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Description  |
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This invention relates to a process for the preparation of polyalkylene
glycol ethers based on saccharose which are valuable starting materials
for the production of hard polyurethane foams.
It is known to react saccharose with alkylene oxides to produce
saccharose-hydroxyalkyl ethers. Saccharose reacts with ethylene oxide in
aqueous solution in the presence of sodium hydroxide (J. W. LeMaistre, R.
B. Seymour, J. Org. Chem. 13, 782 (1948). A process for the preparation of
saccharose-hydroxyalkyl ethers is based on this reaction in which
saccharose is reacted with ethylene oxide or propylene oxide in
concentrated aqueous solution at elevated temperature in the presence of
potassium hydroxide as catalyst (U.S. Pat. Nos. 3,085,085 and 3,153,002,
German Pat. No. 1,443,026).
The reaction of saccharose with alkylene oxides in aqueous solution is
liable to be accompanied by unwanted side reactions, for example the
partial hydrolysis of alkylene oxide by the water which is used as a
reaction medium. The hydrolyzed alkylene oxide, the polyalkylene glycols
formed from them as well as other by-products (indicated by a dark
discoloration of the reaction mixture) have a deleterious effect on the
properties of polyurethane foams produced from such saccharosehydroxyalkyl
ethers. The high proportion of bifunctional linear by-products causes the
functionality of these polyethers to be severly reduced compared with that
of a pure saccharose polyol. The high proportion of bifunctional linear
by-products present means that the saccharose polyethers produced by this
method are only of limited use for the production of valuable polyurethane
foams. This is because the use of such saccharose polyethers is likely to
result in friable foams of moderate strength and non-uniform cell
structure. Another disadvantage of polyurethane foams obtained from
saccharose polyethers which have been prepared in this way is their low
proportion of closed cells which causes them to be poor thermal
insulators.
For this reason an attempt has already been made to carry out the
alkoxylation of saccharose in the absence of water and in the presence of
xylene (U.S. Pat. No. 2,652,394). This process, however, results in badly
discolored products due to caramelization or charring of the saccharose.
The formation of high proportions of bifunctional by-products can be
reduced by using a process in which saccharose is first reacted with 4 to
8 mols of alkylene oxide in a concentrated aqueous solution in the
presence of potassium hydroxide. After this nearly all the water is
removed from the reaction mixture and the addition of alkylene oxide is
then continued (U.S. Pat. No. 3,085,085). Even in this process a high
proportion of the alkylene oxide undergoes reaction in the presence of
relatively large quantities of water in the reaction mixture. Hence even
the products of this process tend to have the disadvantages described
above which occur when the alkoxylation is carried out without an
intermediate stage in which water is removed. One important technical
difficulty of the known process of reacting saccharose with alkylene
oxides in aqueous solution is that the major portion of sugar must be
added at temperatures which are at or only slightly below the boiling
point of water. Another disadvantage of this process is that the reaction
velocity of alkylene oxide addition is relatively low, which greatly
favors the formation of by-products during the alkylene oxide addition
reaction.
It is also known that saccharose, present in a suspension in glycerol, can
be reacted with propylene oxide in the presence of potassium hydroxide and
a small quantity of water, a polyether mixture being obtained which in
addition to propoxylated saccharose contains a high proportion of
propoxylated glycerol (U.S. Pat. No. 3,442,888). The polyethers prepared
by this process still contain a substantial proportion of linear
polypropylene glycols in addition to the propoxylated saccharose and
propoxylated glycerol, due to the reaction of propylene oxide with the
water present in the reaction mixture. This, and particularly the high
proportion of glycerol polyethers, causes the functionality of polyethers
obtained by this process to be much lower than the functionality of a pure
saccharose polyol. This low functionality has an undesirable effect on the
properties of polyurethane foams produced from such saccharose-glycerol
polyols.
It is essential when reacting saccharose with alkylene oxides that the
reaction mixture be freely stirrable. Adequate removal of the large amount
of heat produced in the reaction with alkylene oxides is only possible if
the reaction mixture can be stirred vigorously. The problem of being able
to stir the mixture is particularly difficult when the saccharose is first
introduced and when large quantities of unreacted solid saccharose are
present during the addition of alkylene oxide. Mixtures of saccharose and
alkali metal hydroxide which are difficult to stir may lead to
caramelization or charring reactions on the walls of the reaction vessel
which are inevitably hot due to the heating of the reaction mixture.
Previously one could only insure that the reaction mixtures which contain
saccharose would be freely stirrable by using fairly concentrated
solutions of saccharose in water or by suspending saccharose in a large
quantity of glycerol. These methods have serious disadvantages, as already
described above. The possibilities of reducing the extent of the side
reactions by reducing the water content of aqueous solutions or of
suspensions are limited since mixtures of saccharose and potassium
hydroxide which contain less than 5% of water cannot be easily stirred.
It is therefore an object of this invention to provide a process for the
preparation of saccharose polyethers which makes saccharose polyethers
with a high functionality easily available and substantially eliminates
the disadvantages of the existing processes as described above.
According to the invention, this problem has been solved by subjecting
mixtures of saccharose, a small quantity of water, a small quantity of a
low molecular weight polyol, monoamine or polyamine or any combination of
these to an alkoxylation reaction the reaction being carried out in
suspension in aromatic hydrocarbon solvents and in the presence of alkali
metal hydroxide catalysts.
This invention therefore relates to a process for the preparation of
saccharose-hydroxyalkyl ethers by the alkoxylation of saccharose,
characterized in that a mixture containing
a. 100 parts by weight saccharose,
b. 2 - 5 parts by weight of water,
c. 2 - 20 parts by weight of a low molecular weight higher valent alcohol,
monoamine or polyamine or any combination of these.
d. 40 - 150 parts by weight of an aromatic hydrocarbon solvent and
e. 1 - 5 parts by weight of an alkali metal hydroxide is first prepared at
temperatures of between 20.degree.C and 110.degree.C, and the mixture is
then reacted with alkylene oxides at temperatures of 85.degree. to
130.degree.C and pressures of 1.3 to 5.0 atmospheres.
The process according to the invention is preferably carried out as
follows:
Saccharose is first suspended at room temperature, normally between
10.degree.C and 30.degree.C in an aromatic hydrocarbon solvent, the
quantity of solvent used being 40 to 150%, preferably 50 to 100% of the
weight of saccharose.
A quantity of a water-soluble, short chained polyol, monoamine or polyamine
which is small compared with the quantity of sugar, a small quantity of
water and a small quantity of alkali metal hydroxide used as catalyst are
added in any sequence to this suspension under an atmosphere of nitrogen
at temperatures of between 20.degree.C and 110.degree.C preferably between
50.degree.C and 90.degree.C, the alkali metal hydroxide being preferably
used in the form of a concentrated aqueous solution. The resulting mixture
which is an easily stirrable paste is then heated to the reaction
temperature of 85.degree. to 130.degree.C, preferably 95.degree. to
115.degree.C, and then reacted with alkylene oxide at pressure of 1.3 to
5.0 atmospheres, preferably 1.5 to 3.5 atmospheres. The reaction
temperature is maintained within the range of 85.degree. to 130.degree.C,
preferably 95.degree. to 115.degree.C, either by heating or by cooling of
the reaction mixture, as required. When alkyleneoxide addition has been
completed the alkaline polymer is neutralized with dilute mineral acid. If
desired, an anti-oxidant, e.g. 2,6-di-tert. butyl-p-cresol, may be added
to the neutralized product. The water and hydrocarbon are distilled off
down to a small residue under vacuum at elevated temperatures, about
50.degree. to 130.degree.C, and the salts which separate in the process
are removed by filtration.
Any aromatic hydrocarbon solvents boiling within the range of 80.degree. to
180.degree.C may be used for the process of the invention, for example
benzene, toluene, ethyl benzene, xylenes or chlorobenzene. The preferred
solvent for the process of the invention is toluene. The aromatic
hydrocarbons may also be used as mixtures with aliphatic solvents boiling
within the range of 80.degree. to 180.degree.C.
The polyols, monoamine and/or polyamines used for the process according to
the invention are water-soluble compounds which have melting points below
100.degree.C and molecular weights generally between 60 to 250. Examples
of such compounds are: ethylene glycol, propylene glycol, butane-1,4-diol,
diethylene glycol, dipropylene glycol, trimethylol propane, glycerol,
sorbitol, mannitol, mono-, di- and triethanolamine, mono-, di and
triisopropanolamine, N-alkyl-alkanolamines such as N-methyl-diethanolamine
and N-ethyl-diethanolamine, lower aliphatic monoalkylamines and
dialkylamines, cycloalkylamines, aralkylamines, alkylene diamines such as
ethylene diamine and polyalkylene polyamines such as diethylene triamine
and triethylene tetramine. The preferred compounds for the process of the
invention are higher valent alcohols and amino alcohols.
Instead of the pure compounds there may also be used mixtures of two or
more of the additives described above. In either case, the total quantity
of additives used is 2 to 20%, preferably 3 to 15% of the weight of
saccharose.
According to the invention, the water content of the mixture of saccharose,
additives and catalyst is between 1 and 5%, preferably between 2.0 and
4.5% of the weight of the saccharose portion.
The reaction with the alkylene oxide is carried out in the presence of
alkali metal hydroxides as catalyst, preferably sodium hydroxide or
potassium hydroxide. According to a preferred method of carrying out the
process, potassium hydroxide is used in the form of an approximately 50%
aqueous solution and the quantity of potassium hydroxide used is between
1.0 and 5.0%, preferably between 2.0 and 3.0% of the weight of saccharose.
The alkylene oxides used in the process according to the invention are
preferably ethylene oxide, propylene oxide and/or 1,2-butylene oxide. The
alkoxylation reaction according to the invention may be carried out using
either only one of the above mentioned alkylene oxides or any mixtures of
alkylene oxides. If desired, various alkylene oxides may be added in
succession to a reaction mixture in the process according to the invention
to produce so-called graft polyethers.
The reaction temperatures may vary within a wide range. Temperatures of
between 85.degree. and 130.degree.C and preferably between 95.degree. and
115.degree.C are generally employed. The reaction with alkylene oxides is
carried out at an elevated pressure of between 1.3 and 5.0 atmospheres,
preferably between 1.5 and 3.5 atmospheres.
The process according to the invention may be applied to the preparation of
polyethers which can be reacted with polyisocyanates to produce hard
polyurethane foams. These foams are either directly produced with
polyisocyanates or only after they have been mixed with suitable short
chain diols or polyols or bifunctional or polyfunctional polyalkylene
glycols. When it is desired to make such hard foams the quantity of
alkylene oxide used is such that each saccharose molecule reacts on an
average with about 8 to 20 and preferably about 8 to 15 molecules of
alkylene oxide. The polyethers obtained in this way have hydroxyl numbers
of between 250 and 750, preferably between 350 and 550. The functionality
of the polyethers is above 5.5 in the case of products with a low hydroxyl
number and in the region of 7 or more in the case of products with a high
hydroxyl number.
The polyethers prepared in accordance with the invention are clear,
yellowish to brownish, thick liquid or highly viscous oils. The viscosity
of the products depends on the hydroxyl number and quantity of additives
contained in them and varies from 7000 cP (at 25.degree.C) in the case of
low hydroxyl numbers (about 350) to above 400,000 cP in the case of high
hydroxyl numbers (about 550). By varying the hydroxyl number and the
proportion of additives rather than by varying the small water content it
is possible to produce products whose viscosity is optimally adjusted in
each case to the given use purpose of the product.
The following are the major advantages of the process according to the
invention:
The saccharose can be introduced at room temperature, normally between 10
and 30.degree.C, so that trouble caused by solvent vapors or hot steam can
easily be avoided.
The inert atmosphere which is absolutely essential for the reaction with
alkylene oxides can very easily be achieved since at room temperature
atmospheric oxygen can easily be removed by repeated evacuation of the
reaction vessel and refilling with nitrogen.
The mixtures of starting materials are easily stirrable at every phase of
the reaction. This ensures efficient cooling which is necessary for rapid
reaction with alkylene oxides.
The reaction mixtures are characterized by a relatively high reaction
velocity in the reaction with alkylene oxides.
Due to the ease with which the system can be stirred, saccharose is
prevented from caking on the hot walls of the reaction vessel and
carmelization of saccharose is therefore avoided.
The saccharose undergoes complete reaction with alkylene oxides without any
residue. Due to the small water content of the reaction mixtures, side
reactions of alkylene oxides occur only to a slight extent.
The saccharose polyethers prepared by the process according to the
invention are pale in color and due to the relatively high proportion of
saccharose-hydroxyalkyl ethers in them they have a relatively high
functionality.
The process according to the invention may, of course, also be modified so
that only part of the alkylene oxide is reacted at first and the remainder
is added only after an intermediate removal of water.
The saccharose polyethers obtained by the process according to the
invention are valuable starting materials for the production of hard
polyurethane foams by known processes for the production of polyurethane
foams by reaction with preferably aromatic polyisocyanates in the presence
of the usual auxiliary agents and additives.
The apparatus used for carrying out the practical examples described below
was an autoclave equipped with a heating and cooling device, a stirrer, a
device for displacing air with gaseous nitrogen (e.g. vacuum attachment
and nitrogen inlet) and a device for adding alkylene oxide.
The invention is further illustrated but is not intended to be limited by
the following examples in which all parts and percentages are by weight
unless otherwise specified.
EXAMPLE 1
350 kg of saccharose (1025 mol) were introduced into 182 kg of toluene at
room temperature with stirring. Atmospheric oxygen was removed from the
reaction vessel by twice evacuating the vessel and refilling with
nitrogen. The easily stirrable suspension of saccharose in toluene was
heated and 20 kg of 1,2-propylene glycol, 15.0 kg of 50% aqueous potassium
hydroxide solution and 5.9 kg of water were added successively at
80.degree.C (total quantity of water together with the water used for
dissolving the potassium hydroxide; 13.4 kg; 3.83% of water based on the
quantity of saccharose). The easily stirrable, pasty mixture was heated to
105.degree.C and 874 kg (15070 mol) of propylene oxide were gradually
added at a pressure of 2.3 to 1.6 atmospheres and a temperature of
104.degree. to 105.degree.C (55 kg per hour; propylene oxide introduced
under the surface of the reaction mixture). The reaction temperature was
kept within this range by either cooling or heating the reaction mixture
as required. Stirring was continued for a further 3 hours at 105.degree.C
after all the propylene oxide had been added.
After the addition of 250 kg of water, the alkaline polymer was neutralized
with 51 kg of 12.6% aqueous sulphuric acid (pH of the emulsion 6.4). Water
and toluene were then distilled off under vacuum at 70.degree. to
90.degree.C after the addition of filtering agents (cellulose powder and
synthetic magnesium silicate) and an antioxidant
(2,6-di-tert.-butyl-p-cresol). When the water content of the product was
0.9%, the salts which separated and the filtering agents were filtered off
after the addition of 150 liters of toluene. The filtrate was then
distilled under vacuum of 85.degree. to 99.degree.C for complete removal
of water and toluene.
The resulting pale yellow, viscous product had the following physical
properties:
Hydroxyl number (mg KOH/g)
416
pH 7.3
Water content (%) 0.05
Viscosity n.sub.25.sub..degree.C (cP)
28000
average functionality
(calculated from the quantity of
starting material and hydroxyl
number) 5.95
Remarks:
The hydroxyl numbers given in the examples were determined by the usual
method of acylating the polyether with excess phthalic acid anhydride in
pyridine.
To determine the pH values, a mixture of methanol and water in a volumetric
ratio of 9 : 1 was used as solvent and 10 ml of the polyether and 100 ml
of the solvent were used for the pH determination. The measurement was
carried out using a single-rod glass electrode.
EXAMPLE 2
Introduction of the starting components, addition of alkylene oxide and
working up of the alkaline polymer were carried out as described in
Example 1.
The following starting materials were used:
165 kg of toluene
315 kg (921 mol) of saccharose,
32.7 kg of trimethylol propane,
9.2 kg of propylene glycol,
13.4 kg
5.6 kg of water (total quantity of water 12.3 kg, 3.9% of
water based on the weight of the saccharose)
828 kg (14280 mol) of propylene oxide in 15 hours.
First saccharose was added at room temperature, followed by trimethylol
propane at 60.degree. to 70.degree.C and then by propylene glycol,
potassium hydroxide solution and water in that order at 80.degree.C. The
mixture of starting components was freely stirrable.
The pale yellow, viscous product obtained had the following physical
properties:
hydroxyl number (mg KOH/g)
417
pH 7.3
water content (%) 0.08
viscosity n.sub.25.sub..degree.C (cP)
21300
average functionality
(calculated from the quantity of
starting material and hydroxyl number)
5.75
EXAMPLE 3
The introduction of starting components, addition of alkylene oxide and
working up of the alkaline polymer were carried out as described in
Example 1.
The following starting materials were used:
182 kg of toluene
350 kg (1025 mol) of saccharose,
20 kg of propylene glycol,
15.0 kg of 50% aqueous potassium hydroxide solution,
6.0 kg of water (total quantity of water 13.5 kg; 3.85% based on the weight
of saccharose),
696 kg (12010 mol) of propylene oxide in 13.5 hours.
Saccharose was first added at room temperature and then, at 80.degree.C,
propylene glycol, potassium hydroxide and water in that order. The mixture
of starting components was freely stirrable.
The pale yellow, viscous product obtained had the following physical
properties:
hydroxyl number (mg KOH/g)
470
pH 7.3
water content (%) 0.08
viscosity n.sub.25.sub..degree.C (cP)
104000
average functionality
(calculated from quantity of starting
material and hydroxyl number)
6.30
EXAMPLE 4
The introduction of starting components, addition of alkylene oxide and
working up of the alkaline polymer were carried out as described in
Example 1. The components were introduced in the following sequence:
1,330 g of toluene
2,670 g (7.81 mol) of saccharose at about 25.degree.C,
91.5 g of propylene glycol at 80.degree.C,
73.5 g of water at 80.degree.C,
110.0 g of 50% aqueous potassium hydroxide solution at 80.degree.C (total
quantity of water 128.5 g; 4.8% of water based on the weight of
saccharose),
4,239 g of propylene oxide (73.0 mol) in 14 hours.
The addition of propylene oxide was carried out at 1.4 to 1.6 atmospheres.
The mixture of starting components was freely stirrable.
The brownish yellow, highly viscous product obtained had the following
physical properties:
hydroxyl number (mg KOH/g)
519
(the hydroxyl number was determined with
acetic acid anhydride in pyridine)
pH 6.6
water content (%) 0.05
viscosity n.sub.25.sub..degree.C (cP)
400,000
average functionality
(calculated from the quantity of
starting material and hydroxyl number)
7.18
EXAMPLE 5
The introduction of starting components, addition of alkylene oxide and
working up of the alkaline polymer were carried out as described in
Example 1. The starting components were introduced in the following
sequence:
1,310 g of toluene
2,180 g (6.38 mol) of saccharose at about 25.degree.C,
251 g of triethanolamine at 80.degree.C
46 g of water at 80.degree.C
104 g of 50% aqueous potassium hydroxide solution at 85% (total quantity of
water 98.0 g; 4.5% based on the weight of saccharose),
6,254 g (112.6 mol) of propylene oxide in 20 hours.
The addition of propylene oxide was carried out at 0.4 to 0.6 excess
atmospheres.
The mixture of starting components was freely stirrable.
The brownish yellow, viscous product obtained had the following physical
properties:
hydroxyl number (mg KOH/g)
376
pH 9.05
water content (%) 0.04
viscosity n.sub.25.sub..degree.C (cP)
11780
average functionality
(based on the quantity of starting
material and hydroxyl number)
5.96
EXAMPLE 6
The introduction of starting components, addition of alkylene oxide and
working up of the alkaline polymer were carried out as described in
Example 1. The starting components were added in the following sequence:
125 kg of toluene
291 kg (850 mol) of saccharose at about 25.degree.C,
30.0 kg of trimethylol propane at 70.degree.C,
6.0 kg of water at 80.degree.C,
18.5 kg of 50% aqueous potassium hydroxide solution at 80.degree.C (total
quantity of water 15.25 kg; 5.24% of water based on the weight of
saccharose),
873 kg (15,080 mol) of propylene oxide in 16 hours.
The mixture of starting components was freely stirrable.
The brownish yellow viscous product obtained had the following physical
properties:
hydroxyl number (mg KOH/g)
382
pH 6.9
water content (%) 0.09
viscosity n.sub.25.sub..degree.C (cP)
13825
average functionality
(calculated from quantity of starting
material and hydroxyl number)
5.77
EXAMPLE 7
The introduction of starting components, addition of alkylene oxide and
working up of the alkaline polymer were carried out as described in
Example 1. The starting materials were introduced in the following
sequence:
1,000 g of toluene
1,685 g (4.93 mol) of saccharose at about 25.degree.C,
107 g of ethylene diamine at 80.degree.C
46 g of water at 80.degree.C,
70 g of 50% aqueous potassium hydroxide solution at 80.degree.C (total
quantity of water 81.0 g; 4.8% of water based on the weight of
saccharose),
5,200 g (89.7 mol) of propylene oxide in 23 hours
The addition of propylene oxide was carried out at 0.4 to 0.6 excess
atmosphere.
The mixture of starting components was freely stirrable.
The brownish yellow, viscous product obtained had the following physical
properties:
hydroxyl number (mg KOH/g)
398
pH 10.3
water content (%) 0.159
viscosity n.sub.25.sub..degree. C (cP)
16350
average functionality
(calculated from starting material
and hydroxyl number) 6.01
EXAMPLE 8
In this example there is described the preparation of a saccharose
polyether which was prepared from a mixture of propylene oxide and
ethylene oxide. The introduction of starting components, addition of
alkylene oxides and working up of the alkaline polymer were carried out as
described in Example 1.
The starting materials were introduced in the following sequence:
121 kg of toluene
286 kg (837 mol) of saccharose at about 25.degree.C,
29.8 kg of trimethylol propane at 70.degree. - 75.degree.C,
8.4 kg of propylene glycol at 80.degree. - 85.degree.C,
5.4 kg of water at 85.degree.C,
12.0 kg of 50% aqueous potassium hydroxide solution at 85.degree.C (total
quantity of water 11.4 kg; 3.98% of water based on the weight of
saccharose),
652 kg (11230 mol) of propylene oxide,
218 kg (4960 mol) of ethylene oxide as mixture in 13 hours.
The mixture of starting components was freely stirrable.
The pale yellow, viscous product obtained had the following physical
properties:
hydroxyl number (mg KOH/g)
374
pH 7.4
water content (%) 0.09
viscosity n.sub.25.sub..degree.C (cP)
7500
average functionality
(calculated from starting material
and hydroxyl number) 5.83
EXAMPLE 9
In this example there is described a saccharose polyether which was
prepared by first adding propylene oxide and then adding ethylene oxide
only after all the propylene oxide had been added and the reaction has
been left to continue for 2 hours after the addition of propylene oxide.
The introduction of starting components, addition of alkylene oxides (the
pressure in the reaction vessel was increased to 2 excess atmospheres
during the addition of ethylene oxide) and working up of the alkaline
polymer were carried out as described in Example 1. The starting materials
were introduced in the following sequence:
156 kg of toluene
302 kg (883 mol) of saccharose at about 25.degree.C,
18.1 kg of trimethylol propane at 70.degree. - 75.degree.C,
8.5 kg of propylene glycol at 80.degree.C,
5.0 kg of water at 80.degree.C,
12.0 kg of 50% aqueous potassium hydroxide solution at 80.degree. -
85.degree.C (total quantity of water 11.0 kg; 3.64% of water based on the
weight of saccharose),
819 kg (14120 mol) of propylene oxide in 15 hours
48 kg (1091 mol) of ethylene oxide in 1.2 hours.
The mixture of starting components was freely stirrable. The brownish
yellow, viscous product obtained had the following physical properties:
hydroxyl number (mg KOH/g)
382
pH 7.6
water content (%) 0.05
viscosity n.sub.25.sub..degree.C (cP)
13600
average functionality
(calculated on starting material
and hydroxyl number) 6.00
COMPARISON EXAMPLE
The stirrability of a mixture of 30.0 g of 50% aqueous potassium hydroxide
solution, 11.3 g of water and 500.0 g of saccharose (total quantity of
water 26.3 g; 5.26% of water based on the weight of saccharose) was tested
in a two liter hard glass beaker fitted with lid and blade stirrer with
glass shaft.
Aqueous potassium hydroxide solution and water were introduced into the
beaker. About 100 g of saccharose were first introduced at about
50.degree.C with stirring. Additional saccharose was gradually stirred in
at 90.degree. - 95.degree.C. The thick, pasty mixture obtained after the
addition of a total of 440 g of saccharose was still stirrable. By the
time 500 g of saccharose had been added, the mixture was very tough and no
longer stirrable, there was a marked formation of lumps and the stirrer
broke after a few minutes.
It is to be understood that any of the components and conditions mentioned
as suitable herein can be substituted for its counterpart in the foregoing
examples and that although the invention has been described in
considerable detail in the foregoing, such detail is solely for the
purpose of illustration. Variations can be made in the invention by those
skilled in the art without departing from the spirit and scope of the
invention except as is set forth in the claims.
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