DE2619836A1 - NEW LUBRICANTS FOR THERMOPLASTIC MATERIALS AND A METHOD OF MANUFACTURING THE SAME - Google Patents

Description

Dipl.-Ing. P. WIRTH Dr. V. SCHMiED-KOWARZIK DIpWng. G. DANNENBERG Dr. P. WEINHOLD Dr. D. GUDEL

281134 6 FRANKFURT / M

TEUEFON (061 » orriMimrun im.

ί870Μ GR. ESCHENHEIMER STR. 39

Case Br. 171

SÄPCHIM-FOURNIER-CIMAG

39 Avenue Pierre 1er de Serbie,

Paris, France

"New Lubricants for Thermoplastic Materials and a Process for Making Them."

609847- / 1038

■■ t— "■

The present invention relates to new lubricants for thermoplastic Materialier and a method for making the same.

These lubricants made by reacting behenic acid with aliphatic polyalcohols are produced alone or together with one another and / or with a salt of behenic acid and a divalent metal such as calcium, zinc, cadmium or barium is used.

The lubricants of the present invention are polyesters of behenic acid and one of the following alJ.phathic polyalcohols: Thiodiglycol, 1,4-butanediol, 1,2-propanediol, glycerine, Pentaerythritol, dipentaerythritol, diethyl glycol, triethylene glycol and trimethylol propane.

The polyesters according to the invention can be prepared by reacting behenic acid with an aliphatic polyalcohol in the presence of sodium or potassium hydroxide as a catalyst and removal of the water that forms during the reaction.

The substances according to the invention, which are listed below, are new and as such are the subject of the invention:

1,2-propanediol dibehenate (compound 1) Thiodiglycol dibehenate (compound 2) diethylene glycol dibehenate (compound 3) triethylene glycol dibehenate (compound 4) Triraethylolpropane tribehenate (compound 5) dipentaerythritol pentabehenate (compound 6) 1,4-butanediol dibehenate (compound 7)

On the other hand, the following substances are already known. The invention also relates to new lubricants for thermoplastic Materials that include these:

■ 60984771038

Glyceryl tribehenate (compound 8)
Pentaerythritol tetrabehenate (compound 9)

Thermoplastic materials are known to d & i3 them the surface of the devices in which they are manufactured, stick, and it is therefore necessary to add a lubricant to the synthetic material to make sticking procrastinate as long as possible.

Numerous lubricants for thermoplastic materials are known and generally belong to one of the two following classes:

a) To the external lubricants, which aim to reduce friction at the phase boundary and in an amount of about 0.2 to 0.5 weight percent can be used. Among these agents is glyceryl trimontanate, which is described in the British patent No. 1,314,269, one of the most widely used agents on an industrial scale.

b) The internal lubricants, which are intended to reduce the viscosity of the polymer in the molten state and reduce the shear forces. They are used in an amount of about 0.1 to 1 wt - used.%. Among these agents, one of the most widely used agents in the art is glyceryl trihydroxystearate, described by R. Lefaux in "Les matiores Plastiques dans 1'Industrie Alimentaire" (Compagnie Francaise d ^{1 Editions, 1972).}

Mixed esters of aliphatic polyalcohols and higher aliphatic Mono- and dicarboxylic acids such as those described in French patent specification No. 2,032,841 are known but are not found useful because when used as a lubricant for polyvinyl chloride they provide a Cause a drop in the softening point of the resin. In addition, some of them cause the

^Harz "" 6098 47710

_ ₄ _ 2619838

It has been found that the esters of the invention, used either alone or together, oppose the already known lubricants with respect to one or more Properties generally possessed by such agents are superior.

For example, the compounds according to the invention provide the Quality of the synthetic material by improving either the internal, external or even both lubricating effects.

In addition, they have a low level of toxicity and, when incorporated into a resin to be used in the manufacture of containers, have a high resistance to extraction from the resin into the contents of the containers. These results are important because they are of the latter with respect to the difficulty in containers for food and beverages because of possible contamination by the lubricant provided with polymer from which the container is made of importance.

Finally, the compounds according to the invention are not volatile and under the influence of heat and air, even at high temperatures, resistant, what in terms of processing and the contamination of the workshops in which the various operations are carried out is very important.

As the compounds of the invention are made into synthetic resins used for the manufacture of containers for food and beverages their toxicity was examined first, and those obtained are satisfactory Results justified continuation of the test.

A. Acute toxicity

The acute toxicity (LDc ₀ ) of the compounds listed below was examined by determining the dose of the substance which caused the death of 50% of the treated animals.

as an associate

60984771038

A gummy suspension of the substance under investigation became Orally administered to groups of at least ten mice and the following results were obtained:

link LD ₅₀ ( ^m s / ^k e) Toxic symptoms j 1 V 5000 no 2 > 5000 no 4th > 5000 no . 7th > 5000 no 8th > 5000 no 9 > 5000 no Kaiζium behenate > 5000 no

B. Internal lubricity of the compounds according to the invention n

The compounds according to the invention were with glyceryl trihydroxystearate, which is known to date as the best internal lubricant. The study was carried out with the following composition performed using glyceryl trimontanate as an external lubricant:

Components

Polyvinyl chloride resin anti-shock resin

Acrylic resin

epoxy. Soybean oil chelating agent 1832 Solution of 2-ethyl-potassium-hexanoate, which contains Λ0% potassium 2-phenyl-indole

"Anti-shock resin"

60 98 477103 8

Parts by weight

100 11 0.5 3 0.25

0.025 0.3

Components

Zinc stearate calcium stearate glyceryl trimantanate Internal lubricant

Weight Parts O ,1 O , 3 O , 5 1

The composition of the chelating agent 1832 is as follows:

Diphenyl decyl phosphite: 67 parts by weight

Solution of 10 $ 6 zinc octoate in diisobutyl phthalate: 33 parts by weight

Gel formation

This examination was carried out on a plastoglaph, which is used in
Temperature of 150 ⁰ C worked, rotated at a speed of 30 rpm and a charge of 25 g of powder below
contained constant pressure.

The following results were obtained:

lubricant Start of gel formation
in sec. End of gel formation
in sec. Glyceryl trihydroxy
stearate 75 210 1 120 260 2 110 260 3 120 270 4th 105 265 5 180 380 7th 120 255 8th 180 380 9 360 585

6098477 1038

Glyceryl trihydroxystearate "has a shorter gel time than the compounds of the invention. Among the latter, the gel formation in pentaerythitol tetrabehenate (compound 9) the longest.

It has therefore been found that the behenates of the invention Delay the beginning and the end of gel formation, which is a valuable property - as far as the internal lubricity is concerned acts - represents. Extending the gel time is particularly desirable when degassing the resin necessary is.

2. Dynamic heat resistance of the resin

This examination was also carried out on a plastograph, but operated at a temperature of 210 ° C vairde, spinning at a speed of 60 rpm and containing a charge of 30 g of gelled material.

Two curves were recorded for each lubricant, namely:

A decomposition curve showing the value of the minimum resistance torque (m «kg) and indicates the time of decomposition;

a curve showing self-heating time in relation to temperature indicates.

The self-heating time is defined as the moment in which the temperature of the material exceeds the temperature of the plastograph (210 ⁰ C).

The results given in the table below were obtained from these curves:

6098-477 1038

Measurements Glyceryl
trihydrox}
-stearate 1 link 2 3 4th 5 7th 8th 9
I. minimum
conscious
keitsdret
moment ir
^ n- Ir ρ - 1.075 1.060 1.070 1.050 1.070 1.060 1.070 1.065 1.065 Decomposed
tongue
zext in
Min. 32 34 34 33.5 33.5 34 34 34 35 Self
heating
time in
Min. 14th 10.5 14.5 11.5 11.75 12.5 11 13th 15th

Pentaerythritol tetrabehenate (compound 9) provides re the decomposition and self-heating times gives the best result and is therefore particularly useful for internal lubrication.

Otherwise, the other behenates are equivalent to one another and have a better result than glyceryl trihydroxystearate with regard to the minimum resistance torque.

Some behenates have a self-heating time that is less than that of glyceryl trihydroxystearate, but which is still is completely sufficient for a lubricant.

3 «Gluing the lubricated resin

This study was - carried out by the resin was put in a mixer, the cylinder was heated to 21O ⁰ C, and the material alternate 3 minutes of mixing and a 3-minute break was subjected, wherein the distance between the. Cylinders was 0.25 mm.

80984771038

The following results were obtained:

Measurement link Glyceryl
trihydrox?
-stearate • 1 2 3 4th 5 I.
7th Γ
8th 9 j Resistant
Uceit against
about Kle
ben (min) 19th 21.5 21 22nd 23 27 23 26th 26th

Glyceryl tribehenate (Compound 8) did not stick, but the resin turned black after 26 minutes.

Trimethylol propane tribehenate (Compound 5) stuck and decomposed after 27 minutes.

Finally, pentaerythritol tetrabehenate (compound 9) stuck and decomposed after 26 minutes.

From the above results it can be concluded that the invention Compounds are superior to glyceryl trihydroxystearate in terms of sticking.

4. Conclusion

As far as the internal lubricating effect is concerned, it has been found that the polyalcohol behenates according to the invention are opposite Glyceryl trihydroxystearate, which has heretofore been considered the best lubricant, are superior.

C. External lubricity of the compounds of the invention

The compounds according to the invention were with glyceryl trimontanate, which is currently considered the best external lubricant and does not create opacity.

8098.477 1038

This study was carried out on the following resin composition using glycoryl trihydroxystearate as the internal lubricant was used:

Components

Polyvinyl chloride resin Anti-shock resin

Acrylic resin

epoxy. Soybean oil chelating agent 1832 Solution of 2-ethyl-potassium-hexanoate, which contains 10% potassium, 2-phenyl-indole zinc stearate
Calcium stearate Glyceryl trihydroxystearate External lubricant

Parts by weight

100
11
0.5 3
0.25

0.025

0.3

0.1

0.3

0.3

1. Gel formation

This study was performed on a plastograph, working at a temperature of 150 ⁰ C, rotating at a speed of 30 rpm, and containing a charge of 25 g of powder under constant pressure.

The following results were obtained:

lubricant Beginning of the Gelbil
dung in seconds End of gel
education in seconds Glyceryl trimontanate
1
2
5
7th
8th
9 75
50
40
45
45
50
40 210
210
180
190
210
210
200

609847/1038

The compounds of the invention began before glyceryl triraontanate to gel, whereas the end of the gelation occurred after approximately the same period of time.

As far as the gel formation is concerned, the fulfillment methods have bindings - even if they are not superior to GIy ceryl tr imontanat are - nevertheless, very valuable properties.

2 .. Static heat resistance of the lubricated Resin

This study was carried out using the procedure described in French Patent Specification No. 2,273,841, keeping the temperature of the furnace at 185 ° ^C.

It has been found that glyceryl trimontanate and those according to the invention Joints in terms of static heat resistance similar to lubricated resins. However, -1,2-propanediol dibehenate and thioglycol dibehenate improved those The heat resistance of the resins kept in the oven at 185 ° C for 50 minutes is considerable.

3 »Dynamic heat resistance of the one provided with the lubricant Resin

This examination was carried out on a plastograph operating at 190 ° C, moving at a speed of 60 ^ Rpm and contained a charge of 30 g of gelled material.

Two curves were recorded for each lubricant, and

A decomposition curve showing the value of the minimum resistance torque (m »kg) and indicates the time of decomposition.

A curve showing the self-heating time in relation to temperature indicates.

609847/1038

2613836

The results given in the following table were obtained from these curves:

Measurements ¹ - \
link 1 2 5 7th 8th 9 Minimum
permanent
torque
in m «kg Glyceryl
triraonta-
nat 1.025 1.020 1.055 1.030 1.035 1.030 Decomposition
time in min. 1.075 37.5 33.5 35.5 35 35 34.5 Self-hit
ting time
in min. 32 17.75 14.75 14.75 16 15.5 15.75 14th

These results show that the compounds of the present invention are superior to glyceryl trimontanate in that they are

a weaker s minimum resistance torque a higher decomposition time and
a higher self-heating time

own.

1,2-propanediol dibehenate (compound 1) is the other compounds far superior in this test.

4. Gluing the lubricated resin

This investigation was carried out by placing the resin in a mixer, the cylinders of which ^{were heated to 210 °} C. and the material was alternately subjected to 3-minute mixing and a 3-minute break, the distance between the cylinders being 0.25 mm fraud.

609847/1038

The following results were obtained:

Measurements Glycrylic
trimontp-
nat 1 link 2 20th VJl 7th 8th 9 Resistant
speed against
about gluing
in min. 19th 16 15.5 17th 13th 19th
ι

Albeit sometimes the results of the compounds according to the invention are below those of glyceryl trimontanate, these are nevertheless also in terms of resistance to Glue valuable lubricants.

5. Conclusion

With regard to external lubrication, the time of resistance to sticking is of the utmost importance. In this regard, the compounds of the invention and glyceryl trimontanate can be viewed as more or less equivalent although some behenates are somewhat inferior to glyceryl trimontanate. However, they improve resilience of the resin to the decomposition by heat is considerable, which is the lower internal friction due to is attributable to lower viscosity and was demonstrated by the results obtained with the plastograph.

The latter result confirms the excellent internal lubricating properties of the compounds of the present invention.

609847/1038

D. Lubricity of binary mixtures of the invention Behenate

In this experiment, binary mixtures of polyalcoholic phenates were used with the association Glycerylwrimontanat / Glyceryltrihydroxyearat, the best known external lubricant that does not create any opacity, or the best internal lubricant Represents lubricant compared. This investigation was performed with the following resin composition:

Components parts by weight

Polyvinyl chloride resin 100 anti-shock resin 11

Acrylic resin 0.5

epoxy. Soybean oil 3

Chelating Agent 1832 0.25

Solution of 2-ethyl-potassium-hexanoate,

the 10% potassium contains 0.025

2-phenylindo1 0.3

Zinc stearate 0.1

Calcium stearate 0.3

Internal lubricant 1

External lubricant 0.3

In the experiments with the above binary mixtures of behenates, thiodiglycol dibehenate was compared to glyceryl trihydroxystearate as an internal lubricant and pentaerythritol tetrabehenate, 1,4-butanediol dibehenate and 1,2-propanediol dibehenate as an external lubricant compared to glyceryl trimontanate.

The following mixtures (ratio 10: 3) were investigated:

Glyceryl trihydroxystearate - glyceryl trimontanate (V) thiodiglycol dibehenate - pentaerythritol tetrabehenate (¥) Thiodiglycol dibehenate - 1,4-butanediol dibehenate (X) Thio ^ glycol dibehenate - 1,2-propanediol dibehenate (Y)

609 8 47/1038

The following mongrel (ratio 8: 3) was also examined :

Thiodiglycol dibehenate - pentaerythritol tetrabehenate (Z)

1. Gel formation

This examination was carried out on a plastograph set at 150 ° C worked, rotated at a speed of 30 rpm ui'd a charge of 25 g of constant pressure powder was carried out.

The following results were obtained:

mixture Start of gel formation
in sec. End of gel formation
in sec. V 70 210 ¥ 90 230 X 80 210 Y 70 210 Z 90 270

So it was found that the binary mixtures of the behenates marked the beginning and the end of gelation to a greater extent than Comparative Mixture V, with the exception of Mixture Y, which has a gel time equal to that the latter is identical. This is valuable in terms of the lubrication of thermoplastic materials Characteristic. The extension of the gel formation time is particularly valuable if degassing of the resin is necessary.

The binary mixtures, the pentaerythritol tetrabehenate (W and Z) are most valuable in terms of gel formation.

609847/1038

2. Static heat resistance of the lubricated Karzes

This investigation, which was carried out as indicated above, showed that the discoloration obtained was the same in all cases Intensity bese »3.

2. Dynamic heat resistance of lubricated Resin

This examination was also carried out on a plastograph, but which was operated at a temperature of 190 C, spinning at a speed of 60 rpm and containing a charge of 30 g of gelled material.

Two curves were recorded for each binary mixture, namely:

A decomposition curve showing the value of the minimum resistance torque (m «kg) and indicates the time of decomposition;

a curve showing self-heating time in relation to temperature indicates.

The results given in the following table were obtained from these curves:

mixture Minimum stock
speed rotation
moment in m-kg Measurements Self-heating
time in min. V 1.075 Decomposition
time in min. 14th W. 1.060 32 12th X 1.030 34 12th Y 1.035 35 17th Z 1.040 34.5 12th 32

609847/1038

These results show the superiority of the binary mixtures of behenates over eggs of Mixture V, since they

a lower minimum resistance torque and have a longer replacement time (the same as for mixture Z).

It should be noted that the mixture Y (thiodiglycol dibehenate - 1,2-Propandioldibehenat) a particularly high one Has self-heating time.

4. Gluing the lubricated resin

This study was carried out by placing the resin in "a Mixer was given, the cylinder was heated to 21ü ° C and alternately subjecting the material to 3 minute mixing and 3 minute pause, the interval between the cylinders was 0.25 mm.

The following results were obtained: _r

Measurements mixture V 21.5 X Y Z resistance
opposite Kle
practice in min. 19th 20th 20th 21.5

From the above results it follows that the mixtures according to the invention are superior to Mixture V in terms of gluing.

5. Extrusion and blow molding processes

Resins described above, each containing one of the binary mixtures V, W, X and Y, were treated with a

60984 7/1038

Extruder equipped with a screw with a diameter of 45 mm was extruded. The four resins tested were comparable in terms of friction and extrusion, those containing behenate blends were perfect extruded.

Bottles were molded with the above resins, and the four resins were observed to behave differently gave comparable results in the blow molding process. With the mixtures V, ¥ and X, identical bottles were obtained, while a more transparent bottle was obtained with mixture Y.

6. Conclusion

The comparison mixture, namely glyceryl trihydroxystearate, can be used as a lubricant - Glyceryl trimontanate in very beneficial Xieise can be replaced by the following binary mixtures:

* ■ Thiodiglycol dibehenate - 1,2-propanediol dibehenate Thiodiglycol dibehenate - pentaerythritol tetrabehenate Thiodiglycol dibehenate - 1,4-butanediol dibehenate

E. Synergistic lubricity of binary mixtures of Polyol behenate + metal behenate

This investigation was carried out in two stages:

1) Comparison between the lubrication properties of the binary mixture Glyceryl tribehenate - calcium behenate and those a ^ r known mixtures, such as glyceryl trimontanate-calcium stearate or 1,4-butanediol dimontanate, which neutralize with calcium oxide was.

2) Comparison between the lubricating properties of the mixture glyceryl tribehenate - calcium behenate used for this experiment were chosen for comparison, and those of the binary mixtures of thiodiglycol dibehenate - calcium behenate and penta

60984 771038

erythritol tetrabehenate - calcium behenate.

a) Comparison of glyceryl tribehenate with glyceryl trimontanate This o study was carried out with the following composition:

Components G ^ w. Parts Polyvinyl chloride resin 100 Anti-shock resin 11 Acrylic resin 0.5 epoxy. Soybean oil 3 Chelating Agents 1832 0.25 Solution of 2-ethyl-potassium-hexanoate, which contains 10? fi potassium 0.025 2-phenyl-indole 0.3 Zinc stearate 0.1 Calcium stearate 0.1 Glyceryl trihydroxystearate 1 Glyceryl tribehenate or glyceryl trimontanate 0.5 1. Static heat resistance of the lubricated Resin

It has been used in both glyceryl tribehenate and glyceryl trimontanate the same heat resistance was observed, with both resins showing sudden decomposition after 60 minutes.

2, gel formation

This study was performed on a plastograph, which was operated at a temperature of 150 ⁰ C, rotating at a speed of 30 rpm, and containing a charge of 25 g of powder under constant pressure is performed.

609847/1038

The following results were obtained:

lubricant Start of gel formation
in sec. End of year education
in sec. Glyceryl tribehenate 20th 90 Glyceryl trimontanate 20th 90

So the gel times were the same.

3. Dynamic heat resistance of the lubricated Resin

This study was performed on a Brabender which was operated at 190 ⁰ C and rotating at a speed of 60 rpm, carried out, where the time to decomposition was measured of a gelled material. The minimum resistance torque and temperature were recorded during the test and the self-heating time, ie the time it took for the material to exceed the initial temperature of the plastograph (190 ° G), was noted.

The following results were obtained:

lubricant Minimum stock
speed torque
ment in m »kg Decomposition
time in min. Self-hit
ting time
in min. Glyceryl tribehenate 1.05 18th 8.5 Glyceryl trimontanate 1.13 14.5 6.5

609847/1038

It is clear from the above results that glyceryl tribehenate is far superior to glyceryl trimontanate in terms of decomposition and self-heating time.

4. Gluing the resin mixed with lubricant

This investigation was carried out by placing the resin in a mixer, the cylinder of which was ^{heated to 210 °} C. and the material was alternately subjected to a 3-minute mixing and a 3-minute break, the distance between the cylinders being 0.25 mm fraud.

The following results were obtained:

lubricant Resistance to
via gluing in min. Glyceryl tribehenate
Glyceryl trimontanate 11
13.5

The resistance to sticking can be considered equivalent for both compositions, albeit that of glyceryl tribehenate is somewhat lower.

b) Comparison of calcium behenate with calcium stearate This study was carried out with the following composition.

Components

Polyvinyl chloride AntistoSharz Acrylic acid epoxy. Soybean oil Chelating Agents 1832

Parts by weight 5 100 11 25th O, 3 0,

609847/1038

Components

Solution of 2-ethyl-potassium-hexanoate, which contains 10% potassium

2-pkenyl indole

Zinc stearate

Calcium stearate

Glyceryl trihydroxystearate calcium behenate or calcium stearate

Parts by weight

0.025

0.3

0.1

0.1 1

0.5

1. Static heat resistance

No difference was found between the two resins

2. Gel formation

This study was carried out under the same process conditions as in the previous study, and the the following results were obtained:

lubricant Start of gel formation
in sec. End of gel formation
in sec. Calcium behenate 15th 90 Calcium stearate 10 70

The gel formation times are slightly longer with calcium behenate than with calcium stearate.

3 »Dynamic heat resistance

Using the same conditions as previously described, the following results were obtained:

609847/1038

lubricant Minimum stock
speed torque
ment in m «l: g Decomposition
time in min. Self-hit
time in min. Calcium behenate
Calcium stearate 1.03
1.02 34
35 23
26.5

In this experiment, calcium behenate and calcium stearate gave practically the same results.

4. Gluing

Under the same conditions as before were with Kalziumbelienat and calcium stearate gave the same results with a stickiness resistance of 15.5 minutes.

c) Study of the conditions for optimal synergistic Effect of the binary mixture of glyceryl tribehenate-calcium behenate

This study was made with the following composition performed, the ratio of the amounts between glyceryl tribehenate and calcium behenate has been changed:

Ingredients polyvinyl chloride resin anti-shock resin
Acrylic resin

.epoxy. Soybean Oil Chelating Agent 1832 Solution of 2-ethyl-potassium-hexanoate, which contains 10% potassium, 2-phenyl-indole, zinc stearate
Calcium stearate glyceryl trihydroxystearate glyceryl tribehenate / calcium behenate

609847/1038

Parts by weight 100
11
0.5 3
0.25

0.025

0.3

0.1

0.1

0.5

The ratio of glyceryl tribehenate to calcium behenate varies as follows:

Approach no. 5 6th 7th 8th 9 10 11 12th GlyceryltribeUena c
Parts by weight 0.5 0.4 0.3 0.25 0.2 0.1 0 0 Ka]. ζ iumb marriage 0 0.1 0.2 0.25 0.3 0.4 0.5
- 0

1. Static heat resistance

No difference was observed between the above eight compositions during the first 40 minutes.

After 50 minutes, compositions 5 and 12 were the only ones that decomposed and turned black. After 70 minutes, Composition 7 slowly began to decompose. After 80 For minutes in the oven, composition 8, 9 and 10 performed well.

2. Dynamic heat resistance

The following results were obtained:

Approach no. Ul 6th 7th 8th 9 10 11 12th Minimum resistance
torque in m * kg 1.05 1.09 1.09 1.07 1.06 1.03 1.03 1.11 Decomposition time in min 18th 19.5 21 24.5. 30th 31 34 18th Self-recovery time
in min 8.5 7th 10.5 13.5 22.5. 20th 23 10.25

609847/1038

The decomposition time increases from 18 to 34 when the amount of calcium behenate increases from 0 to 0.5 parts by weight.

3 »Gluing

The following results were obtained:

Approach no. VJl 6th 7th 8th 9 10 11 12th Resistance ge
compared to gluing
in min. 11 14th 14.5 16 17th
I. 16 16.5 6th

The resistance to sticking increases steadily in approaches 5 to 9 from 11 to 17 minutes and falls then turn off at the last approach. which has a synergistic effect for a ratio of glyceryl tribehenate - calcium behenate of 2: 3 indicates.

4. Conclusion

From the above results it can be seen that:

A maximum resistance to sticking of 17 minutes with batch 9, i.e. with a ratio of glyceryl tribehenate to calcium unbehenate of 2: 3 and

a decomposition time that varies with the percentage of calcium behenate increased, was obtained. However, too great an excess of calcium behenate can reduce the transparency of the thermoplastic Affect materials.

From these results it can be seen that a ratio of glyceryl tribehenate to calcium behenate of 2: 3 is the ideal ratio is to obtain maximum resistance to sticking while maintaining good transparency ..

609847/1038

d) Comparison of the "binary mixtures of glyceryl tribehenate - calcium behenate with glyceryl trim ^ ntanate - calcium stearate

The results obtained with the first mixture, which are recorded in the previous section, have been matched with the results compared that "in the mixture glyceryl trimoritanate calcium stearate the latter results being obtained with the same composition as above but which glyceryl trimontanate and calcium stearate have been exchanged.

The ratio between the two lubricants varied as follows:

Approach no. 13th 14th 15th 16 17th 18th 19th Glycyryl trimontanate
Ge Vi. Parts 0.5 0.4 0.3 0.25 0.2 0.1 0 Calcium stearate
Parts by weight 0 0.1 0.2 0.25 0.3 0.4 0.5

1. Static heat resistance

The results were found to be comparable to those obtained with glyceryl tribehenate - calcium behenate are.

2. Dynamic heat resistance and sticking

The results given below were obtained:

609847/1038

Approach no. 13th 14th 15th 16 17th 18th 19th Minimum employability
torque in m «kg ', 13 1.12 1, C3 1.09 1.08 1.06 1.02 Decomposition time
in min. 14.5 19th 25th 27.5 26th 32 35 Self-heating time
■ in min. 6.5 10.5 15.5 15.75 13.5 23 26.5 Resistance to
via gluing in min. 13.5 20th 19th 16 15.5 15.5 15.5

From these results it can be seen that compared to those which were given in the previous section., as a whole, the mixture of glyceryl tribehenate - calcium behenate is more advantageous.

c) Comparison of the mixtures of glyceryl tribehenate - calcium behenate with 1,4-butanediol diinontanate (neutralized with calcium oxide)

Approach 9 - as stated above - was with the same approach, but 0.5 part by weight of 1,4-butanediol dimontanate with calcium oxide was neutralized (batch no. 20), instead of 0.5 part by weight Glyceryl tribehenate - containing calcium behenate (in the ratio 2: 3).

The following results were obtained:

Approach no. in sec. 9 20th Start of gel formation Sec. 100 100 End of gel formation in 290 285

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Approach no. 9 20th Minimum resistance
torque / ¹ : in m «kg 1.06 1.11 Disintegration time in min. 30th 21 Self-heating time in min. 22.5 10 Resistance to
Gluing in min. 17th 11

These results show that the glyceryl tribehenate mixture has calcium behenate lubricating properties similar to those of
of 1,4-butanediol neutralized with calcium oxide are considerably superior.

f) Svnergistic effect of the binary mixture thiodiglvkoldibehenat - calcium behenate

This study was carried out with the following approach;

Components polyvinyl chloride resin anti-shock resin acrylic resin epoxy. Soybean oil chelating agent Solution of 2-ethyl-potassium-hexanoate with Λ0% potassium 2-phenyl-indole zinc stearate calcium stearate glyceryl trihydroxystearate External lubricant

Parts by weight 100
11
0.5 3
0.25

0.025

0.3

0.1

0.1

0.5

609847/1038

In this investigation, the external lubricant was either the binary mixture glyceryl tribehenate - calcium behenate (for Comparison), or thiodiglycol dibehenate alone, or the binary mixture thiooliglycol dibehenate - calcium behenate in different Shares, such as et *, are given in the following table:

1138 11 39 'Approach No. 11 42 1143 1144 1145 lubricant 0.2
0.3 0 , 5 1140 1 141 0,
0, 25th
25th 0.2
0.3 0.1
0.4 0.5 Glyceryl tribehenate
Thiodiglycol
behenat
Kaiζ iumb marriage 0.4
0.1 0.3
0.2

1. Static heat resistance

Good heat resistance was obtained. However, decreasing amounts of thiodiglycol dibehenate resulted in a weak and increasing one Destabilization. After 60 minutes, batch 1139 showed very good color, but quickly decomposed. This latter disadvantage was remedied by adding 0.1 part by weight of calcium behenate.

2. Gel formation

This study was a Brabender which was operated at 150 ⁰ C with a rotational speed of 30 rpm and contained a loading of 25 g of powder under constant pressure is performed.

The following results were obtained:

$ 09847/1038

Approach no. Start of gel formation End of gel formation in sec. in Se "C 1138 80 240 1139 110 240 1140 105 250 1141 90 240 1142 90 24u 1143 90 240 1144 90 240 1145 60 210

The gel formation times were very close to one another, just a start
No. 1145 (calcium behenate alone) had shorter gel times.

3. Gluing

This study was done by placing the resin in a mixer was given, the cylinders of which were heated to 2 0 ° C, and alternating 3-minute mixing and 3-minute pause (the distance between the cylinders was 0.3 mm).

The following results were obtained:

Approach no. Gluing in min. 1138 Glue after 18 minutes 1139 Decomposition and sticking after 19.5 minutes 1140 Decomposition and sticking after 30 minutes 1141 Start sticking at 27 minutes and stick after 29 minutes 1142 Stick after 25 minutes and stick after 27 minutes 1143 Glue after 23.5 minutes 1144 Glue after 24 minutes 1145 Glue after 18 minutes

609847/1038

Batch No. 1140, which contained 4 parts thiodiglkyol dibehenate and 1 part calcium behenate, was the last batch that stuck. However, it could not be selected due to the observed degree of decomposition. Batch 114 " ^1. (Ratio 3: 2"> was the most advantageous in terms of lubrication without decomposition.

It should be noted that under the observed working conditions for the mixture of thiodiglycol dibehenate - calcium behenate (3: 2) a bonding time of 29 minutes compared to the glyceryl tribehenate - calcium behenate mixture was obtained in just 18 minutes.

4. Dynamic heat resistance

This examination was carried out with a plastograph operating at 190 with a speed of rotation of 60 rpm and contained a charge of 30 g of the material.

The following results were obtained:

Approach no. Decomposition
time in min. Minimum resistance
no torque
in m «kg Self-heating
time in min. 1138 41.5 ■ 1.025 34 1139 26.5 1.050 27 1140 34 1.055 34.25 1141 39 1.025 34.33 1142 38 1.020 39 1143 41 - 1.015 34.5 1144 44.5 1,000 45 1145 - 42 1,000 42

609847/1038

- 32 - 2 6 1 9 8 3 p

. Run No. 1141, which was selected according to the adhesion test at 210 ⁰ C, showed a decomposition of 39 minutes and a self-heating time 34.33 minutes, which is at least as good as the effect of the corresponding mixture of glyceryl tribehenate - Kalziumbeiienc.t (No. . 1138).

In terms of dynamic heat resistance, the approach seemed to be No. 1144 is the best with a decomposition of 44.5 minutes to be, but this approach has the disadvantage that it is 0.4 parts by weight Contains calcium behenate, which causes opalescence in the resin.

It can be concluded that the binary mixture is thiodiglycol dibehenate Calcium behenate has a very high degree of synergism of the lubricating properties of each of the behenates of the mixture and has lubricating properties comparable to those of the binary mixture glyceryl tribehenate - calcium behenate or are superior and in any case are superior to those of the binary mixture glyceryl trimontanate - calcium stearate.

g) Synergistic effect of the binary mixture pentaerythritol tetrabehenate - calcium behenate

This study was carried out using the same approach as used in the previous study, with the exception that the mixture thiodiglycol dibehenate calcium behenate by pentaerythrit tetrabehenate - calcium behenate was replaced.

The different approaches examined are given in the table below:

609847/1038

External lubricant Approach no. Pentaerythritol tetra
behenat
Kaiζiumb ehenat 1146 1147 1148 1149 1150 115 "1145 0.5 0.4 0.3 0.25 0.2 0.1 0
0 0.1 -0.2 0.25 0.3 0.4 0.5

1. Static heat resistance

The colors observed were the same as those obtained with the binary mixture of thiodiglycol dibehenate - calcium behenate were obtained. They became lighter as the proportion of pentaerythritol tetrabehenate was increased. A proportion of 0.5 part by weight However, pentaerythritol tetrabehenate is not as beneficial as it leads to rapid decomposition from the 60th minute on (Approach No. 1146).

2. Gel formation

Using the same procedure as the previous one Investigation, the results given below were obtained:

Approach no. Start of gel formation End of gel formation in sec. in sec. 1138 80 240 1146 210 420 1147 180 340 1148 170 330 1149 120 290 1150 120 290 1151 90 250 1145 60 210

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2 G! 9836

The gel times decreased progressively as the level of calcium behenate increased. You are anyway the times that were observed with glyceryl tribehenate - calcium behenate (batch no. 1138).

3. Gluing

Using the same procedure as the previous one Investigation, the results given below were obtained:

Approach no. 138 1 146 1 147 1 148 1 149 1 150 1 151 1 145 1

Sticking after 18 minutes

Glue after 17.5 minutes

Stick after 24 minutes and stick after 28 minutes

Glue after 29 minutes

Stick after 21 minutes and stick after 24 minutes

Stick after 19 minutes and stick after 23 minutes

Sticking after 19.5 minutes

Glue after 18 minutes

The best rating was with batch number 1148, i.e. pentaerythritol tetrabehenate - Calcium behenate (3: 2), obtained. This effect is comparable to that obtained with thiodiglycol dibehenate - calcium behenate (batch no. 1141) was obtained, but it is that of glyceryl tribehenate - calcium behenate, and consequently that of glyceryl trihydroxystearate - glyceryl trimontanate far superior.

4. Dynamic heat resistance

Using the same procedure as the previous one Investigation, the results given below were obtained:

6098477 1 038

Approach no. Decomposition
time in min. Minimum resistance
no torque
in m-kg Self-heating
time in min. 1138 A1.5 1.025 34 1146 26th 1.040 26.33 1147 32 1.030 32.5 1148 37.5 0.995 33 1149 41 1,000 40 1150 42 0.995 34.5 1151 43 0.980 39

The adhesive tests had already shown the value of batch no. 1148. This approach also turned out to be excellent Possessed properties related to heat resistance.

The more calcium behenate the resins contain, the better they are the results in terms of decomposition time, minimum persistence torque and self-heating time, but at the same time the opalescence can be impaired.

F. External lubrication by binary mixtures of polyol behenates enhanced by the addition of metal salts in tin stabilized batches

This study was carried out with the following blends of lubricants carried out:

Mixture 1: glyceryl trihydroxystearate - glyceryl trimontanate Mixture 2: Thiodiglycol dibehenate - pentaerythritol tetrabehenate Mixture 3: Thiodiglycol dibehenate - 1,2-propanediol dibehenate

Mixture 1 was the comparative mix.

The three metal salts chosen were calcium stearate, calcium montanate and calcium behenate.

609847/1038

Parts by weight 5 100 5 10 0, 3 1, 0.3 1 0, 0 or

The following resin formulation was used for this study;

Ingredients Polyvinyl chloride resin Anti-shock resin Acrylic resin Tin stabilizer Internal lubricant External lubricant Calcium salt

Each of the mixtures 1, 2 and 3 were with and without 0, -3 parts by weight of the selected calcium salt investigated.

1) Mixture 1

Four approaches were examined:

Approach No. 1123: without calcium salt

Batch No. 1126: calcium stearate

Approach No. 1127: calcium montanate

Batch No. 1128: calcium behenate

a) Static heat resistance

The colors observed were very similar. The weakest Color was obtained with batch # 1126, that of batch # 1128 came very close to this.

b) gel formation

This study was a Brabender which was operated at 150 ⁰ C with a rotational speed of 30 rpm and contained a loading of 27 g of powder under constant pressure is performed.

The following results were obtained from the gelation curves:

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Approach no. Start of gel formation end of gel formation

in sec. in sec.

1123 80 160

1126 60 160

1127 60 170

1128 90 -90

The gel formation times of calcium stearate (batch no. 112.6) and Calcium montanate (batch # 1127) were very dense; together, while calcium behenate (batch # 1128) has a longer gel time would have.

c) gluing

This investigation was carried out by placing the resin in a mixer, the cylinders of which ^{were heated to 210 °} C. and the material was alternately subjected to a 3-minute mixing and a 3-minute break, the distance between the cylinders being 0.3 mm fraud.

The following results were obtained:

Approach no.

1123 Glue after 45 minutes

1126 Stick after 24 minutes and stick after 28 minutes

1127 sticking after 42 minutes

1128 gluing after 31 minutes

It can be concluded that the addition of a calcium lubricant the resistance to sticking does not improve and that even such resistance is considerably reduced, when calcium stearate and calcium behenate are added and diminished slightly when calcium montanate is added.

609847/1038

- 38 - 2 B I 9 8 3 G

2) mixed breed 2

Ii ¹ Four approaches of resin were used for this study:

Approach N ^ -. 1124: without calcium salts

Batch No. 1126A: Calcium Stearate.

Approach No. 112? A: Calcium montanate

Batch No. 1128A: calcium behenate

a) Static heat resistance

The three batches that contained a calcium salt resulted in colors that matched the color of the packaging resin without the calcium salt (batch No. 1124) were inferior.

b) gel formation

This test was carried out using the same procedure as that used to test Mixture 1.

The following results were obtained:

Batch No. Beginning of gel formation End of gel formation

in sec. in sec.

1124 80 160

1126 A 120 200

1127 A 120 270

1128 A 100 240

Gel time decreased for the resin containing calcium behenate (Approach No. 1128 A), considerably too.

c) gluing

This study was carried out under the same conditions as before.

609847/103 8

The following results were obtained:

Approach no.

1124 Stick at 12 minutes and stick after 19 minutes

1126 A sticking after 18.5 minutes

1127 A stick at 24 minutes and stick after 29 minutes .1128 A Stick at 29 minutes and stick after 35 minutes

The addition of Kalr: ium stearate did not improve the stickiness of Mixture 2, whereas calcium montanate increased the stickiness of Mixture 2 by 10 minutes. The effect of Kaiziumbehenat had been unusually _t doubled during the period of resistance. 3) mixture 3

The following four approaches were examined:

Approach No. 1125: Without calcium salt

Run No. 1126 B: calcium stearate

Approach No. 1127 B: calcium montanate

Approach No. 1128 B: calcium behenate

a) Static heat resistance

Approaches Nos 1126 B and 1128 B resulted in a color that was opposite was inferior to Comparative Batch No. 1125, while Batch No. 1127 B showed a discoloration similar to that of the latter approach was comparable.

b) gel formation

The following results were obtained:

609847/1038

approach 125 No. 1 126 1 127 E. 1 1? 8 B. 1 B.

Beginning of gel formation End of gel formation in sec. in sec.

50 120

60 150

60 155

70 195

Gel times increased as calcium stearate passed through Calcium montantate and the latter replaced by calcium behenate ■ were.

c) gluing

The following results were obtained:

Approach no.

1125 stick at 12 minutes and stick after 19 minutes

1126 B Stick at 24 minutes and stick after 28 minutes

1127 B stick at 30 minutes and stick after 32.5 minutes

1128 B stick at 30 minutes and stick after 35 minutes

Calcium stearate added 9 minutes to sticky time and calcium montanate by 13.5 minutes. Calcium behenate had the best rating as it took the time to stick around 16 minutes extended.

4) General conclusion

With regard to the external lubrication of tin stabilized resins, it has been found that blends of polyol behenates and especially thiodiglycol dibehenate - pentaerythritol tetrabehenate and thiodiglycol dibehenate - 1,2-propanediol behenate with Calcium salts, especially calcium behenate, are tolerated.

609847/1038

26! 9836

In this type of resin, polyol behenates are the well-known lubricants such as glyceryl trihydroxystearate and glyceryl trimontanate. It can be stated that the addition of calcium behenate to mixtures of foyol behenates the 7eit to jium gluing the short can double.

G. Lubricity of the behenates of the invention with respect to copolymers of polyvinyl chloride

The lubricating effect of glyceryl tribehenate - 1,2-propanediol dibehenate for a polyvinyl chloride - polyvinylidene chloride copolymer, the following approach was used examined:

Components Parts by weight Polyvinyl chloride resin 90 Polyvinyl chloride - polyvinylidene chloride copolymer 10 Modifying agents 7th Acrylic resin 2 Tin stabilizers 1.6 2-phenyl-indole 0.3 Antioxidants 0.1 Internal lubricant 0.5 wax 0.25 Silicon oxide 0.2 GIyc eryltrib marriage 0.5 1,2-propanediol dibehenate 0.5 1. Static heat resistance

The color was excellent up to 50 minutes.

2. Gel formation

This study was a Brabender which was operated at 150 ⁰ C with a rotational speed of 30 rpm and a feed of 27 g corresponds powder under constant pressure

609847- / 1038

held, carried out.

The following results were obtained:

Start of gel formation in seconds: 30
End of gel formation in seconds: 210

3. Dynamic heat resistance

This investigation ^T -oirde with a Brabender which was operated at 190 ⁰ C at a revolution speed of 60 rpm and a feed of 30 g containing the material, carried out.

The following "results were obtained:

Decomposition time: 28.5 min.

Minimum resistance torque: 1.205 m "kg self-heating time: 2.5 min at 190 ⁰ C - 27.33 min at 195 ° C

The results obtained were very good taking into account the proportion of the copolymer (10 parts by weight) in the resin.

4. Gluing

No sticking was observed after 45 minutes.

H. Extractability of Lubricants

The lubricants according to the invention can be used to "lubricate" polymers intended for the manufacture of packaging and containers for food and beverages, and it was therefore necessary, despite their low toxicity, to be able to be extracted by various solvents, namely water, ethanol Determine water 50/50, an aqueous solution of acetic acid (3%) and heptane, by simulating food and beverages.

6098477 1038

The following approaches were used for this investigation:

Αηό 913 atz no. 915 916 D - ^ £ * -l · - Q y> * / ί | -4- Λ ·? T Λ 100 100 100 ßesxanQ xexjLe 11 914 11 11 Polyvinyl chloride resin 0.5 100 0.5 0.5 Reinforcing agents 3 11 3 3 Acrylic resin 0.25 0.5 0.25 0.25 epoxy. Soybean oil 0.3 3 0.3 0.3 Chelating Agents 1832 0.1 0.25 0.1 0.1 _m 2-phenyl-indole 0.3 0.3 0.3 0.3 Zinc stearate 1 0.1 1 - Calcium stearate 0.3 0.3 - - Iiodiglycol dibehenate - 1 - - Pentaerythri ttetrabehenat - - 0.3 - 1,4-butanediol dibehenate 0.3 1,2-propanediol dibehenate -

The extractions were carried out in semi-rigid bottles, made with the resins given above.

The bottles had the following characteristics:

Diameter: 62 mm

Height: 170 mm

Contents: 375 ml

Weight: 28 g

The ratio of the volume of the solvent to the surface area of the plastic material that has been subjected to extraction, was about 1: 100 ml of solvent, taking into account the geometric properties of the bottles.

609847/1038

Procedural conditions

Temperature: 49 ⁰ C

Heating: A thermostatically controlled cfen for the non-ignitable solvents (water and Acetic acid)

A thermostated water bath for the flammable solvents (alcohol and heptane)

Duration of the extraction: This was in each case longer than that which would have provided consistent maximum values.

The following periods were observed:

Water: 15 days
Acetic acid (390: 15 days
Aqueous ethanol: 3 to 4 days
Heptane: 3 days

The amount of the extracted lubricant was determined by thin layer chromatography in comparison with a standard evaluation .

A blind test was carried out with comparison bottles that contained no lubricant and a purely negative result was obtained.

The results obtained are shown in the table below. The determined lubricant quantities are in / Ug / ml of the solvent or expressed per cm of the surface subjected to extraction, giving the same result supplies.

609847/1038

approach
No. lubricant Heptane solvent water Vinegar·-
acid, - 913 Thiodiglycol
behenat 1.3 Watery?
Ethanol 0.13 0.4 Pentaerythritol. ^ -
tetrabehenat 0, -26 0.6 0.13 0.26 914 Thiodiglycol
behenat 0.8 0.13 < 0.13 <0.13 1,4-butanediol
dibehenat 0.8 0.13 - * - 0, -53 - £ 0.13 915 Thiodiglycol
behenat 0.6 < 0.13 - 0.13 -: 0.13 1,2-propanediol
behenat 0.26 0.13 -C 0.13 <0.13 916 Thiodiglycol
behenat 0 0 0 Penta e rythri t-
tetrabehenat 0 0 0 0 1,4-butanediol
dibehenat 0 0 0 0 1,2 propanediol
dibehenat 0 0 0 0 0

These results show that the four lubricants tested have a strong resistance to solvents, in particular Water used to simulate food and drinks, which is very important because it is difficult to create containers for mineral water that the latter cannot is contaminated by the addition in the polyvinyl chloride.

The results obtained with water are below
or near the sensitivity threshold of the investigation procedure.

60984 7- / 1038

I. Investigation of the tendency to bubble "in polyvinyl chlorides containing the lubricants according to the invention.

It is known that there is a release of gas during manufacture the resin and especially at the time of extrusion or blow molding is a serious disadvantage, vana objects, such as bottles, as this can lead to the formation of visible bubbles in the plastic.

The following results were recorded:

Lubricant temperature during observations

which blown occur - C

Glyceryl trimontanate 150 Release increasing with temperature

Glyceryl tribehenate 230 Low release

1,2-propanediol dibehenate 250 No release

Pentaerythri tetra-

behenat 195 Low release

When different behenates are combined it is possible to get lubricant associates that are as good or as good are even better than the known associations of Montanaten.

Furthermore, the advantage of the behenates is particularly important with regard to the various types of use of the resins.

In general, the behenates do not release any gas at all as the temperature of the resin increases progressively to 250 ° C.

The lubricants of the invention are generally either alone or in combination in proportions of about 0.5 to 2 parts by weight incorporated into the thermoplastic material.

609847/1038

The following examples serve to illustrate the processes for preparing the substances of the present invention.

example 1

1,2-propanediol dibehenate

To a flask (500 ml) equipped with a central stirrer, dropping funnel, nitrogen source, thermometer, Dean-Stark trap, and vertical condenser was added 256.5 g (0.75 mol) of behenic acid, the became increasingly .erhitzt stirring until complete melting (about 70 ⁰ C), after which 30.4 g (0.4 mol) of 1,2-propanediol and 0.50 g of a 50% aqueous solution of sodium hydroxide were added.

The reaction medium was heated under a nitrogen atmosphere for 3 hours at 195-200 ⁰ C, then for 2 hours at 220 to 225 ° C, and this latter temperature was maintained for about 4 hours has been reached until an acid number less than or equal 12th

The reaction medium was cooled to about 150 ^° C. and the molten material was poured onto a stainless steel plate. After cooling, 272 g of 1,2-propanediol dibehenate were obtained. Mp: 52 ° C - yield: 100%

Using the same procedure but using the appropriate one Starting materials, the following compounds were made:

Compound melting point

1,4-butanediol dibehenate 68 ^° C

Pentaerythritol tetrabehenate 70 ° C

6098 47/1038

Zb ι j öj b

Example 2 Thiodiglycol dibehenate

To a flask (1250 ml) equipped with a central stirrer, dropping funnel, nitrogen source, thermometer, Dean-Stark trap, and vertical condenser was added 224.5 g (0.66 mol) of behenic acid and the medium was heated progressively up to the complete melting of the 3eLenr äure (about 70 ⁰ C), after which 44.25 g (0.28 mol) of thiodiglycol and 0.50 g of a 50% aqueous solution of sodium hydroxide was added with stirring.

The reaction medium was turned on under a nitrogen atmosphere 195 ° C for 3 hours, then heated to 225 ° C for 2 hours, and this latter temperature was maintained for about 4 hours until an acid number below or equal to I2 was reached. The mixture was cooled to about 90 to 95 ° C and the molten material poured onto a stainless steel plate. After cooling, 246 g of thiodiglycol dibehenate were obtained. M.p .: 73 ° C - Yield: 97 #

Example 3 Diethylene glycol dibehenate

Into a flask (2 l) equipped with a central stirrer, thermometer, Vigreux column and a vertical condenser provided with a container were placed 1280 g (3.8 mol) of behenic acid and 226 g (2.13 mol) of diethylene glycol . The reaction medium, under a nitrogen atmosphere, was slowly heated until the mixture completely melted (about 75 ^° C.) and 1.3 g of sodium hydroxide lozenges dissolved in a minimum of water were added. The reaction mixture was gradually heated in the Vigreux column to reflux and then cooled to a temperature at which a distillation of the water from the medium was (about 145-159 ⁰ C), wherein the diethylene glycol was not distilled off. When the temperature had reached 220 ⁰ C, the Yigreux column was removed and the temperature was maintained for about four hours, has been reached until an acid number of about 10 degrees. The reaction medium was cooled to about 70 ^° C. and the molten material was poured onto a stainless steel plate. After cooling, 14O6 g of diethylene glycol

60984 7- / 1038

behenat received.

Melting point: 59 ° C - yield: 99%

Using the same procedure but using the appropriate one Starting materials were the following compounds manufactured:

Compound melting point

Dipentaerythritol pentabehenate 63 ⁰ C

Triethylene glycol 54 ° C

Example 4 Trimethylol propane tribehenate

In a flask (2 1) equipped with a central stirrer, thermometer and a vertical condenser fitted with a container, 1440 g (4.25 moles) of behenic acid and 219.5 g (1.6 moles) of trimethylolpropane were added Reaction medium was heated slowly under a nitrogen atom sphere until the medium was completely melted and 1.4 g of sodium hydroxide lozenges dissolved in a minimum of water were added. The reaction medium was gradually heated to a temperature at which distillation of water from the medium occurred without causing distillation of trimethylpropane. The medium was then heated to 220 ° C. and this temperature was maintained for about 4 hours until an acid number of about 4 was reached. After cooling to 90 ⁰ C, the medium with hydrogen peroxide (200 parts by volume) was entfärbt.Die temperature was maintained, and at about 90 to 90 ⁰ C for 30 minutes, poured the molten material onto a stainless steel plate. After cooling, 1550 g of trimethylolpropane tribehenate were obtained.
Pp: 52 ° C - Yield: 99.3%

Example 5 Glyceryl tribehenate

In a flask (500 ml) equipped with a central stirrer, drip * funnel, nitrogen source, thermometer, Dean-Stark trap

60 9847- / 1038

-50- 26I983G

and a vertical cooler was 344 g
(1 mole) of behenic acid. The medium was gradually taking
Stirring heated, was completely melted until the acid (about 70 ⁰ C), and 35.3 g (0.4 VIoI) Glycerin uid 0.68 g of a 50% - solution of sodium hydroxide were added.

The reaction medium was heated under a nitrogen atmosphere to about 190 to 200 ^° C. for 3 hours and then to about 220 to 225 ^° C. for 2 hours.

The latter temperature was maintained for about 4 hours until an acid number below or equal to 14 was reached.

The reaction medium was cooled to about 140 ^° C. and the molten material was poured onto a stainless steel plate.

After cooling, 357 g of glyceryl tribehenate were obtained.
Melting point: 64 ⁰ C - yield: 100 #

609847/1038

Claims (21)

Claims 1., lubricant, characterized in that it is implemented by of behenic acid with butanediol-14, thiodiglycol, propanediol - 1,2, Glycerin, pentaerythritol, dipentaerythritol, diethylene glycol, triethylene glycol or trimethylolpropane has been produced. 2. Lubricant according to claim 1, characterized in that it comprises glyceryl tribehenate. 3 · lubricant according to claim 1, characterized in that it includes pentaerythritol tetrabehenate. 4. 1,2-propanediol dibehenate. 5. Thiodiglycol dibehenate. 6. Diethylene glycol dibehenate. 7. Triethylene glycol dibehenate. 8. Trimethylol propane tribehenate. 9. Dipentaerythritol pentabehenate. 10. 1,4-butanediol dibehenate. 11. lubricant associate, characterized in that it is at least two compounds from the group: metal salt of behenic acid, 1,2-propanediol dibehenate, thiodiglycol dibehenate, diethylene glycol dibehenate, Triethylene glycol dibehenate, trimethylol tribehenate, dipentaerythritol pentabehenate, 1,4-butanediol dibehenate, Glyceryl tribehenate and pentaerythritol tetrabehenate. 609847/10 38 -52- 2613836 12. Lubricant associate according to claim 11, characterized in that that it contains calcium behenate as the metal salt of behenic acid. 13 - lubricant association "; according to claim 11, characterized in that that it is thiodiglycol dibehenate and pentaerythritol tetrabehenate preferably in a ratio of about 10 to 3, especially about 8 to 3 contains. 14. Lubricant associate according to claim 11, characterized in that that it contains thiodiglycol dibehenate and!, 4-butanediol dibehenate preferably i: i in a ratio of about 10 to 3. 15 lubricant associate according to claim 11, characterized in that that it is thiodiglycol dibshenate and 1,2-propanediol dibehenate preferably in a ratio of about 10 to 3 contains. 16. Lubricant associate according to claim 11-12, characterized in that that it contains glyceryl tribehenate and calcium behenate - preferably in a ratio of about 2 to 3 contains. 17. Lubricant associate according to claim 11-12, characterized in that that it contains thiodiglycol dibehenate and calcium behenate, preferably in a ratio of about 3 to 2. 18. Lubricant associate according to claim 11-12, characterized in that that it is pentaerythritol tetrabehenate and calcium behenate, preferably in a ratio of about 3 to 2 contains. 19. Lubricant associate according to claim 11, characterized in that that it contains thiodiglycol dibehenate, pentaerythritol tetrabehenate and calcium behenate. 20. lubricant associate according to claim 1I _3, characterized in that it is thiodiglykoldibelienst; 1 ₉ 2 = propanediol dibehenate 608847 / 103S and contains calcium behenate. 21. Use of a lubricant according to claims 1-10 or a lubricant association according to claims 11-20 preferably in a proportion of. 0.5 to 5 parts by weight in a thermoplastic material. 60984 7/1038