DE2417990A1 - PROCESS FOR THE PRODUCTION OF PREPARATIONS BASED ON POLYVINYL CHLORIDE OR VINYL CHLORIDE MIXED POLYMERIZED POWDERS - Google Patents

Description

Process for the manufacture of preparations
based on polyvinyl chloride or
Vinyl chloride copolymer powders

(Priority: April 12, 1973 France No. 73 13305)
The invention relates to a process for the production of preparations or mixtures based on powders of polyvinyl chloride or its copolymers, which contain all the additives necessary to ensure good processing conditions and the properties required for the various purposes of the obtained by molding or extrusion Products are necessary.

There are certain parent mixtures known, in general
are made of polyvinyl chloride, which has been mixed at a temperature above the glass transition point of the plastic material with considerable amounts of a certain number of additives, which depending on the intended use

4098A3 / 0931

Purpose have been selected and the stabilizing, plasticizing, lubricating, shock-proofing, antistatic have making, coloring or other properties.

These additive concentrates based on polyvinyl chloride, are intended to be added to the same plastic material to become .. The mixing of the two powders is done in the cold.

Another method is to add the solid additives previously mixed in the cold to polyvinyl chloride and then to mix the whole with heating and when the temperature has exceeded the glass transition point of the polymer has to add the liquid additives and mix to continue up to a temperature of 120 to 130 ° C.

The addition of these additive mixtures or of additive concentrates based on polyvinyl chloride to the plastic powder generally takes place in the course of 10 to 30 minutes at temperatures between 100 and 180 C using slow- or fast-running mixing devices *

These methods have the disadvantage that the treated polyvinyl chloride in the course of the mixing is heated for a certain time to a temperature which is a thermal May cause decomposition. This results in a certain consumption of the stabilizer used, so that it in certain cases it is necessary to add these in a larger amount than would be necessary if one were to use the polyvinyl chloride would only heat up when deformed.

Another disadvantage of this method is that some of the polyvinyl chloride is heated two or three times, once for the preparation of the master mixture containing the additives, optionally a second time in the course of the preparation the final mixture and finally in the deformation of the final mixture obtained. When the final stabilized mixture for 15 to 30 minutes to a temperature between 100 and

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When heated to 150 ° C, one can use two different devices use either a slow-speed mixer that requires external heat to be supplied via a double jacket, or a high-speed mixer whose mechanical friction exerted on the grains by mixing is sufficient to raise the temperature sufficiently. Then, after the penetration of the liquid additives has been achieved, It is necessary to cool the powder to the final temperature of the mixture in order to avoid agglomeration of the granules. To do this, it is either necessary to use the mixer for a longer period of time when cooling down in this device or to use any other device dedicated exclusively to the stabilized final mixture to cool off.

Finally, another method is known which consists in _{using a polymerizate other than polyvinyl chloride /} powder form, used as an impact-resistant agent, which is generally an acrylonitrile-butadiene-styrene elastomer or a methyl methacrylate-butadiene-styrene elastomer, in the Heat in a mixer with variable speed to allow the additives to be absorbed, after which the powdery composition is mixed in the cold with the pure polyvinyl chloride present in powder form.

This method has the advantage that the polyvinyl chloride is heated only once in the course of the deformation, whereby the decomposition of the plastic material is restricted and stabilizer, time and energy are saved.

However, this process requires the necessary presence of an elastomer serving as a carrier material for the additives. In addition, it is necessary to mix the additives in hot at a temperature between 40 and 120 ^° C. in order to promote good penetration of the additives into the elastomer and certain of these additives must be in a liquid state at the temperature of the mixture.

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On the other hand, the proportion of liquid additives that can be introduced into polyvinyl chloride using this method is on 3% and depends on the content and type of elasticizing agent.

All known methods have the disadvantage that at least one heating stage is required, the at least part of the polyvinyl chloride used as the starting material or the stabilizers or both materials must be subjected to at the same time. This results in the above-mentioned disadvantages, so that these manufacturing processes are not suitable for continuous operation.

The method according to the invention now allows all of these To overcome disadvantages.

The invention therefore relates to a process for the production of preparations based on polyvinyl chloride or vinyl chloride mixed polymer powders, which contain at least one normally liquid and at least two normally solid additives, such as stabilizers, plasticizers, lubricants, elasticizers, processing aids, antistatic agents, dyes, gelling agents, crosslinking agents and / or blowing agent, which is characterized in that one or more normally liquid additives are added to the entire polyvinyl chloride or vinyl chloride copolymer powder during any stage of the polymerization or after the polymerization has taken place, separately in the cold a mixture of two or several normally solid additives and then at room temperature a mixture of all of the polyvinyl chloride or vinyl chloride copolymer powder mixed with the liquid additive and only the normally solid A. dditive containing mixture prepared and the final mixture so obtained for a time of less than 10 minutes by stirring, without the temperature of the final mixture exceeds 40 ⁰ C.

409843 / Q931

On the other hand, it is known to produce polyvinyl chloride preparations containing various stabilizers or lubricants included by adding the additives either to the monomer present in the reaction medium or during the polymerization or after the end of the polymerization is added.

The method according to the invention differs from this last-mentioned process in that there is no normally solid additive to the monomer, nor to the reaction medium in the course of the polymerization, to the one already produced Polymer is added without the polymer already being impregnated with the normally liquid additives is.

The invention is based in particular on the finding that the powder impregnated with liquid additive on the basis of polyvinyl chloride at room temperature remarkable absorption properties · for the other, in the solid state present additives. This has the advantage of using some mixture of solid additives can, which can optionally also contain polymers that are not polyvinyl chloride resins.

Due to the fact that the liquid additives from the entirety of the resin used are based on polyvinyl chloride can be absorbed and not by a part of this resin or by the elasticizing agent Content of the liquid additives in the resin can be significantly larger and allow absorption of larger amounts of solid additives. The fact that the resin is already with the liquid. It is impregnated with additives that allow the final mix or to prepare the stabilized mixture without the addition of heat at room temperature by not being based on Polyvinyl chloride-based solid additives, which in turn have been mixed in the cold, are absorbed, causing one a powder obtained, which has improved properties with regard to for the production of various plastic articles and in particular hollow body has improved properties.

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The powders obtained in this way show good homogeneity and excellent fluidity, which enables both continuous and discontinuous processes to be carried out, since these powders flow well in the supply lines and metering or mixing devices without each other interfering agglomeration phenomena, blockages or sticking to the walls result.

The use of automatic metering devices in the case of continuous Process avoids weighing the additives.

Since there is no such thing as homogenization and mixing of the powders When heat is applied, the powders do not undergo thermal degradation of the polyvinyl chloride and yield it significant advantages in terms of heat energy consumption and the possibility of using less complicated materials to use.

The process according to the invention makes it possible to produce the mixtures in a very short time, which is less than 5 minutes and is preferably between 1 and 3 minutes. This results in significant time savings, eliminating the hourly Production quantities can be increased or the volume of the devices used can be reduced.

The advantage of the method according to the invention is also that it can be conveniently used to continuously produce a stabilized final mixture, what. is not possible with the classic methods that require at least one heating stage.

Even if this method requires the use of simpler and smaller mixing devices, it is still possible any available conventional mixing device use without the need to modify the design if the process is operated discontinuously target.

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Due to the fact that the substantial mixing takes place at room temperature in a very short time, the through the The temperature increase caused by friction between the grains is relatively small and lies in the range of 10 to 20 C, whereby the final temperature remains below 40 ° C. It is therefore not necessary to use the stabilized final mixture after Mixing to cool so that it is immediately and directly transferred from the main mixer into the deforming devices can be.

The vinyl chloride-based resin used can be polymerized in bulk, in emulsion or preferably be made in suspension.

The liquid additives can either after the end of the polymerization are added to the polyvinyl chloride, in particular by adding it to the containing the powder suspension Reactor takes place, or can before or during the polymerization be admitted. Nevertheless, it is preferred to make this addition towards the end of the polymerization after the unreacted has been removed Vinyl chloride by degassing, otherwise the liquid additives are entrained with the eliminated gas can be, resulting in a loss or a lower content of these additives in the powder on the basis of Vinyl chloride yields.

As a powder based on polyvibyl chloride you can either use a homopolymer or a copolymer such as a vinyl chloride-vinyl acetate copolymer.

According to a preferred embodiment of the invention takes place the preparation continuously.

Further embodiments, objects and advantages of the invention emerge from the following description, the examples and the drawing.

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The drawing illustrates such a continuous procedure, according to which the two powders are converted into two Container having storage bunker are introduced. The container 1 contains the impregnated with the liquid additives Powder based on vinyl chloride, while the container 2 contains the mixture of solid additives. The two mixtures are introduced simultaneously with the aid of the metering devices 3 into the final mixer 6, which is on the other hand is supplied with a comminuted plastic material with the aid of a conveyor belt 5, which in the distribution funnel 4 is included and that includes the production waste generated during the deformation. The one obtained at the output of the mixer 6 Powder is taken over by a mechanical conveyor 7 and transferred to a storage container 8, from which the material is introduced into the deforming device with the aid of the screw conveyor 9.

The liquid additives can be plasticizers, or lubricants Be stabilizers, the melting point of which is below 40 ° C., preferably 30 or 20 ° C. The additives that are solid at room temperature can be heat or light stabilizers, lubricants, Plasticizers, elasticizers or shockproofing agents, antistatic agents, dyes or colorants, gelling agents, Be blowing agents or crosslinking agents.

The following examples are intended to explain the invention further without, however, restricting it.

example 1

A polyvinyl chloride powder is used which contains 4.5% soybean oil and 1 % glycerol monooleate and which by adding the. these compounds to the polyvinyl chloride suspension obtained in the polymerization in a reactor. 100 parts of this powder are mixed at room temperature with the solid additives of the following previously mixed in the cold. Composition:

40984370931

Shockproof agent
(Acrylonitrile-butadiene-styrene copolymer)

Calcium stearate Zinc stearate dyes

2417990 Parts 10 30 " O, 70 " O, 005 " O,

Mixing takes place for 3 minutes at room temperature in a Lödige mixer, which is operated at 150 rpm and whose agitator blades is designed like a ploughshare.

The same mixture is used for comparison purposes classical process by mixing the solid additives and the polyvinyl chloride powder in a Papenmeier high-speed mixer brings in, which is operated at 1500 rpm. After the .Temperature has reached 70 ° C, epoxidized is sprayed Soybean oil and glycerol monooleate. Mixing, carried out for 20 minutes, is due to the friction an increase in temperature to 130 ° C

The following table shows that the results are just as good as those obtained with the classic mixing methods in the Heat obtained when using the same additives in identical amounts based on the polyvinyl chloride.

Dry, with space
temperature produced
powder Dry, at
130 ⁰ C produced
made powder Thermal stability 48 47 Fluidity 10 - 10 Enamel mass weight, g 36.9 36.5 Bottle weight, g 23.3 23.0 non-melted
materials practically none practically none Appearance homogeneous homogeneous transparency Well Well

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- OK -

The thermal stability - stands for the time it takes for you
A rapid change in color of a sample to dark brown is required, which is placed in the form of a plate in a test tube that is heated to 180 ° C in an oil bath.

The fluidity is determined with the help of a method according to which the minimum opening (diameter in mm) is determined, the
allows the powder to flow into a series of cones with angles of 45 mm and openings of 3 to 30 mm.

The powder obtained has excellent fluidity
and does not cause any difficulty in supplying a HESTA type extrusion blow molding apparatus having a mold
for bottles with a capacity of 0.25 l
is. The properties of the powder are in all respects analogous to those of the powder, which is produced according to a classic process
was produced by increasing the temperature and
a long working through of the final mixture is characterized.

Example 2

As described in Example 1, homogenization is carried out in one
Slow running Lödige mixer for 2 minutes 100 parts
Polyvinyl chloride containing 4.5 % oil and 1 % glycerol monooleate with a cold-prepared mixture of solid additives of the following composition:

Shockproof agent
(Methyl methacrylate-butadiene-styrene copolymer) 10 parts

Processing aids

(Methyl acrylate-ethyl acrylate copolymer) 1 "

Calcium stearate 0.40 "

Zinc stearate 0.40 "

α-phenylindole 0.20 "

Stearic acid. 0.20 "

409843/0931

The extrusion and blow molding process is carried out with the aid of a KAUTEX device with a diameter of 50 mm, which is equipped with a mold for bottles with a capacity of 1 l is.

The fluidity of this mixture is the same as that of a mixture made by conventional procedures Mix for 15 minutes at 130 ° C in a high-speed mixer. The thermal stability, the appearance and impact resistance of the bottles obtained are also identical.

The impact resistance is determined in such a way that the percentage of unbreakable bottles of 50 with Water-filled bottles intended to be dropped from a certain height. '

Dry, with space
temperature herge
made powder Dry, at
130 ° C
made powder Fluidity 5 10 Extrusxon consumption
(kg / h) 18.5 18.3 Bottle weight (g) 39 39 non-melted
materials practically none practically none Appearance homogeneous homogeneous Impact resistance
(Height of the fall = 1.20 m) 82% 78% thermal stability
(Minutes) 58 58

Example 3

100 parts of polyvinyl chloride containing 22% dioctyl phthalate are homogenized at room temperature for 3 minutes with a mixture prepared in the cold from 1 part of glycerol monostearate and 0.75 part of barium cadmium stearate.

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The mixture is extruded through a circular mouthpiece and then blown into a film which has the same properties as a film made from a mixture of the same composition prepared in the heat was prepared.

Dry, with space
temperature herge
made powder Dry, at
130 ° C
made powder Fluidity 15th 15th Extrusion consumption
(kg / h) 14.5 14th Appearance of the slide homogeneous homogeneous non-melted
materials practically none practically none Tensile strength (kg / cm) 340 360 Elongation at break (%) 180 190

The tensile strength and elongation at break values were at one Pulling speed of 100 mm / minute determined.

Example 4

A polyvinyl chloride containing 4% epoxidized soybean oil is mixed continuously, without heating, at room temperature in a drum mixer with a homogenizer in the cold. sizing the following ingredients mixture obtained:

Impact resistant additive
(Methyl methacrylate-butadiene-styrene terpolymer

Calcium stearate

Zinc stearate

Glycerol trihydroxystearate

α-phenylindole

Ultramarine blue

Parts by weight 10 O.4 0.4 1.5 0.2 0.01

Then 104 parts by weight of polyvinyl chloride, which is 4% epoxidized Contains soybean oil, and the premix of the solid additives is metered in with the help of conveyor belts.

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The two more powdery! Mixes are in a mixer introduced, which is provided with a planetary motion executing screw, in which it is at a temperature below 40 C are homogenized. At this stage you can if you want add a comminuted material that has accumulated as waste from previous deformation processes. The mixture obtained in this way is transported by a mechanical transport system (e.g. an Archimedes snail or a spiral screw), in which the material is completely transported to the deforming device is homogenized, with the deformation device in Example 3 used extrusion blow molding device is provided.

The deformability, appearance and properties of the bottles obtained from the mixture of this example are practically identical to the corresponding properties of Bottles that have been made from a mixture made in the classic way in the heat of the following ingredients was prepared:

Solid components parts by weight

Polyvinyl chloride (K value 57) 100

shockproof additive
(Methyl methacrylate-butadiene-styrene terpolymer) 10

Calcium stearate 0.4

Zinc stearate x 0.4

Glycerol trihydroxystearate 1.5

oc-phenylindole 0.2

Ultramarine blue 0.01

Liquid component

Epoxidized soybean oil 4

409843/093 1

The solid constituents are introduced into a high-speed Papenmeier mixer which is operated at 1500 rpm. By Mechanical friction between the particles increases the temperature up to 70 C, whereupon the epoxidized soybean oil is applied to the solid Ingredients sprays. Mixing is continued until the temperature has increased by itself to 125 ° C. The mixing takes place for 20 minutes. The mixture is then placed in a container equipped with a stirring system and then cooled to a temperature below 40 ° C.

Dry, with space
temperature herge
made powder Dry, at
130 ° C
made powder Extrusion consumption
(kg / h) 19.2 19.3 Bottle weight (g) 39 39 non-melted
materials practically none practically none Appearance homogeneous homogeneous Impact resistance
(Height of the fall = 1.20 m) 80 % 76% thermal stability
(Minutes) 56 56

Example 5

As described in Example 1, mixing is carried out in a low-speed Lödige mixer for 2 minutes at room temperature 106.2 parts by weight of a vinyl chloride-vinyl acetate copolymer (Monomer ratio 90:10) with a K value of 55, the 5% epoxidized soybean oil, 1% glycerol monooleate and 0.2% Contains zinc ethyl hexoate, with a powdery mixture prepared at room temperature and having the following composition:

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Impact resistant additive
(Acrylonitrile-butadiene-styrene terpolymer) 5 parts by weight

Calcium stearate 0.5 "

a-phenylindole 0.3 "

Stearic acid 0.2 "

Dye · 0.05 »'

For comparison purposes, mix in the heat according to the in Example 1 described technique 100 parts of the vinyl chloride-vinyl acetate copolymer with a K value of 55 and a monomer ratio of 90:10 in a fast-running one Papenmeier mixer operating at 1500 rpm with a Mixture of solid additives of the following composition:

Impact resistant additive
(Acrylonitrile-butadiene-styrene terpolymer) 5 parts

Calcium stearate, 0.5

a-phenylindole 0.3 "

Stearic acid 0.2 "

Dye 0.05 "

This mixture is worked through until the temperature reaches 70.degree. A mixture of liquid additives of the following is then added by dispersing with stirring for 2 to 3 minutes Composition a:

Epoxidized soybean oil

Glycerol monooleate

Zinc ethyl hexoate

The mixture is mixed until the temperature reaches 125 ° C.

The two mixtures are then deformed using a flat mouthpiece, leaving sheets with a thickness of 1.2 mm and a width of 350 mm. These sheets are used to make cups and by thermoforming other hollow bodies.

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5 2 Parts 1 Il O, ti

There is practically no difference in the properties of the mixtures and those due to thermal deformation received products.

Dry, with space
temperature herge
made powder Dry, at
130 ° C her
made powder Fluidity (diameter
the opening in mm) 10 10 thermal stability
(Minutes) 36 34 Supply of
Extrusion press Well Well Extrusion consumption
(kg / h) 22.5 23.5 Appearance of the leaf satisfactory satisfactory. non-melted
materials practically none practically none,
few Conduct at ther
mix deform satisfactory satisfactory.

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Claims (5)

Claims 1.} Process for the manufacture of preparations based on of polyvinyl chloride or vinyl chloride copolymer powders, which contain at least one normally liquid and at least two normally solid additives, such as stabilizers, plasticizers, lubricants, elasticizers, Processing aids, antistatic agents, dyes, gelling agents, crosslinking agents and / or blowing agents, characterized in that the entire polyvinyl chloride or vinyl chloride copolymer powder during any stage of the polymerization or after polymerization with one or more normally added liquid additives, separately in the cold a mixture of two or more normally solid additives and then at room temperature a mixture of the whole, with the liquid additive added polyvinyl chloride or vinyl chloride mixed polymer powder and which produces the mixture containing only the normally solid additives and the mixture thus obtained The final mixture is stirred for a period of less than 10 minutes without the temperature of the final mixture increasing to 40 ° C exceeds. 2.) Process according to claim 1, characterized in that the powder used is a pulverulent vinyl chloride-vinyl acetate copolymer begins. 3.) The method according to claim 1, characterized in that the liquid additives are entered into the container in after the end of the polymerization, the suspension of the polyvinyl chloride or vinyl chloride mixed polymer powder is included. 4.) The method according to claim 1, characterized in that the stirring of the mixed with the liquid additives Polyvinyl chloride or vinyl chloride mixed polymer powder 409843/09 3 1 takes place with the mixing of the solid additives for less than 5 minutes. 5.) The method according to claim 1, characterized in that all of the poly- • vinyl chloride or vinyl chloride copolymer powder containing the liquid additives
is continuously added to the mixture prepared in the cold from the solid additives and continuously supplied to a mixer with the two components previously prepared in this way, the residence time of the final mixture in the mixer being less than 10 minutes and
the temperature of the mixture does not exceed 40 ° C. 409843/0931