Novel branched-chain monoalcohols and derivatives thereof, lubricant compositions for polymers and wax compositions in which these novel products are incorporated

Novel branched-chain monoalcohols and derivatives thereof are disclosed. Such derivatives are selected from the group consisting of PA0 (a) esters of aromatic, aliphatic or cycloaliphatic acids having at least 2 carbon atoms and 1, 2 or 3 carboxyl groups; PA0 (b) urethanes of aromatic, aliphatic or cycloaliphatic isocyanates; PA0 (c) monoethers of polyalkylene oxide glycols having 2 to 50 alkylene oxide units each containing 2 or 3 carbon atoms and the alkylpolyoxyalkylene sulfates derived therefrom; PA0 (d) sulfates. The branched-chain monoalcohols are obtained by reduction of branched-chain monocarboxylic acids or esters thereof. Said acids are telomeric acids obtained by the free radical addition of 1 mole of acetic anhydride to at least three moles of hexene and/or higher olefins containing up to 30 or more carbon atoms (C.sub.30+) in the presence of a trivalent manganese compound. The products of this invention are suitable for use in engine lubricating oils, lubricant compositions for polymers and wax compositions.

The invention relates to novel branched monoalcohols having at least 20 
carbon atoms, and the derivatives thereof selected from the group 
consisting of 
(a) esters of aromatic, aliphatic or cycloaliphatic acids having at least 2 
carbon atoms and 1, 2 or 3 carboxyl groups; 
(b) urethanes of aromatic, aliphatic or cycloaliphatic isocyanates; 
(c) monoethers of polyalkylene oxide glycols having 2 to 50 alkylene oxide 
units each containing 2 or 3 carbon atoms and the alkylpolyoxyalkylene 
sulfates derived therefrom; 
(d) sulfates, to lubricant compositions for polymers which are entirely or 
partly composed of one or more of these alcohols and/or derivatives 
thereof, and to wax compositions for entirely or partly replacing carnauba 
or montan wax and substantially consisting of one or more of these 
alcohols and/or derivatives thereof. Branched-chain monoalcohols and the 
esters derived therefrom are known from, inter alia, U.S. Pat. No. 
2,862,013. The alcohols are obtained by Guerbet condensation of lower 
alcohols. A drawback to this method of preparation is that it is 
relatively costly. 
Moreover, the alcohols obtained have not more than 24 to 28 carbon atoms. 
Also the German Patent Specification No. 2 613 996 describes a process for 
the preparation of branched-chain alcohols and the esters built up 
therefrom. According to the general formula alcohols having not more than 
18 carbon atoms are obtained. The examples merely include the preparation 
of 2,4-diethyloctanol, i.e. an alcohol having 12 carbon atoms. 
Applicant has found that the preparation of branched-chain alcohols and the 
esters derived therefrom having a product composition which entirely 
differs from the one described in the above-mentioned patent 
specifications leads to products having remarkably better properties for 
quite a number of uses. 
The present invention provides a novel class of branched-chain monoalcohols 
and derivatives therefrom. 
The invention consists in that the alcohols, from which also the 
derivatives of the known type mentioned in the opening paragraph are 
derived, conform to the formula: 
##STR1## 
where 
x=0, if y=2 or x=2, if y=0 
R=CH.sub.3 (CH.sub.2).sub.n, where n represents an integer from 3 to 42; b 
is 0 or 1, where if b=0, Q represents a hydrogen atom, and if b=1, Q 
represents a CH.sub.2 -group, and a=0 or 1, where if a=0, Z represents a 
hydrogen atom, and if a=1, Z represents a CH.sub.2 -group. 
It has been found that in the preparation for a large number of uses of the 
derivatives it is preferred that they should be derived from alcohols 
where n=3 to 17. These derivatives find application as lubricant for 
polymers and in the preparation of surface active compounds and engine 
lubricants. Particularly with the use of the alcohols as such, for 
instance as lubricant in resin compositions for polymers and in wax 
compositions, it is preferred to employ branched-chain alcohols of the 
above formula where n represents an integer of from 17 to 42. 
For the preparation of the novel esters according to the present invention 
it is preferred to start from an aliphatic acid having 1 to 30 carbon 
atoms. For most uses, as in lubricant compositions for polymers, the 
object will be to obtain good processing properties in combination with 
minimum volatility. According to the invention the branched-chain alcohols 
are therefore often esterified with a di- or a tricarboxylic acid. 
Particularly the esters derived from acetylene dicarboxylic acid, fumaric 
acid, maleic acid or adipic acid are found to lead to products which are 
excellently suitable for entirely or partly replacing carnauba wax. 
Representative examples of monocarboxylic acids to be used according to the 
invention include acetic acid, propionic acid, butyric acid, cyclohexyl 
carboxylic acid, valeric acid, pivalic acid, oleic acid and lauric acid. 
Representative examples of dicarboxylic acids to be used according to the 
invention include sebacic acid, cyclohexane-1,4-dicarboxylic acid, adipic 
acid, glutaric acid, succinic acid, oxalic acid, azelaic acid, furan 
3,4-dicarboxylic acid, terephthalic acid and isophthalic acid. 
An example of an acid having three carboxyl groups is citric acid. The acid 
number of these esters is preferably lower than 30 and the hydroxyl number 
lower than 40. The esterification reaction may be carried out in the usual 
manner. The reaction mixture is heated in the presence or not of a 
catalyst at a temperature in the range of 100.degree. to 300.degree. C. 
and the water evolved in the reaction is carried off. The esterification 
is usually carried out at a temperature in the range of 140.degree. to 
280.degree. C. 
Optionally, use may be made of an esterification catalyst. This may be an 
acid such as sulphuric acid, phosphoric acid, alkylsulphonic acids and 
arylsulphonic acids such as p-toluene sulphonic acid and methane sulphonic 
acid, and a variety of metal compounds such as dibutyl tin oxide, 
tetrabutyl titanate, zinc acetate, stanno-oxalate, iron oxide, 
ferristearate, manganostearate, cobalt (II) stearate and manganoacetate. 
The catalyst is usually employed in an amount of 0.1 to 1% by weight, based 
on the reaction mixture. Optionally, use may be made of an inert thinner 
such as benzene, toluene or xylene, which together with water forms an 
azeotrope. 
In the process use is generally made of stoichiometric amounts of acid and 
alcohol. Esterification may take place at atmospheric pressure, but may be 
carried out at reduced pressure (2-50 mm Hg). Under such conditions water 
and other volatile constituents can readily be removed upon completion of 
the reaction. The resulting esters are as a rule directly suitable for one 
or more of the above-mentioned uses. Under some circumstances, however, it 
may be advisable also to apply a purification step, for instance by 
treating the compositions with bleaching earth, ozone, peroxide, 
hypochlorite or some other suitable bleaching agent. The preparation also 
may include a treatment with active carbon. 
The isocyanates to be used in the preparation of the urethanes of the 
present invention may be of an aliphatic, cycloaliphatic or aromatic 
character. If few or no coloured products are desired, then it is 
preferred to use aliphatic isocyanates. Preference is further given to 
isocyanates of the general formula A-R.sub.1 --NCO, where R.sub.1 
represents a (cyclo) aliphatic hydrocarbon having at least 6 carbon atoms, 
a phenyl group or naphthyl group, which groups may be substituted or not 
with one or more lower alkyl groups having 1 to 8, and preferably 1 to 6 
carbon atoms, lower alkoxy groups having 1 to 8, and preferably 1 to 6 
carbon atoms, aryl, for instance phenyl, and halogen such as chlorine or 
bromine, and A represents a --NCO group, or a --R.sub.2 --(CH.sub.2 
--R.sub.3 --NCO).sub.n R.sub.4 NCO group where R.sub.2 has the meaning of 
a simple bond or an aliphatic hydrocarbon group having 1 to 4 carbon 
atoms, n is equal to 0 or higher, and R.sub.3 and R.sub.4 may be the same 
or different and may or may not have the same meaning as R.sub.1. 
As examples of suitable monoisocyanates may be mentioned ethyl isocyanate, 
hexyl isocyanate, 2-ethylhexyl isocyanate, butyl isocyanate, stearyl 
isocyanate. As examples of diisocyanates which can be defined by the 
formula OCNRNCO, where R represents a divalent aliphatic, alicyclic or 
aromatic group, may be mentioned: 
hexamethylene diisocyanate; 
dimethyl hexamethylene diisocyanate; 
trimethyl hexamethylene diisocyanate; 
metaxylene diisocyanate; 
paraxylene diisocyanate; 
tetramethylene diisocyanate. 
In the case where R represents an aromatic group, it may be substituted 
with a halogen, a lower alkyl or a lower alkoxy group. 
As examples of such diisocyanates may be mentioned: 
1-chloro-2,4-phenylene diisocyanate; 
2,4-toluene diisocyanate; 
a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate; 
tetramethylphenylene diisocyanate; 
diphenylmethane-4,4'-diisocyanate; 
metaphenylene diisocyanate; 
paraphenylene diisocyanate; 
1,5-naphthalene diisocyanate; 
biphenyl-4,4'-diisocyanate; 
diphenylmethane-4,4'-diisocyanate; 
4,4'-isopropylidene diphenylisocyanate; 
benzophenone-4,4'-diisocyanate; 
diphenylether diisocyanate or diphenylsulphide diisocyanate; 
3,3'-dimethyldiphenyl-4,4'-diisocyanate; 
3,3'-dimethoxydiphenyl-4,4'-diisocyanate; 
3,3'-dichlorodiphenyl-4,4'-diisocyanate; 
benzofuran-2,7-diisocyanate. 
Examples of diisocyanates having an cycloaliphatic group include isophoron 
diisocyanate, dicyclohexyl methane diisocyanate and 1,4-cyclohexane 
diisocyanate. 
The temperature at which the reaction takes place between the alcohol and 
the isocyanate should be established experimentally. It will generally be 
in the range of 60.degree. to 200.degree. C. 
The reaction of the alcohols according to the invention with the isocyanate 
compounds is carried out in a manner known in itself. The conversion may 
be carried out in the melt or in an inert solvent. Examples of suitable 
solvents include methylene chloride, carbon tetrachloride, benzene, 
chlorobenzene, methylethyl ketone, tetrahydrofuran, dioxane, 
glycolmonomethylether acetate, glycol formal, dichlorobenzene, 
trichlorobenzene, nitrobenzene, benzoic methyl ester or acetophenone. If 
the conversion is carried out in solvents, especially relatively low 
boiling ones, such as methylene chloride, the solvents may be distilled 
off as the reaction progresses. 
The preparation of the monoethers of the present invention is usually 
carried out in two steps: (a) addition of ethylene oxide and/or propylene 
oxide to the alcohol to form a monoadduct, followed by (b) subsequent 
addition(s) of ethylene oxide and/or propylene oxide in a polymerization 
reaction. The alkoxylation reaction is catalysed by bases such as NaOH, 
NaOCH.sub.3 or KOH in an amount of about 0,005 to 0,05 mole of base per 
mole of alcohol. The reaction temperature is generally chosen between 
100.degree. and 200.degree. C. The alkoxylation is generally carried out 
as a batch reaction. After the reaction is complete, the catalyst is 
neutralized and the product is discharged to storage or packaged. The 
alkylpolyoxyalkylene sulfates are prepared with amidosulfuric acid as the 
sulfating agent. This sulfation technique leads directly to the formation 
of the ammonium salt. Sodium salts can be prepared by adding caustic soda 
and driving off the ammonia with heat. Though the ammonium and/or sodium 
ion can be replaced by an innumerous number of different cations, 
preference is given to a cation selected from the group of ammonium, 
sodium, potassium, magnesium, diethanolamine and triethanolamine. The 
alcohols of the present invention may also be sulfated directly in the 
same manner as described hereabove for the sulfation of 
alkylpolyoxyalkylene oxide glycol with the aid of amidosulfuric acid. 
Preference is given for the same cations as is the case for the 
alkylpolyalkylene sulfates. 
The alcohols of the first-mentioned formula can be obtained by reduction in 
a manner known in itself of an acid, or of an ester thereof having the 
formula 
##STR2## 
where R, Z, Q, a, b, x and y have the above-indicated meanings and R.sup.1 
represents a hydrogen atom (for the acid), or a preferably lower alkyl 
group having 1 to 4 carbon atoms. 
Reduction with hydrogen may for instance be carried out in the presence of 
a copper chromite catalyst at a pressure of 170 to 230 atmospheres and a 
temperature of 100.degree. to 320.degree. C. 
The starting product required for the preparation of the present alcohols 
is obtained by esterification of the corresponding acid with a lower 
aliphatic alcohol or the acid itself. 
The preparation of the acid is effected by reacting an .alpha.-olefin 
having 6 to 45 carbon atoms with acetic anhydride at a temperature in the 
range of 100.degree. to 140.degree. C. in the presence of a catalytic 
amount of an at least trivalent manganese compound. The .alpha.-olefin may 
consist of a pure olefin fraction, such as 1-octene, or of a mixture of 
.alpha.-olefins having 6 to 45 carbon atoms. If use is made of a mixture 
of .alpha.-olefins the number for n in each separate R-radical may, 
independently of the other R-radicals in the structural formula of the 
acid and of the alcohol to be prepared therefrom, assume any value equal 
to the number of carbon atoms minus two of an .alpha.-olefin present in 
the mixture. The most favourable results are generally obtained at a 
reaction temperature in the range of 115.degree. to 125.degree. C. in the 
presence of manganic acetate as initiator. To prevent oxidation of the 
substrate the concentration of the manganic acetate is preferably chosen 
between 10.sup.-3 and 10.sup.-10 moles per liter. 
The concentration of the olefin fraction is dependent on the desired 
percentage of branched-chain monocarboxylic acids in the reaction product. 
If use is made of an olefin fraction having not more than 12 carbon atoms, 
preference is usually given to a relatively high percentage of 
branched-chain acids. If, however, use is made of an olefin fraction 
having 20 to 45 carbon atoms, then there is found to be a strong 
preference to a mixture of monocarboxylic acids which contains at least 
70% by weight of the addition product of 1 mole of olefin to 1 mole of 
acetic acid. In all cases the reaction conditions will be so chosen that 
ultimately at least 10% by weight of the branched-chain alcohols conforms 
to the first-mentioned structural formula. For the preparation of 
branched-chain monocarboxylic acids from which the esters according to the 
above formula are derived, the molar ratio of converted olefin to manganic 
acetate is at least 4. It has been found that under these last-mentioned 
conditions the composition in weight % of the mixture of telomeric acids 
and, hence, of the alcohols prepared therefrom is for n&lt;17 only dependent 
on the molar ratio of .alpha.-olefin to manganic acetate and the 
concentration of the .alpha.-olefin during the reaction. 
With a monocarboxylic acid obtained by reacting one .alpha.-olefin with 
acetic acid being indicated by R.sub.1, a monocarboxylic acid obtained by 
reaction with two .alpha.-olefins by R.sub.2, a monocarboxylic acid 
obtained by reaction with three .alpha.-olefins by R.sub.3, etc., then, 
for instance, the following weight distributions were obtained 
respectively before and after removal of the R.sub.1 -fraction. 
______________________________________ 
before distillation after distillation 
wt % wt % 
______________________________________ 
R.sub.1 30,7 0,3 
R.sub.2 20,4 19,8 
R.sub.3 21,4 33,6 
R.sub.4 13,0 21,5 
R.sub.5 9,4 15,9 
R .gtoreq.6 
5,1 8,8 
______________________________________ 
The structural formulae of R.sub.3, R.sub.4 and R.sub.5 all conform to the 
first-mentioned formula. R.sub.1 is an unbranched acid of the formula 
R(CH.sub.2).sub.3 COOH and, if n=3 to 9, it is preferably removed from the 
reaction mixture after esterification of the mixture with a lower 
aliphatic monofunctional alcohol. 
The fraction of R.sub.2 is formed by two acids of the formula: 
##STR3## 
For a man skilled in the art it is obvious that, especially if use is made 
of an olefin fraction having 30 or more carbon atoms, it is not possible 
in actual practice to separate the linear acids and the acids having a 
very high molecular weight and a high degree of telomerization and the 
derived esters and alcohols. 
The following is a typical example of a weight distribution of the 
monocarboxylic acids obtained under said conditions and, hence, of the 
alcohols prepared therefrom. 
______________________________________ 
degree of telomerization 
wt % 
______________________________________ 
m = 1 78,0 
m = 2 6,3 
m = 3 6,5 
m = 4 4,0 
m = 5 3,1 
m .gtoreq. 6 2,0 
______________________________________ 
It has been found that as far as the above-mentioned field of application 
of polymers, wax compositions, etc., is concerned the use of mixtures of 
alcohols derived from these branched-chain and straight-chain carboxylic 
acids and the derivatives thereof lead to compositions having unexpectedly 
favourable properties, which remarkably favourably compare with the known 
compositions, which only contain straight-chain alcohols or the 
derivatives thereof. 
The commercially available olefin fractions having 20 to 45 carbon atoms 
are found to contain 60 to 80% by weight of .alpha.-olefins and for the 
rest predominantly consist of vinylidene compounds. 
The resulting alcohols are .gamma.-branched monoalcohols, with the alcohol 
having the formula 
##STR4## 
where R.sub.1 and R.sub.2 represent linear alkyl groups which together 
have the same number of carbon atoms as the group R. 
Separation of these vinylidene groups-containing fractions from the 
.alpha.-olefins would give rise to so many technological problems that it 
must be considered impracticable for economic reasons. It has been found, 
however, that for most uses products having exceptionally good properties 
are obtained if besides the branched-chain alcohols having the above 
formulae or the derivatives thereof there is present an amount of 40 to 60 
percent by weight of the alcohol fraction or of the derivatives thereof 
which consists of or is derived from linear aliphatic monoalcohols, with 
the alcohol having the formula R CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OH, 
where R represents a CH.sub.3 (CH.sub.2).sub.n group, with n being an 
integer of from 17 to 42. 
The invention also relates to a resin composition having improved internal 
and external lubricating properties, comprising a polymer or copolymer of 
vinyl chloride and 0,1 to 5% by weight, calculated on the polymer, of an 
alcohol or a derivative thereof according to the opening paragraph, 
characterized in that at least 40 percent by weight of the alcohol present 
as such, or at least 40 percent by weight of the alcohol from which the 
derivatives are derived, have a branched-chain structure, and at least 10 
percent by weight thereof conform to the above first-mentioned formula. 
It has been found that the quality of the resin compositions is not 
detrimentally influenced if besides the branched-chain alcohols and/or the 
derivatives thereof, with the alcohol having the above first-mentioned 
formula, there is still present an alcohol and/or a derivative thereof 
with the alcohol having the formula: 
##STR5## 
where R has the meaning given for it with the first-mentioned formula. As 
indicated above, the commercially available olefin fractions having 24 to 
50 or more carbon atoms in considerable part consist of vinylidene 
compounds. 
These cannot be removed or only with very great difficulty. It has been 
found, however, that resin compositions having excellent processing 
properties can be obtained if besides the branched-chain alcohols and/or 
the derivatives thereof with the alcohols having the first-mentioned 
formula and the two last-mentioned ones, there is present an amount of 40 
to 60 percent by weight of linear aliphatic monoalcohols and/or 
derivatives thereof, with the alcohol having the formula R(CH.sub.2).sub.3 
CH.sub.2 OH, where R has the meaning given for it with the first-mentioned 
formula, and about 30 to 40 percent by weight of .gamma.-branched primary 
alcohols and/or the derivatives thereof, with the alcohol having the 
formula 
##STR6## 
where R.sub.1 and R.sub.2 represent linear alkyl groups which together 
have the same number of carbon atoms as the group R. 
By polyvinyl chloride and copolymers of polyvinylchloride are to be 
understood here all possible types of homopolymers of vinyl chloride, and 
post-chlorinated polyvinyl chloride, and also copolymers whose most 
important constituent is vinyl chloride, and a small proportion of other 
copolymerizable monomers, such as copolymers of vinyl chloride and vinyl 
acetate, copolymers of vinyl chloride and vinylidene chloride, copolymers 
of vinyl chloride and acrylonitrile, copolymers of vinyl chloride and 
maleic or fumaric esters and copolymers of vinyl chloride and styrene, and 
also mixtures containing a high percentage of polyvinyl chloride resin and 
a small percentage of some other synthetic resin, such as chlorinated 
polyethylene, copolymers of acrylonitrile, butadiene and styrene. 
The lubricants may be incorporated into the polyvinyl chloride or 
copolymers thereof in the usual manner. This may be done by mixing on a 
roll or in a mixer of the Banbury type. 
Alternatively, the lubricant may be dissolved or dispersed in some 
appropriate solvent. 
The lubricant may be added along with other composition ingredients such as 
stabilizers, fillers and plasticizers, or in a separate step. The physical 
properties of the formulated resin composition may be considerably varied 
by changing the amount and the nature of the constituents to be 
incorporated therein without detracting from the lubricating properties of 
the present lubricants. 
For a man skilled in the art it will generally not be difficult to find the 
most suitable percentage for obtaining an optimum effect for each use 
envisaged. In a number of cases it will be posible for the alcohols or 
derivatives according to the present invention to be used as such, i.e. 
without admixing other known polymer and/or engine lubricating agents, but 
generally it will be preferred that other products should be admixed in 
order to obtain more favourable physical and/or chemical properties. 
The invention further relates to a wax composition for entirely or partly 
replacing carnauba wax or montan wax and substantially consisting of one 
or more alcohols and/or derivatives thereof characterized in that at least 
40 percent by weight of the alcohol present as such, or at least 40 
percent by weight of the alcohol from which the derivatives are derived, 
is branched, and at least 10 percent by weight thereof conforms to the 
above first-mentioned formula. 
It has been found that the quality of the wax compositions is not 
detrimentally influenced if besides the branched-chain alcohols or the 
derivatives thereof, with the alcohol having the above first-mentioned 
formula, there is present an alcohol or derivative thereof, with the 
alcohol having the formula 
##STR7## 
where R has the meaning given for it with the first-mentioned formula. 
As mentioned above, the commercially available olefin fractions having 24 
to 50 or more carbon atoms in considerable part consist of vinylidene 
compounds. They cannot be removed or only with great difficulty. It has 
been found, however, that wax compositions having excellent properties can 
be obtained if besides the branched-chain alcohols or the derivatives 
thereof, with the alcohols having the first-mentioned formula and the two 
last-mentioned ones, there is present an amount of 40 to 60 percent by 
weight of linear aliphatic mono alcohols or derivatives thereof, with the 
alcohol having the formula R(CH.sub.2).sub.3 CH.sub.2 OH, where R has the 
meaning given for it with the first-mentioned formula, and about 30 to 40 
percent by weight of .gamma.-branched primary alcohols or the derivatives 
thereof, with the alcohol having the formula: 
##STR8## 
where R.sub.1 and R.sub.2 represent linear alkyl groups which together 
have the same number of carbon atoms as the group R.

The invention is further described in, but not limited by the following 
examples. 
EXAMPLE I 
For the preparation of branched-chain acids use was made of a commercially 
available starting mixture of olefins consisting of about 22% by weight of 
olefins having not more than 28 carbon atoms and about 78% by weight of 
olefins having at least 30 carbon atoms (C.sub.30 +olefins), about 66% by 
weight of the olefins being .alpha.-olefins. The remaining olefin 
compounds were vinylidene compounds. The reaction was carried out in a 
stirred (700 r.p.m.) reactor provided with 8 baffles and equipped with a 
stirrer having 6 diametrically opposed blades. Into this reaction vessel 
there were charged 12,5 liters (132 moles) of acetic anhydride. The liquid 
was heated to 120.degree. C. while nitrogen was slowly passed through to 
remove the oxygen present in it. With the liquid being kept at 120.degree. 
C., first of all the C.sub.30+ olefin mixture was added. Of this mixture 
in all 1175 g (2,5 moles) were added over a period of 210 minutes. 12 
minutes after a start had been made with adding olefin a slurry of 0,625 
moles Mn (III) acetate in 2,5 l acetic anhydride was added over a period 
of 216 minutes (so for a period of 18 minutes after the last of the olefin 
had been added addition of Mn (III) acetate was continued to ensure 
complete conversion of the olefin). 
The mixture was subsequently filtered to remove the Mn(II) acetate that had 
formed. Next, acetic anhydride and the acetic acid formed were removed by 
distillation. To the residue there were added 2,5 l acetic acid and 0,3 l 
water. With vigorous stirring the mixture was boiled with refluxing to 
hydrolyse the obtained anhydrides. Finally, the water-acetic acid layer 
was separated off, the product washed 3 times with hot water and dried. 
The resulting mixture of straight-chain and branched-chain acids had an 
acid number of 86. 
Of the acid thus obtained 1025 g were transferred to an autoclave which was 
heated to about 100.degree. C. To the molten acid 51,25 g of a 
barium-promoted copperchromite catalyst were added, after which the system 
was rinsed three times with nitrogen and once with hydrogen. 
Subsequently, hydrogen was fed in up to a pressure of 174 atmospheres. The 
temperature was then allowed to rise from 100.degree. to 310.degree. C. 
over a period of 50 minutes, after which the pressure rose to 223 
atmospheres. Over a period of 23 minutes hydrogen was used up to such a 
degree that the pressure decreased to 178 atmospheres. 
Next, the temperature was decreased to 100.degree. C. and hydrogen fed in 
under a pressure of up to 174 atmospheres. The temperature was again 
allowed to rise over a period of 50 minutes to a value of 310.degree. C., 
at which temperature a pressure of 229 atmospheres was obtained. 
Afterwards no longer any decrease in pressure was observed, so that the 
reaction could be considered completed. After filtration of the reaction 
mixture a light coloured product was obtained having a residual acid 
number of &lt;5 and a hydroxyl number of 81. 
EXAMPLE II 
In this example use was made of a starting mixture of telomeric acids 
derived from n-decene. This mixture had been obtained by removing the 
lower telomeric fraction and was composed as follows: 
______________________________________ 
wt % 
______________________________________ 
n = 1 &lt;5 
n = 2 30 
n = 3 35 
n = 4 15 
n = 5 10 
n = 6 5 
______________________________________ 
Using the same procedure as indicated in Example I 817 g of this mixture 
(acid number 104) were mixed with 40,85 g of barium-promoted copper 
chromite (5% by weight, calculated on the substrate). 
After 3.times.rinsing with nitrogen and 1.times.with hydrogen at a pressure 
of 20 atmospheres and a temperature of 25.degree. C. hydrogen was fed in 
up to a pressure of 179 atmospheres. Subsequently, over a period of 55 
minutes, the temperature was increased to 310.degree. C. After 55 minutes 
at 310.degree. C. the pressure had dropped from 247 atmospheres to 199 
atmospheres. The system was cooled to 90.degree. C., and hydrogen was fed 
in up to a pressure of 176 atmospheres, after which the temperature was 
increased to 310.degree. C. over a period of 45 minutes. When after 3 
hours no longer any pressure drop was observed, the product was isolated 
by filtration. The residual acid number was 5 and the hydroxyl number 106. 
EXAMPLE III 
In this example an illustration is given of the fitness as lubricant in a 
polyvinyl chloride (PVC) formulation of the novel monoalcohols and the 
esters derived therefrom according to the present invention and a 
comparison is made with a few commercially available lubricants. 
Product A=butane diol ester of montanic acid of which 40% is saponified 
with calcium. 
Product B=a mixture composed of tridecyl stearate and equal parts by weight 
of glycerol mono-oleate and pentaerythritol adipate/oleate. 
Product C=a mixture of mono-alcohols prepared from an olefin fraction 
having 22-26 carbon atoms. 
Product D=a mixture of mono-alcohols prepared from an olefin fraction 
having 26 to 30 carbon atoms. 
Use was made of the following test methods: 
1. Brabender test for determining the rheological properties, the most 
important parameters being the gelation time and the melt viscosity 
(torque upon gelation and the torque 5 minutes after gelation). 
2. High speed mill test for studying the behaviour during processing, such 
as calendering. 
The polymer is observed for sticking to the roll (stick time) and change in 
colour both at elevated temperature and at high speeds. 
3. Clarity. This property was determined by moulding formulated PVC 
mixtures into plates about 1 mm thick and subsequently visually evaluating 
the clarity. 
Procedure 
Each formulation was intensively mixed on a Papenmeier mixer. Part of the 
mixture was used for testing in the Brabender Plasticorder under the 
following conditions: 
______________________________________ 
temperature 170.degree. C. 
speed 30 revolutions per minute 
sample weight 30 g 
______________________________________ 
Another part of the mixture was thoroughly mixed on a roll mill at 
160.degree. C. until the mixture was entirely homogeneous. The required 
samples were cut out of a rolled sheet about 2 mm thick. 
The samples were heated in an air circulation oven at 185.degree. C., from 
which they were removed at 10 minute intervals, after which they were 
visually evaluated for change in colour. This colour change was taken as a 
measure of the decomposition rate of the PVC compound. The results of the 
experiments are combined in the following table and rated from 1 to 5, 
where 
3=slow gradual change; 
4=good early colour, rapid colour change; 
5=good 
1=poor 
2=fairly rapid gradual degradation. 
The formulation of the polyvinyl chloride used in this example was as 
follows: 
______________________________________ 
Parts by weight 
______________________________________ 
PVC - suspension polymer 100 
dibutyl-tin-bis-laurylmercaptan 
1,0 
mixture of monobutyl tin trisisooctyl- 
thioglycolate 
dibutyl tin bisisooctylthioglycolate 
1,0 
epoxidized soybean oil 
phenolic antioxidant 
lubricant 0,5 
______________________________________ 
1. Brabender test 
______________________________________ 
lubricant (parts by weight) 
0,5 
type of lubricant gelation time (s) 
______________________________________ 
control 85 
product A 330 
product B 105 
product C (invention) 
70 
product D (invention) 
145 
torque upon gelation 
control 650 
product A 540 
product B 610 
product C (invention) 
640 
product D (invention) 
620 
______________________________________ 
2. High speed mill test 
______________________________________ 
lubricant (parts by weight) 
0,5 
time (min.) after which 
type of lubricant polymer sticks to roll 
______________________________________ 
control 10 
product A 40 
product B 35 
product C (invention) 
20 
product D (invention) 
40 (no discoloration) 
______________________________________ 
The above test results show that the products according to the invention 
may best be considered an external lubricant. Rather surprising is that at 
a relatively high concentration of 0,5 parts by weight per 100 parts of 
polymer the clarity of the polymer was still excellent where use made of 
the product C. 
3. Clarity and thermal stability 
______________________________________ 
lubricant (parts by weight) 
0,5 
0,5 thermal 
type of lubricant 
clarity stability 
______________________________________ 
control good 3 
product A poor 3 
product B -- 4 
product C (invention) 
excellent 3 
product D (invention) 
poor 3 
______________________________________ 
EXAMPLE IV 
In this example the test results are given for the C.sub.30+ alcohols 
prepared according to Example I and the urethane of toluene diisocyanate 
and the acetic esters, adipic esters and C.sub.30+ acid ester thereof in a 
PVC-formulation. The formulation of the PVC used was as follows: 
______________________________________ 
parts by weight 
______________________________________ 
PVC-suspension polymer 
100 
di(.beta.-carbobutoxyethyl)tin bisiso 
octylthioglycolate 2 
lubricant 0,3-1,0 
______________________________________ 
Each formulation was intensively mixed on a Papenmeier mixer. Part of the 
mixture was used for testing in the Brabender Plasticorder under the 
following conditions: 
______________________________________ 
temperature 160.degree. C. 
speed 30 revolutions per minute 
sample weight 32,5 g 
pressure 5 kg 
______________________________________ 
Clarity 
To determine the influence of the lubricant on the clarity of the 
stabilized formulations 3 mm thick sheets had been pressed at 190.degree. 
C. Samples of the gelation experiments were taken 10 minutes after 
gelation. The transmission of these sheets was measured with a Bausch and 
Lomb spectrophotometer. The transmission at 690 nm was used as a measure 
of the clarity of the sheet. 
The results of the Brabender gelation tests and clarity tests on the 
above-mentioned lubricants are summarized in the table below. 
__________________________________________________________________________ 
Brabender gelation test 
torque 10 temp. 
clarity of 3 mm 
gelation 
fusion 
min. after 
temp. at 
after 
thick pressed 
time torque 
gelation 
fusion 
10 min. 
sheet at 690 nm 
lubricant 
phr 
(min.) 
(m grams) 
(m grams) 
(.degree.C.) 
(.degree.C.) 
% T 
__________________________________________________________________________ 
C.sub.30+ alcohols 
0,3 
5,1 2600 2850 163 170 73 
0,5 
11,6 2550 2800 167 171 40 
acetic acid esters 
0,3 
5,1 2575 2850 163 170 76 
of C.sub.30+ alcohols 
0,5 
9,6 2575 2850 164 171 50 
adipic acid 
diesters of C.sub.30+ 
0,3 
6,7 2550 2850 163 171 47 
alcohols 0,5 
25,3 2400 2700 163 170 23 
C.sub.30+ acid esters 
0,3 
4,2 2500 2850 162 170 76 
of C.sub.30+ alcohols 
0,5 
8,8 2500 2850 163 170 54 
diurethane of 
toluene diisocya- 
0,3 
6,3 2550 2875 163 170 75 
nate and C.sub.30+ 
0,5 
10,1 2575 2800 165 170 44 
alcohol 
control -- 1,2 2700 2850 156 171 85 
ethylene glycol 
0,3 
2,7 2600 2950 150 169 83 
ester of monta- 
nic acid 0,5 
6,3 2575 2900 163 171 69 
__________________________________________________________________________ 
The above results clearly show that both the C.sub.30+ alcohols and the 
esters derived therefrom have the effect of an external lubricant. 
EXAMPLE V 
In this example the results are given of tests on a C.sub.10 alcohol TP 
(derived from n-decene) and, the oleic acid ester and the diurethane 
thereof and diphenylmethane-4,4'-diisocyanate (MDI). TP standing for total 
product, i.e. the mixture of telomeric alcohols as it is obtained without 
the n=1 fraction having been removed. The composition was about as 
follows: 
______________________________________ 
wt % 
______________________________________ 
n = 1 30-40 
n = 2 15-20 
n = 3 20-25 
n = 4 12-15 
n = 5 8-10 
n .gtoreq. 6 4-6 
______________________________________ 
The formulation of the PVC used was the same as the one used in Example IV. 
The results are summarized in the table below. The concentration of the 
lubricant was in all formulations 0,5 phr. 
__________________________________________________________________________ 
Brabender gelation tests 
torque 10 temp. 
clarity of 3 mm 
gelation 
fusion 
min. after 
temp. at 
after 10 
thick pressed 
time torque 
gelation 
fusion 
min. sheet at 690 nm 
lubricant 
(min.) 
(m grams) 
(m grams) 
(.degree.C.) 
(.degree.C.) 
% T 
__________________________________________________________________________ 
-- 1,2 2700 2850 156 171 85 
oleic acid ester 
of TP.sub.10 alcohol 
6,4 2600 2900 162 170 66 
urethane of TP.sub.10 
4,1 2600 2950 159 170 84 
alcohol and 
MDI 
TP.sub.10 alcohol 
3,0 2600 2850 159 169 84 
glycol mono 
oleate 2,1 2600 2850 160 171 85 
n-butyl stearate 
2,3 2500 2850 158 171 85 
__________________________________________________________________________ 
EXAMPLE VI 
The C.sub.30+ alcohol prepared according to Example I and the urethane of 
toluene diisocyanate and the acetic acid ester, adipic acid diester and 
C.sub.30+ acid ester derived therefrom were tested for their being 
suitable entirely or partially to replace the known Carnauba and/or 
montanic acid waxes. The following properties were measured. 
1. Ubbelohde dropping point .degree.C. (heating rate 1.degree. C./min.) 
which is a measure of the "melting point" of the wax composition. The 
dropping point was determined with a Mettler FP 53 tester. 
2. Ubbelohde dropping point .degree.C. (heating rate 1.degree. C./min.) as 
under 1, but after mixing 1 part of wax with 4 parts of paraffin. 
3. Penetration of paraffin mixture, in accordance with ASTM D 1321-70. In 
this way an indication of the hardness increasing effect of the esters is 
obtained. 
4. Continental solid point, in accordance with ASTM D 938-49. This point 
corresponds to the congealing point of 1 part of wax, 4 parts of paraffin 
and 15 parts of turpentine. 
5. Consistency of paste, as described in "Vom Wachs, Hoechster Beitrage zur 
Kenntnis der Wachse", Farbw. Hoechst, Frankfurt-Hoechst, Vol. II, Beitrag 
II, p. 50-51. In that test a stamp of some particular weight and 
dimensions is slowly, while subjected to a gradually increasing pressure, 
brought into contact with the paste. 
6. Solvent retention, to determine this property 1 part of the wax to be 
examined was mixed with 4 parts of paraffin and 15 parts of turpentine and 
the resulting mixture was brought into a tin. After the closed tin had 
been left for 17 hours at 23.degree. C., it waspplaced in a ventilated 
oven. After it had been in the oven for 7 days at 32.degree. C. and 
subsequently on a table for another 7 days at 20.degree. C., the solvent 
retention was measured. It is expressed as follows: solvent retention= 
##EQU1## 
The results are listed in the following table and compared with those of 
the known wax compositions or components thereof. 
______________________________________ 
drop- pene- 
ping.sup.a 
tration.sup.a 
point of of 
drop- paraffin paraffin 
ping mixture mixture 
Wax point (.degree.C.) 
(0,1 mm) 
______________________________________ 
paraffin 60 (60) 17 
carnauba prime yellow.sup.b 
85 81 7 
montanic acids 86 79 5 
montanic acid ethylene 
glycol ester 83 77 7 
montanic acid 1,3-butane- 
diol ester-40% calcium soap 
102 90 5 
C.sub.30+ alcohols or the 
derived 88 73 10,5 
acetic acid ester 81 68 14,5 
adipic acid diester 90 74 9,0 
C.sub.30+ acid ester of C.sub.30+ 
.sub.d 94 80 7,5 
alcohol 
diurethane of toluene 98 85 7,5 
diisocyanate and C.sub.30+ alco- 
hol 
______________________________________ 
.sup.a Paraffin mixture: 1 part of wax + 4 parts of paraffin 
.sup.b Carnauba wax, which is a natural wax, containing 80% of esters of 
acidslong-chain (&gt; C24) and substituted or unsubstituted cinnamic acid 
and longchain (&gt;C30) alcohols 
.sup.d Derived from straightchain and branchedchain C.sub.30+ alcohols 
according to the invention. 
__________________________________________________________________________ 
paste con- 
continental.sup.c 
solvent 
sistency 
solid point 
retention 
Wax (g/cm.sup.2) 
(.degree.C.) 
(%) 
__________________________________________________________________________ 
Carnauba fatty gray 
1500 40 31 
montanic acids 700 40 20 
montanic acid 1,3-butane- 
diol ester-40% calcium soap 
765 40 51 
C.sub.30+ alcohols or the 
derived 1140 46 84 
acetic ester 820 42 76 
adipic diester 1170 43 82 
.sub.d 
C.sub.30+ acetic ester 
950 45 63 
diurethane of toluene 
diisocyanate and C.sub.30+ 
alcohol 1170 45 80 
__________________________________________________________________________ 
.sup.c Paste composition: 1 part of wax, 4 parts of paraffin; 15 parts of 
turpentine.