described in this invention.
The composition used in the Sequence VE tests above are as follows. The components are listed as weight percent based on the weight of the lubricating composition.

Table 6. LubricatinP comPositions for Use in Se~uence VE
Wear Tests Component Weight Percent 1. Base oil, lOON HT ~.~hl~n~l, Cattlesburg 72.2 2. Base oil, 325N HT p~hl~n~, Cattlesburg 9.9 3. Viscosity Ln~r~ ., c~ .c 91.4% Ashland, Cattlesburg lOOHT; 8.20 0.1% 2,6 di di~ lyl paracresol 8.5% Uniroyal cc-988 copolymer 4. Polymeth~crylate pour point depressalll 0.20 5. Performance package 9.50 The pelro~ ce package is listed below. The weight p~rcent of o each component is based on its weight based on the weight of the lubrica~ng compositions.
Table 7. Performance Packa~e Component Weight Percent 1. High molecular weight succinimide dispersant contains 55% dil oil 4.03 2. lOON dil oil 0.86 3. Succinate dispe~&nt, contains 45% lOON dil oil 1.37 4. Zinc dithiophosphate, contains 9% lOON dil oil 0.92 5. Nonylated diphenylamine, contains 12% lOON dil oil 0.68 6. Sulfi~rized ~-olefins contain 15% lOON dil oil 0.30 7. 255 TBN Ca overbased sulfurized dodecyl phenol, contains 39% 0.51 dil oil 8. 300 TBN Ca overbased sulfonate contains 41% dil oil 0.38 -Component (Cont'd.) Weight Percent 9. 300 TBN Na overbased 1000 Mn polyisobutylene substituted0.20 acylating agent, contains 40% dil oil 10. 400 TBN Mg overbased sulfonate, contains 32% dil oil 0.25 11. Silicone antifoaming - Dow 0.09 The difrt;rence in the compositions whose wear data are reported above for the Sequence VE wear test is that composition 2. contains a low chlorine cont~ining succinimide dispersant prepared in accordance with this invention. The chlorine cont~ining dispersant is prepared by reacting Mn 2000 polyisobutylene with maleic anhydride in the presence of chlorine to form a chlorine cont~ining substitute~ acylating agent. The chlorine content of the acylating agent may vary but would normally be in the range of about 0.7-1.5 weight percent. The chlorinecontent of the chlorine cont~ining acylating agent is then reduced using 0.6 equivalents of sulfur per equivalent of anhydride. This is based on two equivalents of sulfur per equivalent of tetrahydrophthalic anhydride units in the substituted acylating reaction ~ ure. The sulfur reaction is carried out at 210~C in the presence of 0.02 weight percent zinc acetate dihydrate for a period of eight hours.
The substituted acylating agent has a reduced chlorine content of about 0.12 weight percent based on the weight of the acylating agent.

Example 3. High Molecular Weight Sllccinimide Having Low Chlorine Content The chlorine cont~ining substituted acylating agent described hereinabove, 4.04 equivalents, 2645.2 grams is heated to 110~C with about 3.335 L lOON dil oil and 10 drops antifoam agent. To this stirred mixture is added 3.37 equivalents of Union Carbide PM 1969 polyamine lll;~Lure cont~ining about 25%
diethylenetriamine and 72% amine bottoms. The mixture is held at 110~C for one hour, when the temperature is increased to 15S-160~C for 4 hours, cooled to 50~C. The mi~ re is then heated again to 140~C, filter aid added, 183 grams, and -CA 0220~643 1997-05-16 the ~ ure is filtered. The reaction above is now under a 0.25CFM N2 purge.
The chlorine content of the succinimide dispersant - low chlorine content substitllted carboxylic acylating derivative - made by the process is about 0.05weight percent.
For the components listed above in Tables 6. and 7., many of the products are commercially available. The HT base oils are commercially available. The pour point depressalll is a polymetha~rylate. The viscosity Lnpro~er, in addition to the oil and di-t-butyl cresol can be Uniroyal cc-988, an olefin copolymer or Uniroyal X-3548, an olefin copolymer.
The high molecular weight dispersants of Table 7. can be made as described hereinabove or as described in U.S. Patent 4,234,435. The succinate dispersant can be made as in F~mple 13 of the '435 patent which describes the reaction of apolyisobutylene succinic acylating agent and pentaerythritol (an alcohol) and ethylene polyamines.
Zinc dithiophosphate and nonylated diphenyl amine may be purchased as is well-known to those skilled in the art. The sulfurized olefins are C~5-CI8 olefins reacted with S2Cl2 and then with Na2S. Sulfurization reactions may be found in U.S. Patents 2,708,199; 3,471,404; 4,191,659; 3,498,915 and 4,582,618 which are incorporated herein by reference for disclosure of sulfurization reactions.
The calcium overbased sulfurized docecylphenol as listed above is described in U.S. Patent 5,328,620 which is incorporated herein by reference forits disclosure of overbased sulfurized phenols. The phenol composition as used above contains about 5 weight percent Mn 1000 polyisobutylene substituted acylating agent and about 3 weight percent on a chemical basis of an overbased calcium sulfonate having TBN 30. The latter two additives to the sulfurized overbased phenol aid in compatibility.
The calcium overbased sulfonate having 300 TBN is a well-known type of detergent to those skilled in the art. The overbased calcium salt is a mixture cont~ining roughly 40% dil oil and 3.5 weight percent of 1000 Mn polyisobutylenesubstituted acylating agent and 2.5 weight percent of the calcium salt of a formaldehyde coupled phenol-mi~Lure. The latter contains 69% dil oil.

The sodium overbased carboxylate is a 1000 Mn polyisobutylene substituted acylating agent having TBN of 300. This type of compound is described in U.S.
Patent 5,449,470 which is incorporated herein by reference for compounds of thistype. The specific 300 TBN of this example also contains 2 weight percent 5 dodecylphenol.
The magnesium overbased sulfonate with 400 TBN is well known to those skilled in the art. The particular magnesium salt used above has 32 weight percent dil oil and conlaills 5 weight percent 1000 Mn polyisobutylene substituted acylating agent which aids cGll,palibility of this component.
It will be recognized by those skilled in the art, the compositions of this invention, while useful in themselves, are also useful in oils for lubrication, fuels, greases, hydraulic fluids and the like either alone or in mixtures with other additives.
Generally the lubricants of the present invention contain a lubricating 15 improving amount of one or more of the compositions of this invention, e.g., sufflcient to provide it with improved detergent/dispersant and/or viscosity properties. Normally, the amount employed will be about 0.05% to about 20%, preferably about 0.1% to about 10% of the total weight of the lubricating composition. This amount is exclusive of solvent/diluent medium. In lubricating 20 compositions operated under extremely adverse conditions, such as lubAcating compositions for marine diesel engines, the metal salts of this invention may bepresent in amounts of up to about 30% by weight or more, of the total weight of the lubricating composition.
The invention also contemplates the use of other additives in combination 25 with the compositions of this invention. Such additives include, for example,detergents and dispersants of the ash-producing or ashless type, corrosion- and oxidation-inhibiting agents, pour point depressing agents, extreme pressure agents, antiwear agents, color stabilizers and antifoam agents.
The ash-producing detergents are exemplified by oil-soluble neutral and 30 basic salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids, or organic phosphorus acids ~characterized by at least one direct carbon-to-phosphorus linkage such as those prepared by the treatment of an olefin polymer (e.g., polyisobutene having a molecular weight of 1000) with a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pent~l)lfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphorothioic chloride. The most commonly used salts of such acids are those of sodium pot~ssi~lm, lithium, calcium, magnesium, strontium and barium.
The purposes of this invention, techniques for their preparalion and their uses are described in U.S. Pat. Nos. 2,387,501; 2,015,748; 2,655,479; 1,815,022;10 2,191,498; 2,666,746; 2,721,877; 2,721,878; and 3,250,715 which are hereby incorporated by reference for their relevant disclosures.
Antifoam agents are used to reduce or prevent the formation of stable foam. Typical antifoam agents include silicones or organic polymers. Additional antifoam compositions are described in "Foam Control Agents", by Henry T.
15 Kerner (Noyes Data Corporation, 1976), pages 125-162.
The compositions of this invention can be added directly to the fuels or lubricants. Preferably, however, they are diluted with a substantially inert, normally liquid organic diluent such as mineral oil, naphtha, benzene, toluene or xylene, to form an additive concentrate. These concentrates usually contain from20 about 10% to 80% by weight of the composition of this invention, and 20% to 90% by weight of the inert diluents. The concentrates also may contain one or more other additives known in the art or described hereinabove.

Claims (24)

1. A polyalkylene substituted carboxylic acylating agent composition having reduced halogen content, said composition comprising reaction products formed by reacting (A.) halogen containing substituted carboxylic acylating agent composition reaction products formed by reacting chlorine and/or bromine with Mn 140-10,000 polyalkylene derived from C2-C16 olefins and maleic anhydride to produce said halogen containing reaction products; with (B.) a component selected from the group consisting of:
(a) sulfur;
(b) sulfur containing compounds;
(c) sulfur and a Lewis acid in any order;
(d) sulfur and a mineral acid in any order;
whereby said reduced halogen composition is produced.

2. A composition according to claim 1, said composition further comprising iodine containing polyalkylene substituted carboxylic acylating agents having reduced halogen content, said composition comprising reaction products formed by reacting (A.) iodine containing reaction products formed by reacting said composition of 1(A.) with a component selected from the group consisting of:
(a) iodine;
(b) iodine and a Lewis acid in any order;
(c) iodine and a mineral acid in any order;
to produce said iodine containing reaction products; with (B.) a component of 1(B.);
whereby said iodine containing reduced halogen composition is produced.

3. A composition according to claim 1 or 2, wherein said reaction products from 1(A.) comprise halogen containing polyalkylene substituted succinic anhydrides; polyalkylene substituted tetrahydrophthalic anhydrides; and polyalkylene substituted disuccinic anhydrides and wherein said tetrahydrophthalic components are converted to their phthalic analogs in 1(B.)

4. A composition according to claim 1, wherein said polyalkylene is polyisobutylene.

5. A composition according to claims 1 or 2, wherein said halogen content of said reaction products of 1(A.) is greater than said halogen content of reaction products of 1(B.), 2(A.), and 2(B.) as determined by weight percent halogen in said reaction products.

6. A composition of matter according to claim 1, wherein said halogen content of said reaction products of 1(A.) is about 2 weight percent or less based on the weight of said reaction products of 1(A.).

7. A composition of matter according to claims 1 or 2, wherein said halogen content of said reaction products of 1(B.), 2(A.), and 2(B.) is about 0.5 weight percent or less based on the weight of said reaction products.

8. A composition of matter according to claim 7, wherein said halogen content is less than about 0.15 weight percent.

9. A composition according to claim 1 or 2, wherein said 1(B.) and 2(B.) reaction products contain about 3 weight percent or less sulfur based on the weight of said reaction products of 1(B.) and 2(B.).

10. A composition according to claim 1 or 2, wherein said sulfur containing compounds are vulcanizing agents.

11. A composition according to claim 1 or 2, wherein said halogen is chlorine.

12. A composition according to claim 1 or 2, wherein said component selected is sulfur.

13. A composition of matter comprising halogen containing Mn 140-10,000 polyalkylene substituted carboxylic acylating agents, said composition comprising a halogen content of 0.5 weight percent or less based on the weight percent of said composition, said carboxylic acylating agents further comprising:
(A) polyalkylene substituted succinic anhydrides;

(B) polyalkylene substituted phthalic anhydrides; and (C) polyalkylene substituted disuccinic anhydrides.

14. A composition according to claim 13, wherein said composition further comprises polyalkylene substituted tetrahydro phthalic anhydrides.

15. A composition according to claim 1, wherein the 100°C kinematic viscosity of said reaction products of 1(B.) is greater than said reaction products of 1(A.)

16. A composition according to claim 1, wherein the reaction products of 1(B.) are more thermally stable than reaction products of 1(A.) as determinedby TGA.

17. A composition of matter having reduced halogen content, said composition comprising:
reaction products prepared by reacting a component selected from the group consisting of:
(A) reduced halogen composition of 1(B.);
(B) iodine containing reduced halogen composition of 2(B.);
or mixtures thereof with a reactant selected from the group consisting of:
(a) amine characterized by the presence within its structure of at least one H-N< group;
(b) an alcohol;
(c) a reactive metal or reactive metal compound;
(d) a mixture of two or more components of (a)-(c) wherein the components of (d) are reacted with said reduced halogen compositions; simultaneously or sequentially in any order.

18. A composition according to claim 17, wherein said halogen is chlorine.

19. A composition according to claim 18, wherein said composition further comprises sulfur.

20. A composition of matter having reduced halogen content, said composition comprising:
reaction products prepared by post reacting the reaction products of claim 17 with a reagent selected from the group consisting of:
(1) boron containing agents;
(2) sulfur containing agents including dimercaptothiadiazole and derivatives thereof;
(3) phosphorus containing agents;
(4) nitrogen containing agents;
(5) metal containing agents;
(6) carboxylate containing agents;
and mixtures thereof.

21. A method of making reduced chlorine content polyalkylene substituted phthalic anhydrides of formulas:

where R = polyalkylene [C1] R' = CH3 or H

said method comprising reacting a Mn 140-10,000 chlorine containing polyalkylenesubstituted tetrahydro phthalic anhydride with a compound selected from the group consisting of:
(a) sulfur;
(b) iodine;
(c) iodine and sulfur in any order.

22. The compounds formed by the method of claim 21.

23. A composition of matter comprising a fluid selected from the group consisting of:
(A) metalworking fluids;
(13) hydraulic fluids;
(C) transmission fluids;
and incorporated therein a composition selected from the group consisting of the products from claims 1, 2, 13, 17, 20 or 22.

24. A composition of matter comprising a major amount of a component selected from the group consisting of:
(A) oils of lubricating viscosity;
(B) fuels;

(C) greases;
and a minor amount of a composition selected from the group consisting of the products from claims 1, 2, 13, 17, 20 or 22.