CA1103026A - Poly(oxyalkylene) carbamate in fuel composition - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
FUEL COMPOSITIONS CONTAINING DEPOSIT CONTROL ADDITIVES
Fuel compositions for internal combustion engines are provided which contain deposit control additives which maintain cleanliness of intake systems without contributing to combustion chamber deposits. The additives are polyoxyalkylene carbamates comprising a hydroxy- or hydrocarbyloxy-terminated polyloxy-alkylene chain of 2-5 carbon oxyalkylene units bonded through an oxycarbonyl group to a nitrogen atom of polyamine having from 2 to 10 amine nitrogens and from 2 to 40 carbons with a carbon:nitrogen ration between about 1:1 and 10:1.

Description

-` 11(~3Q26 BACE~GRQUND_O~ THE INV~NTION

2 Field__f the_Inven_ion

3 In recent years, num~rous fuel detergents or ~deposit

4 control~ additives hare been developed. ~hese materials when added to hydrocarbon fuels employed in internal combustion 6 engines effectiYely reduce deposit formation which ordinarily 7 occurs in carburetor ports, throttle bodies, ~enturies, intake 8 ports and intake valves. The reduction of these deposit levels 9 has resulted in increased ~ngine efficiency and a reduction in the level of hydrocarbon and carbon monoxide emissions.
11 Thus, the introduction of fuel compositions containin~
12 deposit control additives has resulted in many cases in the 13 reduction of harmful atmospheric pollutants and, since greater 14 engine efficiencies are ~aintained, fuel savings.
A complicating factor has, however, recently arisen.
16 ~ith the advent of automobile engines that require the use of non--17 leaded gasolines (t~ prevent disablement of catalytic coGverters 18 used to reduce emissions), a serious problem has arisen in 19 providing gasoline of high enough octane to prevent knocking and the concomitant damage ~hich it causes. The chief problem lies 21 in the area of the degree of octane requ'rement increase, herein 22 called 'IORI'I, vhich is caused by deposits formed in the 23 combustion chamber ~hile the engine is operating on commercial 24 gasoline.
The basis of the ORI problem is as follo~s: each 26 engi~e, ~hen new, requires a certain minimum octane fuel in or~ar 27 to operate satisfactorily ~ithout pinging a~d/or knocking. As 28 the engine is operated on a~y gasoline, this minimu~ octane 29 incraases ana, in most cases, if the engine is operatea on the ~0 samP fuel for ~ prolonged period will reach equilibrium. This is 31 apparently _aused by an amount of deposits in the combustion 3~26 1 chamber. E~uilibrium is typically reached after 5000 to 15,000 2 miles of aut~mobile operation.
3 Octane raquirement increases at equilibrium with 4 commercial gasolines, in particular engines will vary from S or 6 octane units to as high as 12 or 15 units, depending upon the 6 gasoline co~positions, engine design and type of operation. The 7 seriousness of the problem is thus apparent. A typical 1975 or a 1976 autom~bile ~ith a research octane requirement of 85 ~hen ne~
9 may after a few months of operation require 97 research octane gasoline for proper operation, and little unleaded gasoline of 11 that octane is available. The ORI problem exists in some degree 12 ~ith engines operated on leaded fuels. U.S. Patents 3,144,311 13 and 3,146,203 disclose lead-containing fuel compositions having 14 reduced ORI properties.
It is believed, ho~ever, by many experts that the ORI
16 problem, while present with leaded gasolines, is much more 17 serious with unleaded fuel because of the different nature of the 18 deposits for~ed with the respective fuals, the size of lncrease, 19 and because of the lesser availa~ility of high-octa~e no~-leaded fuels. This problem is compou~ded by the act that the most 21 common means of enhancing the octane of unleaded gasoline, 22 incraasing its aro~tic content, also appears to increase the 23 aventual octane reguirement of the engine.
24 The problem is compounded by the recently discovered fact that some of the presently used nitrogen-containing deposit 26 control additives and the mineral oil or polymer carriers 2~ commonly used with such additives appear to contribute 28 significantly to th3 ORI of engines operated on unleaded fuel.
~,....................... .
29 It is, therefore, highly desira~le to provide fuel compositions which contain deposit control additives which 31 effectively control deposits in intake systems (carburetor, 1~(}3~?26 1 Yal~es, et~.) of en~ines operatad with fuels containi~g them, but 2 do not contribute to the combustion chamber deposits ~hich cause 3 increased octane requireme~ts.
4 D E SCRIPTIQ~I_OF_THE_PRI O R ART
U.S. Pate~t 3,359,303 discloses reaction products of 6 polyalkyleneoxy alkyl 1-aziridine carboxylates wit~ polyamines.
7 These materials are disclosed as being ~uring agents ~cross-8 linking agents~ for epo~y resins. ~he alkyleneoxy chains contain 9 a ma~imum of 22 alkyleneoxy units.
U.S. Patent 3,658,882 discloses certain aryl carbamates 11 and quaternary derivatives thereof useful as antistatic agents.
12 SgMMARY_OP THE_I~VENTION
13 Deposit control additives are provided ~hich maintain 14 cleanliness of engine intake systems an~ do ~ot themselv2s contribute t~ com~u~tion chamber deposits. The deposit control 16 additivas are poly~xyalkylene~ carbamates soluble in a 17 hydrocarbon fuel boiling in the gasoline range. The carbamates 18 comprise at least one hydroxy- or hydrocarbyloxy-terminated 19 poly(oxyalkylene) chain of 2 to 5 carbon atom oxyalkylene units bonded through an oYycarbonyl group to ~ ~itrogen atom of a 21 polyamine hlving from 2 to 10 amine nitrogens and from 2 to 40 22 carbons with a carbon-to-nitroge~ ratio between about 1:1 and 23 10:1. The ~lk~xy group will contain from 1 to 30, preferably 2 24 to 20 carbon atoms. The compounds will have molecular weights in the range of about 500 to 10,000, preferably from 800 to 5000.
26 The preferred compounds may b2 described by the 27 following general formula:

A R~N ~ ~ _Rl ~ N~S N~c,(Rl)d~ )e, R

28 ~herei~ R is the same or different constitutent selected from 2~ (I) hydrogem, 3~26 1 (II) hydrocarbyl of 1 to 10 carbon atoms, 2 (III) hydrocarbonyl of 2 to 10 carbon atoms, and 3 (IV) a qroup of the formula o -C-O ~ C ( H ) c~ ~ M ) h- ( C~12 ) i ~ [ ClIg ~ ~ ( C II 2 ) ~ ]
~[C(H)gll (M)h~ (CH2) ~ ]j" Z
4 in which g, g' and g" are integers 1 to 2; h, h' and h" are 0 or 1; i, i' and i" are integers 1 to 3; the sum of g and h is 2; M
6 is methyl or ethyl; ;, j' and ;" are integers and the sum of 7 j+j'~" is such that the molecular weight of IV is in the range 8 of 500 to 5000. Z is H or hydrocarbyl of 1 to 30 carbons. Rl is 9 the same or diffPrent alkylene or hydroYy-substituted alkylene radical of 2 to 6 carbon atoms, R2 is c~rbonyl~ alkyl carbonyl or 11 alkyle~e of 2 to 4 carbon atoms with vi~inal linkages. At least 12 one, and pra~erably not more than two of the R groups are IV and.
13 sufficient of the oxyalkylene units in IV are other than 14 ethyleneoxy to ren~ar the compound soluble in hydrocarbo~ fuel 15 boiling in the gasoline rangea' is 0 or 1, preferably 1; b' is ~6 an integer 0 to 4, preferably 0 to 2; c' is 0 or 1, pref~rably 0;
17 d' is 0 or 1, prefarably 0; e' is 0 or 1, pref~rably 1; and f' is 18 0 or 1, and equal to 1 ~hen c' is 0.
19 The preferred, but not all, polyoxyalkylene o~ycarbonyl radical substituted amines ~hich find use in this invention can 21 be broadly describea by the following ganeral formula: .

B -[N~-(uN~ ~ (u~ N )bR CR3~a-c]
... . ., . . . _ _ . . .
2.2 ~herein U is an alkylene having from 2 to 6 carbon atoms, there 23 being at la~st 2 carbon atoms between the nitrogen atoms and 24 preferably of from 2 to 3 carbon atoms; a is an integer from 0 to

5, and preferably of from 0 to 4; b is 0 or 1, preferably 0 whe~
26 a is greater than 0; a~2b is equal to a~ integer between 0 and 5;

11~3~2~

1 c is an integer ~rom 1 to ~, for the averags composition bei~g in 2 the range of about 1 to 3, on the average there being fewer R~
3 groups than nitroqen atoms; R is the same or different 4 constitutent selected from hydrogen or ~ Ct to Cl~ hydrocarbyl or the mono-keto, mono-nitro, monohydroxy, alkyleneoxy or alkoxy

6 derivative thereof; and R' is a poly(oxyalkylene~oxycarbonyl

7 radical derivel from polymerizing alkylene oxides from 2 to 5

8 carbon atoms, preferably from 2 to 4 carbon atoms, and more

9 preferably from ethylene oxide and propylene oxide, and having an average molecular weigh~ in tha range of 600 to 5000 and chlor~-11 for~ylating said radical with phosgene. Illustrative compounds 12 within the ~bove formula are N-~poly(oxypropylene)oYycarbonyl]
13 ethylenediamine, Nlpoly(oxypropylene)polyoxyethyleneoxycarbonyl]
14 dieth~lenetriamine.
~he additives are usually prepared by the reaction of a 16 suitable polyether ~lcohol with phosgens to form a chlor~formate 17 followed by reactio~ of the chloroformate with a mono- or 18 polyamine to form the active carbamate.
19 DBT~LED_pBSCRIPTIQN_OF_T~E_~VENTION
~ _iaQ
21 The amlnes employed in preparing the additiYes are as 22 described in ormula A with the exception that R will not be of 23 Type IV ~which is derived from the polyether chloroformate).
24 e_l~am~ae_C--po-a-at ~ha polyamine component embodies a broad class of 26 amines having from 2 to 10 amine nitrogens and from 2 to 40 27 carbons vith a carbon to nitrogen xatio between about 1 and 10:1.
28 In many instances, the amine component is not a pure single 29 product, but rather a mixture of compounds having a major quantity of the designated amine. Por the more complicated 31 polyamines, the compositions will be a mixture of amines having - ', , ': ' ' :

11~30Z6 1 as the major product the compound indicated in the average 2 composition and ha~ing minor amounts of analogous compounds 3 relatively close in compositions .o the dominant compounds.
4 EYemplary R groups of the amine precursor include S alkyls such as methyl, ethyl, propyl, butyl, isobutyl, pentyl, 6 hexyl, octyl, etc., alkenyls such as propenyl, isobutenyl, 7 hexenyl, octenyl, etc., hydroxyalkyls, such as 2-hydroYyethyl, 3-8 hydroxypropyl, hydroxy-isopropyl, 4-hydro~ybutyl, 8-hydroxyoctyl, 9 etc., ketoalkyls such as 2-ketopropyl, 6-ketooctyl, etc., alkory and lover alkyleneoxy alkyls, such as ethoxyethyl, etho~ypropyl, 11 proporyethyl, propoxypropyl, diethyleneoYyethyl, triethyleneoxy-12 ethyl, tetr~ethyleneoxyethyl, diethyleneoxyhexyl, diethylene-13 oxyoctyl, etc., acetyls such as propionyl, etc. The preferred R
14 groups are hydrogen, C~ to C6 alkyls and Cl to C6 hydroYyalkyls.
Illustratire Rt groups are ethylene, 1,2-propylene, 16 2,2-dimethyl propylene, trimethylene, tetramethylene, 17 hexa~ethylene, 1,3-2-hydroxypropylene, etc. The preferred 18 alkylene groups are ethylene and trimethylene.
19 As already indicated, in many instances a single compound ~ill not be used as a reactant in the preparation of the 21 compositions of this invention. ~hat is, miYtures will ~e used 22 in which o~e or two compounds will predominate with the average 23 composition or molecular weight as indicated. Por e~ample, 24 tetraethylene pentamine prepared by the polymerization of aziridine or reaction of dichloroethylene and ammonia will have 26 both lower ~nd higher amino members, e.g., triethylene tetramine, 27 substituted piperazines and pentaethylene hexamine, but the 28 composition will be mainly tetraethylene pentamine and the 29 empirical formula of the total composition will closely approximate that of tetraethyle~e pentamine.

11~3~)26 . ~
1 - The Polyethers 2 ~he polyethers or poly(oxyalkylene3 materials which are 3 utilized in preparing the polyether carbamates are conde~sation 4 polymers of the lower aliphatic oxiaes such as ethylene oxide, propylene o~ide, the butylene oxides and the pentylene oxides.
6 The preferred ~aterials are the propyl ne oxide polymers or 7 poly(propylene glycol). ~hese materials may be terminated or 8 capped on one end by a suitable hydrocarbyl group. For example, 9 particularly prefecred materials are capped ~itb a butyl, oleyl groups, etc. Also suitable are materials which are capped vith 11 mixtures of alkyl groups, i.e., ~ith a ~ixture of C~, C1A and ~ C20 alkyls. ~ile ~aterials with two terminal hydroxyl groups 13 can be emplayed, the use of a material containing but one is 14 preferred since chloroformylation ~ill produce a praferred monochloroformate ~hich can then be reacted with a suitable amine 16 to produce the preferred carbamyl material. ~o~ever, e~en though 17 some dicarbamate Yill be formed ~ith the dihydrosy materials, the 18 presence of smaLl ~ounts of these materi~ls are, though not 19 preferred, not detrimental to the performance of tha materlals.
The materials may be prepared from mixture of oxide 21 monomers, i.e. Yhen the reacti~ities of the oxides are relativ~ly 22 egual, random polymers can be prepared. In certain cases, with 23 ethylene o~ide, in combination with other oxides, the ethylene 24 oxide react~on rate is much greater, ana random polymers cannot 25 be easily prepared. In those cases, block copolymers are 26 prepared.
27 A particular type of polymer that can be prepared and 28 has been commercially prepared are represented by materials ~hich .0 29 are prepared by polymerizing propylene oxide to form a first material and then polymerizing ethylene oxide on one or both enas 31 of the poly(oxypropylene~. ~aterials of this type are marketed 32 by ~ya~dotte Chemicals as "Pluronics".
~ T~a61em~r~ 8 -~i~'3~DZ6 1 PreP_r_ti_n _f_the_P_l ye_h~r_Carbam_tes-2 The additives of this invention may be most 3 conveniently prepared, as has baen previously noted, by reaction 4 of phosgene ~ith the poly(oxyalkylene) compound follo~ed by reaction of the product with a suitable amine.
6 The reaction of the poly(oxyalkylene) material is 7 carrie~ out ~n an essentially eguimolar basis utilizing only a 8 slight excess of phosgene, although an ~Ycess of phosgene is not 9 detrimental. The reaction may be carriad out at temperatures from -10 to 100C, preferably in the range of 0 to 30C. The 11 reaction ~ill usually be complete within 1/4 to 5 hours. Times 12 of reaction ~ill usually be in the rang~ of from 1~2 to 3 hours.
13 A solvent may be used in the chloroformylation 14 reactimn. Suitable solrents include benze~e, toluene, etc. It is preferred that the phosgene be dissolved in a suitable sol~ent 16 before reaction vith the poly(oxyalkylene) material.
17 The reaction of the chloroformate with the amine may be 18 carried out neat or in solution. The m~lar ratio of amine to 19 chloroformate v~ll usually be in the range of 0.5 t~ 5.
~emperatures of from -10 to 200C may be utilized. The desired 21 product may be obtained by ~ater wash and stripping, usually by 22 the aid of vacuum, of any residual solvent.
23 The mol ratio of the polyether chloroformates to amin~
24 will generally be i~ the range from about 0.2 to 20 mols of amine J
per mol of chloroformate, and mor6 usually 0.5 to 5 mols of amine 26 per mol of chloroformate. The mol ratio ~ill depena upo~ tbe~
27 particular chlorof~rmate a~d the desired ratio of polyether to 28 amine. If suppression of PolYsubstitution of the al~ylene 29 polyamines is desired, large mol excesses of the amine ~ill be used. ~or example, in particular, preparation ~ith 31 ethylenediamine an amine-chloroformate ratio of 2.5 to 1 has _ g _ .

. . .

~ 3~26 1 yielded a basic nitrogen to total nitrogen ratio in the product 2 of 0.27, whereas raising the amine chloroformate ratio of 9.1 to 3 1 gives 0.42 basic nitrogen to total nitrogen ratio, showing a 4 much higher amount of monocarbamate in the material.
The reaction or reactions may be conducted ~ith or 6 ~ithout the presence of a reaction solvent. a reaction sol~ent 7 is generally e~ployed whenever necessary to reduce the ~iscosity a of the reaction product. These solvents should be stable and 9 inert to the reactants and reaction product. Preferred solvents include aliphatic or aromatic hydrocarbons. Depending on the 11 temperature of the reaction, the particular chloroformate used, 12 the mol ratios and the particular amine, as ~ell as the reactant 13 concentrations, the time may vary from 1/4 to 24 hours, more 14 usually from about 2 to 3 hours. Times greatly in excess of 3 hours do not particularly enhance the yield and may lead to 16 undes~rable degradation, especially at higher temperatures. It 17 is therefore preferred to limit the reaction time to less than 3 1 a hours.
19 After the reaction has been carried out for a sufficient langth of time, the reaction miYture may ~e subjectea 21 to extraction ~ith z hydrocarbon or hydrocarbon-alcohol medium to 22 free the product from any low-molecular-Yeight amine salts ~hich 23 ha~e formed and any unreacted alkylene polyamines. The product 24 may then be isolated by evaporation of the sol~ent~ Small amounts of halogen may be present as the hydrohalide salt of the 26 polyether carbamates.
27 Depending on the particular application of the 2~ composition of this inYention, the reaction may be carried out in .~,~ . .
29 the medium in ~hich it ~ill ultima~ely find use, e.g. polyether carriers ana be formed at concentrations ~hich provide a 31 concentrate of the detergent composition. Thus, the final :

11(~3~Z6 1 mixture may be in a form to be used directly for blending in 2 fuels.
3 The preferred polyoxyalkyleneoYycarbonyl radical 4 substituted alkylen- polyamine compositions have the following formula:

C [---N[(--CHz)fN -la[(--CH2~fN S N -~ R~CR3+~ c 6 The above symbols are defined as follows: a is an integer from 0 7 to 5, preferably an integer of from 0 to 4; b is an integer from 8 0 to 1, prefer~bLy 0 ~hen a is greater than 0; a~2b is equal to a 9 number bet~een 0 a~d 5; c is an integer in the range of 1 to 3, on the aver~ge there being fewer R groups than nitrogen atoms; f 11 is an integer from 2 to 3; R is the same or different 12 constitutent selected from hydrogen or 3 Cl to C~O hydrocarbyl or 13 the monoketo, mononitro, monohydrosy, alkyleneoxy or alkoxy 14 derivative thereof: and Rl' is a poly(oxyalkylene)oxycarbonyl radical of 600 to 5000 average molecular weight.
16 The above formulas represent broad and simplified 17 versioQs of the preferred poly(oYyalkylene) carbamates ~hich may 18 be employed in the practice of the instant in~ention. It should 19 be recognized that numerous polyether c~rbamates not defined by the abo~e formulas may be present in mi~or guantiti2s. ~hus, 21 while the abore formulas define preferred poly(oxyalkylene) J
22 carbamates present in ma~or quantities, they should not be 23 interpreted as excluding minor amounts of other components.
24 The polyether carbamates will generally be employed i~
a hydrocarbon distillate fuel. The proper concentration of 26 additive necessary in order to achieve the desired detergency a~d 27 dispersancy varies depending upon the type of fuel employed, the 2~ presence of other detergents, dispersants and other additives, ~1~3026 1 etc. Generally, ho~ever, from 30 to 2000 weight parts per 2 million, preferably from 100 to 700 pp~ of polyethercarbamate per 3 part of base fuel is needed to achie~e the best results. ~hen 4 other detergents are presen~, a lesser amount of polyether carbamate may be used. For performance as a carburetor detergent 6 only, lo~er concentrations, for example 30 to 70 parts per 7 million may be preferred.
8 The detergent-dispersant additive ~ay be formulated as 9 a conceutrate, using an inert stable oleophilic organic solvent boiling in the range of about 1~0 to 400F. Preferably, am 11 aliphatic or an aromatic hydrocarbon solvent is used, such as 12 benzene, toluene, Yylene or higher-boiling aromatics or ar~matic 13 thinners. Aliphatic alcohols of about 3 to 8 carbon atoms, such 14 as isopropanol, isobutylcarbinol, n-butanol and the like, in combination vith hydrocarbon solvents are also suitable for use 16 ~ith the detergent-dispersant additive. In the concentrate, the 17 amount of the additive will be ordinarily at least 10 percent by 18 weight and generally not exceed 70 percent by weight and 19 preferably from 20 to 60 weight percent.
In gasoli~e fuels, other fuel additives may also be 21 included such as antiknock agents, e.g., methylcyclopentadienyl 22 manganese tricarbonyl, tetramethyl or tetraethyl lead, or other 23 dispersants or detergents such as various substituted 24 succinimides, amines, etc. Also included may be leaa scavengers such as aryl halides, e.g., dichlorobenzene or alkyl halides, 26 e.g., ethylene aibromide. Additionally, antioxidants, metal 2~ deacti~ators a~d demulsifiers may be present.
28 A particularly use~ul additive is a fuel-soluble 29 carrier oil. Exemplary carrier oils include nonvolatile poly(oxyalkylene)s; other synthetic lubricants or lubricating 31 miLeral oil. Particularly preferred carrier oils are poly(oxy-, - - , . ' ':

~1~¢3~Z6 1 alkylene) mono and polyols, such as the Pluronics marketed by 2 ~ASF Wyandotte Corp., and the UCON LB-series fluids marketed by 3 Union Carbide Corp. When used, these oils are believed to act as 4 a carrier for the detergent and assist in remoring and retarding deposits. rhey have been found to display synergistic effects 6 vhen combined ~ith the polyether carbamates. They are employed 7 in amounts from about 0.05 to 0.5 percent by volume, based on the 8 final gasoline composition.
9 The folloYing examples are pr_sented to illustrate specific embodiments of the practice of this in~ention aLd should 11 not be interpreted as limitations upon the scope of the 12 invention.
13 ~x_mDle 1~ eaCtlon_Qf__hQ_~ th_PQly[OX~rQ~Ylen_l 14 A 99 g (1.0 mol) portion of phosgene ~as condensed into 750 ml of toluen~ at 0C. A 450 g (0.17 mol) portion of 16 monobutyl polyoxypropylene having a molecular Yeight of about 17 2400 was adaed as a slo~ stream to the phosgene-toluene Disture 18 over a period of 1/2 hour ~hila maintaining the temperature at 0-19 10C. 200 ml of ~enzene ~ere added. The temperature ~as raised to 80 and eYcess phosgene and benzene ~ere distill~d from the 21 product. ~ small sample was taken; toluene was evaporated from 22 it. Infrared analysis shoved a strong chloroformate absorption 23 at 1790 cm~l.
24 Example 2 -- Reaction of Poly(oxy-2~o~y-l-n--c~ -f_rma___~ith-Amine 26 One half of the product from Example 1 (in toluene 27 solution) ~as added at room temperature to 154 g t1.5 mols) of 28 diethylenetriamine in S00 ml of toluene. Immediate precipitatiom 29 of an amine hydrochloride occurred.~The mixture ~as stirred for one-half hour, filtered and the toluena ~as remoYed in a rotary 31 evaporator.
lra ~e~a,~, .

3~
1 The residue was dissolved in 1-1/2 volumes of hot n-2 butanol and extracted three times ~ith 100-200 ml of hot water.
3 The butanol was removed by vacuum providing 200 g of a product 4 vhich contained 1.17~ nitrogen and 0.80g basic nitrogen by AST~
D-2896. Infrared analysis revealed a typical car~amate 6 absorption at 1725 cm-l. This product is designated Compound I.
7 ExamPl__3 8 Pollowing the procedures of Esamples 1 and 2, polyether 9 carbamate amines vere prepared from the same butyl-capped poly(oxypropylene~ and the follo~ing amines giving products 11 ha~ing the designated percent nitrogen.
12 ~t. ~
13 Co_~ __Am_ne__________ _ Nitr~en 14 II triethylenetetramine 1.46 III dimethylaminopropylamine 1.07 16 IV hydroYyethylethylenediamine 0.84 17 ExamPle_4 18 Following the procedure of Ex~mples 1 and 2, but using 19 a monobutyl-capped poly(oxypropylene) of about 1800 molecular weight, the following carbamates were prepared.
21 ~t. %
22 C_mEou~ ______A~ins_______ Nitr_a_n 23 V ethylenediamine 0.83 24 VI diethylenetriamine 1.36 A 35.4 g portion of product VI was chromatographed on a 26 silica gel column (2" dia. x 7"~, eluting with 1 liter of ethyl 27 acetate ethyl acetate:methanol, 4:1; and ethyl acetate:meth-28 anol:isopropyl amine, 7:2:1. The first fraction, 13.8 g, ~as 29 found by infrared to be predominantly unreacted poly~osy-propylene). The latter two fractions, 20.7 g, were identified by 31 the carbonyl absorption as the desir~d carbamate~ This material 32 was designated VIa.

ExamPle_5 2 Phosgene (27 ml, 37.5 g, 379 ~mols) was condensed into 3 an ice trap, and vas them transferred to a 2 1, 3-neck flask 4 containing toluene ~500 ml) at -10C. The flask was equipped vith a gas inlet, mechanical stirrer, addition funneL and gas 6 outlet leading to a caustic trap. Polypropylene glycol monobutyl 7 ether, mw 1~10 (500 g, 276 mmols) was then added over about 1 ô hour. ~fter addition ~as complete, the mixture was stirred an 9 additional half-hour at room temperature and then sat overnight under a nitrogen blanket. A small sample stripped of toluene on 11 the rotary avaporator showed a strong infrared absorptiQn at 1790 12 cm-l, indicating formation of the chlorofor~ate.
13 o~e half of the above product (138 mmols~ ~as added 14 with stirring to diethylenetriamine (138 g, 1340 mm~ls~ in toluene (150 ml~. The reaction was eYothermic, the temperature 16 rising to 42C. White amine hydrochloride salts precipitated 17 immediately. The mixture was stirred 2 hours, stripped of 13 toluene, diluted ~ith 3 volumes of n-butanol, and washed four 19 times with hot water (80C, 200 ml). The organic phase was stripped of n-butanol on the rotary evaporator to yield 240 g of 21 the carbamata as a colorless oil. ~ Nitrogen - 1.42~ or 64~ of 22 theory based on 1900 mv. The product aYhi~ited a strong infrared 23 absorption at 1725 cm-~, and the 1790 cm-~ band was gone.
24 E~am~ 6_-- Pr_par__aon_of P_lyl_~Yb__yl_neL
The e~periment was carried out in dry glassware under 26 an inert atmosp~ere. Potassium (1.17 g, 0.03 mol) was added to 27 26.34 g (0.1 ~ol) of a phenol alkylated with propylene tetramer.
28 The mixture was stirred and heated to 50C for 24 h~urs until the 29 potassium dissolved. The pot temperature was raised to 80C and 1,2-epoxybutane (215 ml, 2.5 mols) was added at a rate slov 31 enough to prevent flooding of the condenser. The reaction vas ' 3~iZ6 1 stirred and heated at reflux until the pot temperature reached 2 125C. The product was extracted into 2 volumes of diethyl ether 3 and washed ~ith two volumes of 0.5 N HCl. Diethyl ather (250 ml~
4 was added to the ethereal layer, and it was washed four times with 250-ml aliquots of vater. THe solvent was removed and the 6 product was azeotroped with toluene to remove traces of water. A
7 yield of 145 g of a viscous liquid of molecular weight approxi-8 mately 1500 ~as obtained.
9 ExamPle 7_-- Reacti_n_of p-ly~Qxybu-ylene ~ with_PhQsqene Phosgene (14 31, 0.198 mol) was condensed and 11 transferred to a ~lask containing 150 ml of toluene. This 12 mixture was cooled and stirred in an ice bath vhile the poly( 13 butylene~ o~ E~ample 6 (140 g, 0.09 mol~ ~as added dropwise.
14 After the addition was complete, the ice bath ~as remo~ed and the mixture was stirred for about 1 hour. An aliquot was taken, and 16 the infra-red spectrum of its non-volatile residue shoved a 17 strong chloroformate absortpion at 1785 nm.
18 EYample B -- Reaction of Poly(oxy-19 butYl-ne--hl-orof-Ema-te-ylth AmlBe Ethylenediamine (41 ml, 0.61 mol) ~as stirred rapidly 21 and cooled in an iC9 bath. The chlorofmrmate o~ Exampl~ 7 ~as 22 diluted with four volumes of toluene and added to the 23 ethylenediamine at such a rate that the pot temperature did not 24 exceed 30C. After the addition was co~pleted, the ice bath was removed and the mixture was stirred for about 1 hour.
26 The miYture ~as extracted into 500-ml of hot n-butanol 27 and washed four timas with 500-ml aliquots of hot water. The 28 solvent was removed and the product was a~eotroped ~ith toluene 29 to remove traces of water, giving 1~ g of a viscous amber liquia of molecular weight about 1600. The product contained 1.20X by 31 weight nitrogen and dispersed sludgé at 200-400 ppm after 20 32 minutes.

.

.. . ..
:- . .

~3~

Exa m plc_9 2 The procedures used for the polymerization of 1,2-3 epo~ybutane ~as the same as that employed in Example 6, execpt 4 that a monobuto~y-capped poly(oxypropylene) material of molecular ~eight about 800, UCON LB165, was used in place of the phenol 6 alkylated with propylene tetramer. The preparation of the 7 chloroformate and ethylenediamine carbamate were also similar t~
8 the preceding examples.
9 The product, an amber liquid of molecular ~eight about 1800, contained 1.52~ by veight nitrogen.
11 ExamPl_10 12 In a manner similar to that described abova, poly(oYy-13 propylene) carbamates were prepared from amines having the 14 follo~ing structures:
A. ~CH2-CH2 HN ,,NH
16 ~CH2-CH2 o 17 HN N-cHz-cH2-NH2 1 a HN ",N-CH2-CH2-OH

19 The polyether carbamates were blended in gasoline and their deposit reducing capacity tested in an ASTM/CFR Single-21 Cylinder Engine ~est. f 22 In carrying out the tests, a ~aukesha C~ single-23 cylinder engine is used. The run is carried out for 15 hours, at 24 the end of which time the intake valve is removed, vashed with `
hesane and weighed. The previously determined ~eight of the 26 clean valve is substracted from the weight of the valve. The 27 differences between the two weights is the ~eight of the deposit 28 with a lesser amount of deposit measured connoting a superior .

~1~3~:D26 1 additive. The operating conditions of the test are as follows:
2 vater ~acket temperature 100C (212F~; manifold vacuum of 12 in 3 ~q, intake miYture temperature of 50.2C (125F~; air-fuel ratio 4 of 12; ignition spark timing of 40 BTC; engine speed is 1800 rpm; the crankcase oil is a comm~rcial 30N oil. The amount of 6 carbonaceous deposit in milligrams on the intake valves is 7 measured and reported in the following rable I.
ô The base fuel tested in the above extended detergency 9 test is a regular octane unleaded gasoline containing no fuel detergent. The base fuel is admixed with varying amounts of 11 detergent additives.
12 ~BLE I
____ 13 Int-k--val---DepQ-lt-est-14 Additive Carrier Averaqe_N_shed DePosit,_m~
_ DescriPtiQn___Ppm11 A_2nqine 12~_Engine 16 Base Fuel _ 2592 1~23 18 PPG-1450~ 300 P~G-1800~ 167 21 v 200 33 18 22 PPG-1450~ 300 24 VIa 125 14 45 PPG-1800~ 375 26 VIa 125 16 23 27 PPG-1450~ 275 28 tSingle evaluations unless noted.
29 2Average of 8 runs.
3Average of 4 runs.
31 ~The designation PPG-x refers to a monobutyl-capped 32 polyloxypropylene) glycol of about x moleculac weight.
33 The~above results sho~ the significant reduction in 34 valYe deposits achieved compared with b3se fuel.
In order to sho~ the effect of addition of a poly(oYy-36 alkylene) c3rrier o~ deposits, 12~ Engine Deposit Tests ~ere ~03026 1 performed as above using various combin~tions of Additive VI and 2 PPG-1450 (see description above). ~hese results are set forth in 3 Table IA.
4 ~ABLE_IA
S Intake Valve Deposit Tests on Combinations of 6 pQlyoEyalkvlene-c-Ebam3te-3nd-polyox~alkylene GlycQl 7 ~otal Addi- Average Washed 8 Run tive,_~pm__ y~a,_PPm PPG-145_~_2Pm D_POS1tS~ ~m 12 4 250 125 125 64,12 17 These results show that the poly~oxyalkylene) glycol 18 functions as more than a conventional carrier. For example, Ru~s 19 3, 4 and 5 containing equal total quantities of glycol and carbamate were much more effective than the carbamate alone of 21 Ru~ 6 or the glycol alone of Run 8.
22 The additives ~ere evaluated in a laboratory 23 dispersancy test. The hexane-insoluble, chloroform-soluble 24 portion of sludge scraped from the crankcase of high mileage engines was added as a chloroform solution to a typical base 26 gasoline containing varying amounts of the test additive. The 27 concentrati~n of ad~itive necessary to prevent coagulation and 28 precipitation of the sludge for at least 30 minutes ~as measure~
29 Table II sets forth these results:
~BLE II
31 ComPound N~ C_n_.~_P~m 34 III ~00 _ 1 9 _ 3~

1 The data indicate that all of these additives are 2 effective dispersants and should, therefore, iDhibit valve deposit formation.
4 The tendency of the additives to contribute to oaI Yas -evaluated in a laboratory engine test. The test engi~e is a CLR
6 single-cylinder, balanced, high-speed, four-cycle engine designed 7 primarily for oil t2st and research work. It is manufactured by 8 the Laboratory Equipment Corporation of ~ooresville, Indiana.
9 The major engine dimensio~s are:
Bore 3.80 In.
11 Stroke 3.75 In.
12 Displacement 42.5 Cu. In.
13 Compression Ratio 8:1 14 The carburetor, intake manifold, and distributor have been slightly modified to facilitate our test procedure. These 16 modifications haYe made the engine's ORI characteristics 17 comparable to modern-day automobiles.
18 The test procedure involves engine operation for 80 19 hours (24 h~urs a day~ on a prescribed load and speed schedule representative of typical vehicle driving conditions. The cycle 21 for engine operation during the test is as follows:

. , ,. . ' ' ' ' ' ' 3~

2De~_sit_Accumul_tlon Cycle-cLR-slnqle-cyllndeE
3Time in ~anifold Engine 4Mode, Vacuum, Speed, 5__________MQae ~ _ _ _ _Sec. _ _In._H~_ _r~m__ 6 1. Idle 140 16900 7 2. Heavy Cruise, Low Speed 70 7 2000 8 3. Light Cruise, Low Speed 14013 2000 9 4. Deceleration 140 181~00 5. Heavy Cruise, lo~ Speed 70 7 2000 11 6. Light Cruise, Lo~ Speed 14013 2000 12 7. Idle 210 16900 13 8. Hea~y Cruise, Low Speed 70 7 2000 14 9. Light Cruise, Low Speed 70 13 2000

10. Heavy Cruise, ~igh Speed 70 9 2500 16 11. Light Cruise, High Speed 14015 2500 17 12. Deceleration 140 181800 18 All o~ the test runs were made ~ith the same base gasoline, 19 which vas representative of commercial unleaded fuel. The results are set forth in Table IV.

22 Lab-ratQr~-oRI-Test-Res-lts 23 Combustion 24 Additive, Carrier Concentra- Chamber Run~ DescE Pt~_n _ _ ii_a _~Pm_ DePosits,_c ORI
26 159 -- -- -- 3.4 27 161. Commercially a~ailable 467 -- 7.1 28 nitrogen-containing DCA
29 Mineral carrier oil1600 163 -- -- 1.2 2.4 31 164 VI 500 1.6 4.2 32 165 (Same as 161) 300 2.1 5.5 33 (same as 161) 1000 34 167* VI 500 1.6 5.8 168 -- -- 1.4 3.6 36 169 V 286 1.3 2.5 37 peG-145o~ 214 38 170 V 286 1.6 2.4 39 PPG-1450** . 214 .... . ..
~Air-fuel ratio during the idle portions of the test cycle 41 was off specification during Run 167.
42 *~See Table I.

11(~302~

1 Simple arithmetic averages of the results indicate:
2 base fuel gives an ORI of 3.1 and combustion chamber deposits 3 ~eighing 1.3 g, the commercial additives averaged 6.3 units ORI
4 a~d had combustion chamber deposits weighing 2.1 g, and the polyether carbamates gave an ORI of 3.7 (3.0 omitting Run 167) 6 and combustion chamber deposits averaging 1.5 g. Generally, 7 these results indicate that the polyether carbamates, which have 8 been demonstrated to be escellsnt inlet system deposit control 9 additives, do not contribute significantly to increasing octane requirements (over base fuel) of the engines in which they are 11 employed.

12 The test for evaluating the ability of fual additives

13 to control carburetor deposits employs a 1973 model year, 240

14 CID, 6-cylinder Ford engine. The internal bore of the carburetor throttle body is eguipped ~ith a thin, removable aluminum sleeve.
16 The difference between sleeve ~eights determined before and after 17 an engine rln represents the change in ~mount of surface deposit 1 a occurring during that run.
19 F~r additive evaluation, t~o test phases are run as set forth in Table V.

- ~ .

11(~3~Z6 1 T~BLE_V
2CaEburetoE_DePosit_Te_t Proedure 31. Dirty-Up Phase (Starting 4v th Cl_an Sle_v__ _ __ Objective: Establish deposits on carburetor slee~e.
6 Durati~n: 15 hours.
7 Operating Cycle: 7 minutes moderate load and speed, 4 8 minutes idle.
9 Engine Setup: Crankcase blowby gases routed to carburetor air inlet.
11 Fuel: Deposit-rorming fuel containing heavy 12 FCC component.
13 2valuation: Sleeve weighLs are determined at the 14 beginning and end of the dirty-up phase, and sleeve deposits are rated visually 16 on a scale of 0 to 10 (1o = clean).
17 2. Cleanup Phase (3egins with Sleeve 18p~sits PQrmed_Durinq_Dirtv-UP Ph_se 19 Objective: Measure additive performance in cleaning up deposits.
21 Duration: 4 hours.
22 Operatlng Cycle: Same as dirty-up phase.
23 Engine Setup: Crankcase blowby cases diverted from 24 ~arburetor inlet - EGa shutoff.
~uel: Commercial-type gasoline containing 26 additive under test.
27 Evaluation: The sleeve is reweighed and rerated 28 visually. Differences betYeen initial 29 and final values represent additive effectiveness.
31Table VI presents average values for the performance of 32 PPG-amine carbamate additives. Also, presented are values for a 33 commercial deposit control additive having recognized performance 34 in the field. Deposit level changes with a commercial-type unleaded gasoline ~ithout additive are also shown.

3C~Z6 1 TABLE_VI
2 C3rburet_r_Te_t_ReS_l_5-3 Avera~ QAddltlve-peE
4 Deposit Concen- Neight 6 tration, Reduc 7 Runs __ppm_ tion,_~ Initial Final _~_ 9Carbamate2 4 200 88 4.9~ -> 8.1~ 3.2 11Carbamate3 1 150 93 4.4 -> 8.1 3.7 12Commercial 13additive 8 150 91 5.3 -> 8.4 3.1 14 ~one 2 - 63 4.6 -> 6.0 1.4 ~Yisual Deposit rating (10 = clean~.
16 2Similar to Compound V of Example 4.
17 3Similar to Compound VI of Example 4.
18 ~Data for 3 runs only.
19 These data shov that the polyether carbamates are as effective aarburetor deposit control additives as the recognized commerci~l 21 additive.
22 The three additives tested gave carburetor daposit 23 weight reductions ranging from 85~-95% and improvements in visu~l 24 deposit ratings from initial leYels of 5 to final levels as high as 9 on a scale of 10.
26 All specific embodiments of the invention have been 27 described in detail, and it should be understood that the 28 invention is to be given the broadest possible interpretation 29 Yithin the terms of the following claims.

. - 24 -

Claims (25)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A fuel composition comprising a major portion of hydro-carbons boiling in the gasoline range and from 30 to 2000 ppm of a poly(oxyalkylene) carbamate having at least one C1-C30 hydro-carbyloxy-terminated poly(oxyalkylene) chain of 2 to 5 carbon oxyalkylene units bonded through an oxycarbonyl group to a nitro-gen atom of a polyamine; said polyamine having from 2 to 10 amine nitrogens, from 2 to 40 carbon atoms and a carbon to nitrogen ratio in the range of about 1:1 to 10:1, said carbamate having a molecular weight of from about 500 to 10,000.

2. The composition of claim 1 wherein the oxyalkylene units contain 3 carbon atoms.

3. The composition of claim 2 wherein the molecular weight is from about 800 to 5,000.

4. The composition of claim 2 wherein the groups termin-ating the poly(oxyalkylene) chain is an alkoxy group containing from 2 to 20 carbon atoms.

5. The composition of claim 4 wherein the alkoxy group is butoxy.

6. The composition of claim 4 wherein the alkoxy group contains 18 carbon atoms.

7. The composition of claim 4 wherein the alkoxy group contains 16 to 20 carbon atoms.

8. The composition of claim 7 wherein the alkoxy groups comprise a mixture of C16, C18 and C20 carbon groups.

9. The composition of claim 2 wherein the amine is ethyl-enediamine.

10. The composition of claim 2 wherein the amine is diethy-lenetriamine.

11. A fuel composition comprising a major portion of hydro-carbons boiling in the gasoline range and from 30 to 2000 ppm of a compound of the formula I

I

wherein R is the same or different constituent selected from (I) hydrogen, (II) hydrocarbyl of 1 to 10 carbon atoms, (III) hydrocarbonyl of 2 to 10 carbon atoms, and (IV) a group of the formula in which g, g' and g" are integers 1 to 2; h, h' and h" are 0 or 1; i, i' and i" are integers 1 to 3; the sum of g and h is 2; M
is methyl or ethyl; j, j' and j" are integers and the sum of j, j' and j" is such that the molecular weight of (IV) is 500 to 5,000; Z is hydrocarbyl of 1 to 30 carbon atoms; R1 is the same or different alkylene or hydroxy-substituted alkylene radical of 2 to 6 carbon atoms; R2 is carbonyl, alkyl carbonyl or alky-lene of 2 to 4 carbon atoms with vicinal linkages, at least one of the R groups are (IV) and sufficient of the oxyalkylene units in (IV) are other than ethyleneoxy to render the compounds solu-ble in hydrocarbon fuel boiling in the gasoline range; a' is 0 or 1, b' is an integer 0 to 4, c' is 0 or 1, d' is 0 or 1, e' is 0 or 1 and f' is 0 or 1 and equal to 1 when c' is 0, and the com-pound of formula I apart from said at least one (IV) group has a carbon to nitrogen ratio in the range of about 1:1 to 10:1.

12. The composition of claim 11 wherein M is methyl; and g, g', g", h, h', h", i, i' and i" are each equal to 1.

13. The composition of claim 12 in which f', a', b', and e' are each equal to 1 and c' and d' are each 0.

14. The composition of claim 13 in which R1 is propylene.

15. The composition of claim 13 in which R1 is ethylene.

16. The composition of claim 12 in which f', a' and b' are each equal to 1 and c', d' and e' are each 0.

17. The composition of claim 16 in which R1 is propylene.

18. The composition of claim 16 in which R1 is ethylene.

19. The composition of any one of claims 11, 12 and 13 wherein not more than two of the R groups are (IV).

20. The composition of any one of claims 14, 15 and 16 wherein not more than two of the R groups are (IV).

21. The composition of claim 17 or claim 18 wherein not more than two of the R groups are (IV).

22. The fuel composition of claim 1 which contains in addition from 100 to 5,000 ppm of a fuel-soluble poly(oxyalkylene).

23. The fuel composition of claim 22 in which the poly(oxyalkylene) is poly(oxypropylene).

24. A concentrate comprising an inert stable oleophyllic organic solvent boiling in the range of about 150° to 400°F and from 10 to 20 weight percent of the compound of claim 2.

25. A concentrate according to claim 24 wherein there is present in addition poly(oxypropylene) in the amount of from 7.5 to 80 weight percent.