PL242560B1 - Polymer surfactants with plasticizing properties - Google Patents

Abstract

A polymeric surfactant that is a polyether ester with a molecular weight of 1000 to 3000 Da, a copolymer of succinic acid, monohydroxy alcohol, and polyoxypropylenediol (Rokopol D450) and a compound with the formula: where: R1 is the residue of a monohydroxy alcohol selected from: 2-ethylhexyl or caprylic alcohol, capric, lauryl, myristyl, cetyl or stearyl, isostearic or elaidic, or oleic, or linoleic or elaidolinol, linolenic, ricinoleic, arachidyl, behenyl or erucyl. n - is a natural number from the range 2-4, p - is a natural number from the range 5-6. The application also relates to the use of the compound as a plasticizer, in particular for the production of plastics or varnishes.

Description

Description of the invention

The subject of the invention are new biodegradable polymeric surfactants which are a copolymer of succinic acid, monohydroxy alcohol and polyoxypropylene diol (Rokopol D450). The compounds of the invention are suitable for use as plasticizers for plastics, especially biodegradable plastics.

Application WO90/01521 describes biodegradable plastics obtained on the basis of polylactide (i.e. poly(lactic acid), abbreviated PLA) plasticized with lactic acid or lactide residues, as well as plastics obtained from a mixture of PLA and polyolefin polymers such as PVC, PE, PVA e.t.c.

Currently, the available monomeric and polymeric plasticizers, which are used as plasticizing additives for plastics, in particular for PLA and PVC, are mainly monomeric citric acid esters, such as: tributyl citrate, tributyl acetyl citrate, triethyl acetyl citrate, as well as glycerol triacetate, dioctyl terephthalate, dioctyl adipate or dioctyl succinate, while polymeric plasticizers such as polyesters based on adipic acid with a molecular weight of 800 to 6000 Da and polyesters based on sebacic acid are also playing an increasingly important role (see US6235825, JP2002146170, US5726220, WO2008075775). Due to the lack of harmful properties for the human body, these products are called green plasticizers. The use of green plasticizers is wide, as they are used, among others, in in products such as: toys, equipment and medical devices, including tubes, blood containers, drips, stents made of PLA, foils and biodegradable packaging, especially dedicated to food, as well as cutlery, plates, bowls or cups. In addition, plasticizers based on esters of citric, succinic, terephthalic, sebacic or adipic acids are used in products such as: cables, additives for wallpapers, roofing membranes, structural elements in cars (internal and external), and gaskets in refrigerators.

The key parameters characterizing the effectiveness of the plasticizer in the plasticization of the plastic are: high resistance to solvent extraction, including organic solvents and water, low migration and volatility of the plasticizer from the plastic and during the storage of the final product made of it.

The disadvantage of the available monomeric plasticizers is their excessive migration from the plastic, in particular from PLA, progressing during the use of the plastic and at elevated temperatures. Plasticizer migration is a consequence of its low molecular weight, a molecular structure that contributes to insufficient compatibility with the material as well as with other ingredients of the formulation. Plasticizer migration leads to such undesirable effects as disintegration of the structure of the final product, discoloration, loss of physical properties, e.g. increased brittleness, lack of tensile strength.

The aim of the invention is to provide new compounds - polymer surfactants - suitable for use as plasticizers, especially for biodegradable plastics such as PLA-containing polymers. It is desirable that the new plasticizers are also characterized by biodegradability and reduced migration from the plastic. At the same time, it is desirable that they are surface-active compounds that lower the surface tension at the water-air interface and have the ability to form micelles (low cmc concentration).

It is a particular object of the present invention to provide the ability to obtain a poly(lactic acid) composition with significantly improved elongation at break and impact strength while maintaining clarity and providing good mold release properties after processing.

In a particular embodiment of the invention, it is desirable to be able to use the new plasticizers in polymeric cosmetic products such as nail polishes.

The subject of the invention is a polymeric surfactant which is a polyether ester with a molecular weight of 1000 to 3000 g/mol, a copolymer of succinic acid, monohydroxy alcohol and polyoxypropylenediol (Rokopol D450) and a compound of the following formula:

Where:

Ri is a monohydroxy alcohol residue selected from 2-ethylhexyl or caprylic, capric, lauryl, myristyl, cetyl or stearyl, isostearyl or elaidine or oleic or linoleic or elaidolinol, linolenic, ricinoleic, arachidyl, behenyl or erucyl alcohols.

n - is a natural number from the range 2-4, p - is a natural number from the range 5-6.

Preferably, the polymeric surfactant of the invention is a compound selected from:

- a copolymer of succinic acid, lauryl alcohol and polyoxypropylene diol (Rokopol D450), with the average molecular weight of this copolymer being 1836 g/mol,

- a copolymer of succinic acid, 2-ethylhexyl or caprylic alcohol and polyoxypropylenediol (Rokopol D450), the average molecular weight of this copolymer being 1780 g/mol,

- a copolymer of succinic acid, capric alcohol and polyoxypropylene diol (Rokopol D450), with the average molecular weight of this copolymer being 1808 g/mol,

- a copolymer of succinic acid, myristyl alcohol and polyoxypropylenediol (Rokopol D450), with the average molecular weight of this copolymer being 1864 g/mol,

- a copolymer of succinic acid, cetyl alcohol and polyoxypropylene diol (Rokopol D450), with the average molecular weight of this copolymer being 1892 g/mol,

- a copolymer of succinic acid, stearyl alcohol and polyoxypropylenediol (Rokopol D450), with the average molecular weight of this copolymer being 1920 g/mol,

- a copolymer of succinic acid, arachidyl alcohol and polyoxypropylenediol (Rokopol D450), the average molecular weight of this copolymer being 1948 g/mol, or

- a copolymer of succinic acid, behenyl alcohol and polyoxypropylene diol (Rokopol D450), the average molecular weight of this copolymer being 1976 g/mol.

A further object of the invention is the use of the compound defined above as a plasticizer, in particular for the production of plastics or varnishes. Preferably, the varnish to be produced is a nail polish. Preferably, the plastic produced is a poly(lactic acid) or poly(vinyl chloride) material.

The presented polymeric surfactants with plasticizing properties are distinguished by the possibility of designing their structure by increasing or decreasing hydrophilic or hydrophobic units in the molecule chain, expressed by the HLB coefficient. Designing the structure of a polymeric surfactant with plasticizing properties is possible thanks to the use of an innovative production method, which results in strict control of the chain structure and adjustment of the molecular structure of the plasticizer to the structure of the target material, and above all PLA.

The presented polymeric surfactants with plasticizing properties show surface-active properties, because they reduce the surface tension at the water-air interface in the range of 37-40 mN/m in a 0.1% solution at a measurement temperature of 25°C, and also under these conditions they have cmc, i.e. critical micellization concentration below 1 g/l. These products can be characterized by HLB. The HLB value of the compounds of the invention ranges from 1.5 to 3.2. This makes them suitable for use as rheology modifiers, emulsifiers or as plasticizing additives.

Specific embodiments of the compounds of the invention are discussed in the following. Their physicochemical properties are summarized in the table below.

PL 242560 B1

Table 1. Physical and chemical properties of the compounds according to the invention

Character at 25°C Form at 40°C Water content HLB (From NMR)* Color Smell Density at 40°C (g/ml) Viscosity at 40°C (cP) Solubility in water White solid Colorless liquid <0.2% 3.2 <40.0 odorless 0.995 1.005 80.0 200.0 insoluble

‘The size of HLB was determined experimentally using 1H NMR studies.

Description of the method of synthesis

The general scheme for the synthesis of the compounds of the invention is shown below:

The compounds of the invention can be obtained by using a catalysed esterification and/or transesterification process using organic acids and organic mono and polyhydric alcohols. The essence of the process is the use of a bifunctional catalytic system consisting of: a heterophasic catalyst of the ion-exchange resin type and a homophasic catalyst in the form of organic tin and/or titanium compounds. Thanks to the use of a two-function reaction system, a high degree of raw material conversion of >95% is obtained. The products obtained in this way are polyether esters and are characterized by a strictly defined molecular weight and surface-active properties reflected by the HLB coefficient. In addition, the use of a mixture of adsorbents during the synthesis allows removing catalyst residues from the reaction mixture and obtaining products with a low final color. Thanks to such a synthesis process, the obtained polymer surfactants are suitable for use as O/W emulsifiers in cosmetic formulations, solubilizers and plasticizing additives for plastics.

For a better explanation of the essence of the invention, descriptions of its exemplary embodiments are presented below.

Example 1. Polyether ester built of succinic acid, lauryl alcohol, Rokopol D450 (polyoxypropylene diol)

Ri - lauryl alcohol 0.2, n - 3, p =6

Average molecular weight [g/mol] = 1836

Description of the synthesis

0.3 dm ³ of a heterophasic catalyst bed in the form of a strong acidic ion exchange resin (Amberlyst A46) is placed in the flow reactor. 86.4 g of lauryl alcohol together with 450.0 g of Rokopol D450 are introduced into the mixing reactor, the mechanical stirrer and jacket heating of the mixing reactor are started. The vacuum pump is then activated and generates a vacuum of 600 mmHg. Subsequently, the flow of water at a temperature of 25°C through the condenser is started and the reaction solution is bubbled with nitrogen in the amount of 5 Ndm ³ /h. When the temperature in the mixing reactor reaches 60°C, the dosing of 59.0 g of succinic acid begins. During dosing of the remaining components of the reaction mixture, the electric heating of the distillation column and jacket heating of the flow reactor are switched on. After dosing all the succinic acid and its complete dissolution and reaching the temperature of 120°C by the reaction solution, the distillation process begins at a pressure of 600 mmHg. Vapors of water and alcohol leave the reactor into the distillation column. Vapors of water and alcohol condense

PL 242560 Β1 in the condenser and separator, and then they are directed to the separator. The dehydrated alcohol is transferred to the distillation column by overflow from the separator, and the water is stored in a suitable operating tank. After stabilizing the distillation process, the circulation pump is started, which ensures a constant flow of the reaction mixture through the heterophasic catalyst bed in the amount of 2.0 dm ³ /h and the esterification and transesterification process is continued, removing water and alcohol formed in the synthesis from the reaction zone. The reactor is maintained at a temperature of 120°C, stirrer rotation in the range of 17.0 rad/s, pressure at a constant level of 600 mmHg, nitrogen 5 Ndm ³ /h. Condensed water is collected in appropriate tanks. After reaching the required concentration of water (0.03% m/m) and determining the acid number (41.3 mgKOH/g), dosing of the homophasic catalyst into the synthesis system, which is a solution of 1.5% titanium catalyst in laurel alcohol, begins. After adding the homophasic catalyst, the temperature of the reaction mixture is increased to 180°C and the pressure is reduced to 350 mmHg. After stabilizing the temperature of the reaction mixture, 59.0 g of succinic acid are dosed into the reaction system, and then, after the acid dosing is completed, 50.0 g of lauryl alcohol and 10 g of Rokopol D450 are dosed.

The esterification process ends when the reaction solution reaches an acid number of 0.1 mgKOH/g and a water content of 0.01% m/m. At the temperature of 105°C, 30.0 g of demineralized water is dosed into the mixing reactor in order to complete the synthesis process of low- and/or medium-molecular polymer surfactants. When the post-reaction mixture is cooled to 85°C, 3.0 g of a mixture of adsorbents consisting of 0.5 g of activated carbon, 2.0 g of diatomaceous earth, 0.5 g of Amberlyst A26OH alkaline ion exchange resin is dosed. The contacting process is carried out for 4 hours at the temperature of 85°C under nitrogen bubbling in the amount of 3 dm ³ /h, keeping the suspension evenly suspended in the working space of the reactor. After the process of refining polymer surfactants, the product is filtered at 90°C under nitrogen pressure of 1 MPa.

Table 2. Physical and chemical parameters characterizing the obtained product

Average molecular weight (M _w ), g/mol Index HLB Color on the scale of Pt-Co, Hazen Water content, % w/w Acid number, [mg KOH/g] Hydroxyl number [mg KOH/g] Viscosity [mPas] Density, [g/ml] 1836 3.2 <40 <0.2 <0.2 48-70 80.0- 200.0 0.9951.005

Analytical methods

1. HLB factor measurement

A 5-7 mg sample of the polyetherester was transferred to an NMR probe and dissolved in 660 µL of deuterated, deacidified chloroform (CDCl2). 1H NMR measurements were performed at room temperature and atmospheric pressure on a Bruker Avance III 600 MHz Spectrometer. Then, based on the collected proton spectra, the hydrophilic-hydrophobic coefficients for each of the products were determined.

2. Measurement of surface tension and determination of cmc (critical micellization concentration)

A sample of polyetherester in the amount of 0.1 g was added to a 100 ml beaker and supplemented with demineralized water to 100 g. The solution prepared in this way was thermostated for 1 hour at 25°C. 50 ml of the obtained solution was introduced into the cell of the Kruss K100C tensiometer. Surface tension was measured by the platinum plate method at 25°C.

In order to measure cmc, a 200 ml volumetric flask was prepared and 0.4 g of the test sample was placed in it. Demineralized water was added to the line. 50 ml of the tested solution with a concentration of 2 g/l was introduced into the measuring cell of the tensiometer and the measurement of the surface tension was started. In the next stage, demineralized water was dosed in order to obtain the dependence of the surface tension on the concentration of the tested product. cmc was determined as the point of intersection of the curves from the obtained dependencies.

3. Pt-Co color (Hazen scale) ml of the liquid sample was poured into a glass cuvette with a diameter of 24 mm. Color was tested in triplicate in the Regular Transmission mode. The cuvette was rotated 45° between each repetition. Color measurement was performed on a Hunter Lab VISTA Spectrophotometer, LED light source, optical length 100 mm.

4. Sample preparation for measurements

Polyetherester samples are solid at room temperature. Before the measurement, in order to melt them, the samples were heated for 1 hour at 40°C.

5. Density measurement ml of the liquid sample was dosed into the measuring cell with a syringe. Density was tested using an EKMA DA 640 density meter at 40°C for 60 seconds.

6. Viscosity measurement

Viscosity was determined using a Cone and Plate RST-CPS rheometer, Brookfield Engineering, connected to a PolyScience cryostat. A spindle type: RCT-75-1 was used for the measurement. 2 ml of the sample liquid was dispensed into the lower measuring plate with a syringe. Viscosity measurement was carried out for 60 seconds for 60 measurement points, at a temperature of 40°C, at a spindle speed of 10 to 15 rpm.

7. Water content measurement

Water content in the range from 0.001% to 2% was determined by the Karl Fischer method on the Metrohm 917 coulometer using anolyte A (composition: methanol, chloroform, imidazole, sulfur dioxide). 1 g of the liquid sample was dispensed through the septum into the measurement cell using a syringe with a needle. The measurement was performed in two repetitions.

8. Determination of the acid number

Determination of the acid number was performed by classical titration. 1 g of the liquid sample was placed in a conical flask with a capacity of 100 ml, 25 ml of solvent (xylene/ethanol mixture) and 3 drops of indicator (methyl orange and bromothymol blue mixture) were added. The solution was titrated with 0.1M KOH in ethanol until the color changed.

9. Determination of the hydroxyl number

Determination of the hydroxyl number was performed by classical titration. 1 g of the sample liquid was placed in a round bottom flask with a stirrer, then 5 ml of ethyl acetate was added. The closed flask was placed in a 50°C water bath and stirred until the sample was completely dissolved. Then, 5 ml of acetylating agent was added to the solution and stirring was continued for 15 minutes. After this time, 2 ml of demineralized water were added (while stirring) and then 10 ml of a pyridine/water mixture (3:1). The solution was removed from the bath, stirred for an additional 5 minutes. Additionally, 10 ml of m/m xylene/ethanol mixture (1:1) and indicator (mixture of methyl orange and bromothymol blue) were added and titrated with 0.5 M KOH in ethanol until the color changed.

Example 2. Polyetherester built of succinic acid, caprylic alcohol or 2-ethylhexanol, Rokopol D450 (polyoxypropylene diol).

The synthesis of polyetherester based on succinic acid and polyoxypropylenediol (Rokopol D450) is carried out as in example 1 with the difference that in the first stage 65.0 g of 2-ethylhexanol or caprylic alcohol is used instead of lauryl alcohol, and in the second stage 65.0 g of 2-ethylhexanol or caprylic alcohol is used instead of lauryl alcohol 39.0 g of 2-ethylhexanol or caprylyl alcohol.

Example 3. Polyether ester built of succinic acid, capric alcohol, Rokopol D450 (Polyoxypropylene diol).

The synthesis of polyether ester based on succinic acid and polyoxypropylene diol (Rokopol D450) is carried out as in example 1 with the difference that in the first stage 79.2 g of capric alcohol is used instead of lauryl alcohol, and 47.5 g of capric alcohol is used instead of lauryl alcohol in the second stage g of capric alcohol.

Example 4. Polyether ester built from succinic acid, myristyl alcohol, Rokopol D450 (polyoxypropylene diol).

The synthesis of polyether ester based on succinic acid and polyoxypropylene diol (Rokopol D450) is carried out as in example 1 with the difference that in the first stage 107.2 g of myristyl alcohol is used instead of lauryl alcohol, and 64.3 g of myristyl alcohol is used in the second stage instead of lauryl alcohol g of myristyl alcohol.

Example 5. Polyether ester built of succinic acid, cetyl or palmitoleic alcohol, Rokopol D450 (polyoxypropylene diol).

PL 242560 B1

The synthesis of polyether ester based on succinic acid and polyoxypropylene diol (Rokopol D450) is carried out as in example 1 with the difference that in the first stage 121.2 g of cetyl or palmitoleic alcohol is used instead of lauryl alcohol, and 72 g of lauryl alcohol is used in the second stage .7 g of cetyl or palmitoleic alcohol.

Example 6. Polyether ester composed of succinic acid, stearyl alcohol or isostearyl or elaidic or oleic alcohol or linoleic or elaidolinol, linolenic or ricinoleic alcohol and Rokopol D450 (Polyoxypropylenediol).

The synthesis of polyether ester based on succinic acid and polyoxypropylene diol (Rokopol D450) is carried out as in example 1, with the difference that in the first stage, instead of lauryl alcohol, 135.2 g of stearyl or isostearyl or elaidine or oleic or linoleic or elaidolinol or linolenic alcohol are used , ricinoleic alcohol, and in the second step, 81.2 g of stearyl or isostearyl or elaidic or oleic or linoleic or elaidolinol, linolenic, ricinole alcohol is used instead of lauryl alcohol.

Example 7.

The synthesis of polyether ester based on succinic acid and polyoxypropylenediol (Rokopol D450) is carried out as in example 1 with the difference that in the first stage 149.2 g of arachidyl alcohol is used instead of lauryl alcohol, and 89.6 g of arachidyl alcohol is used in the second stage instead of lauryl alcohol g of arachidyl alcohol.

Example 8.

The synthesis of polyether ester based on succinic acid and polyoxypropylene diol (Rokopol D450) is carried out as in example 1 with the difference that in the first stage 163.3 g of behenyl or erucyl alcohol is used instead of lauryl alcohol, and 98 g of erucyl alcohol is used instead of lauryl alcohol in the second stage. 0 g of behenyl or erucyl alcohol.

Table 3. Molar masses and HLB for the products of Examples 1-8.

Polyetherester Average molecular weight (M _w ), g/mol HLB Example 1* 1836 3.2 Example 2 1780 3.1 Example 3 1808 3.1 Example 4 1864 2.9 Example 5 1892 2.9 Example 6** 1920 2.8 Example 7 1948 2.8 Example 8*** 1976 2.7

* Average molecular weight of the compound containing 2-ethylhexyl alcohol and its isomer **Average molecular weight of the compound containing stearyl alcohol and its isomers ***Average molecular weight of the compound containing behenyl alcohol and its isomer

Example 9. Use of the compounds of the invention as plasticizers contained in the formulation of nail polishes.

The compound obtained in any of Examples 1-8 was used to prepare an exemplary nail polish composition.

Ingredients:

- nitrocellulose

- ethyl acetate: solvent

- butyl acetate: solvent

- isopropanol: solvent, damping agent

- pigment: Red No. 6 D&C Lake, Liguid

- UV absorber: benzophenone-1

- any compound from examples 1-8 - a new, polymeric plasticizer replacing the commonly used eg acetyl tributyl citrate (ATBC).

The lacquer composition was prepared according to the following procedure:

- A solvent mixture consisting of ethyl acetate, butyl acetate, isopropyl alcohol is prepared - Mixture A.

- In a separate vessel, the compound of example 1 is dissolved in a small amount of solvents (ethyl acetate and butyl acetate 1:1 by weight) until homogeneous - Mixture B.

In a separate vessel, the UV Absorber is dissolved in Mixture A. The whole thing is stirred for 30 minutes - Mixture C.

Execution:

In the first step of the process, a mixture of diluents (Mixture A) is introduced. Stirring is started (150-200 rpm) and then nitrocellulose is added, which is completely immersed in the solvent. Mix B and Mix C are added sequentially and stirring is continued. In the final stage, pigment is added.

Mixing (conditions: is continued for several hours or until all ingredients are completely dissolved. The nitrocellulose preparation process is complete when the solution is clear, i.e. completely transparent. The solution must not be milky and show insoluble particles. then pumped through a filter press or passed through a centrifuge to remove any foreign material or insoluble particles.This process improves the gloss and clarity of the solution.The preparation of clear coats consists of a nitrocellulose dissolving step, the addition of a plasticizer, and the pigment addition step is omitted.

The properties of the obtained varnish coating were tested. In the tests carried out, it was found that the properties of the coating obtained from the varnish containing the compound according to the invention are extremely favorable. In particular, the application properties were improved, including: coating hardness (measured on the basis of the damping of a pendulum set on a painted test plate with two varnish thicknesses, i.e. 100 and 200 μm), adhesion of the varnish to the tested surface (by measuring the adhesion of the varnish coating) and scratch resistance (measured with a sclerometer) for paints prepared with a commonly used plasticizer, i.e. acetyl tributyl citrate (ATBC).

Example 10. Use of the compounds according to the invention as plasticizers for the production of plastics.

PLA material

Ingredients:

- PLA - Polylactide (poly(lactic acid), (polylactic acid, polylactide)

- any of the bundles from examples 1-8, i.e. a new, polymeric plasticizer

- starch or TPS (thermoplastic starch prepared, for example, from native starch and glycerol as starch plasticizer or other starch plasticizer)

The possibility of making a PLA film is presented below.

Execution:

In the first step of the process, PLA (30%-75% (w/w)), plasticizer (3%-15% (w/w)) and starch or thermoplastic starch are mixed in a twin-screw extruder with temperature profiles of 100-200°C and extruded. The resulting cylindrical profiles are cooled in a water bath at 20-25°C and granulated. In the second step, the obtained granulate is mixed with starch or TPS again and extruded in a twin-screw extruder with temperature profiles of 100-160°C. In the next step, the cylindrical profiles are granulated and extruded in a single screw extruder to produce extrusion blown films with temperature profiles of 100-150°C. The resulting film is checked for mechanical properties, including the determination of the maximum tear strength in two axes and the percentage elongation at break.

In the tests carried out, it was found that the properties of the PLA material obtained from the formulation containing the compound according to the invention as a plasticizer are exceptionally advantageous. In particular, the glass transition temperature of PLA significantly decreased, which improved the flexibility of the material. Compatibility of the plasticizer with the polymer allowed for obtaining favorable mechanical properties of the material manifested as an increase in elongation at break, as well as increased tear strength in two axes.

PL 242560 B1

PVC material

Ingredients:

- PVC (i.e. polyvinyl chloride))

- any compound from examples 1-8, i.e. a new polymeric plasticizer

- stabilizer: inorganic metal salts or soaps or metal complexes or organotin compounds or epoxy compounds or organic phosphates or others, eg Cd/Ba stabilizer, calcium stearate.

The performance of the PVC material with the dry-blend method is presented below, i.e. Execution 1

Execution 1

In the first step of the process, PVC (60%-70% (w/w)) is introduced into the Fielder mixer chamber at a temperature of 70-80°C and heated for about 4-8 minutes. The temperature is then adjusted to 120-130°C and a plasticizer and stabilizer ((2-5% (w/w)) are added. The whole is mixed at 1000-1200 rpm until a temperature of 120°C is reached in about 10-15 minutes. After this After this time, the mixture is unloaded and cooled in a cooling chamber, then the dry-blend mixture is introduced into the mixer chamber equipped with roller-type blades attached to a Brabender rheometer at a temperature of 80-100 ° C. The temperature is then increased to 200-220 ° C. C and stirred at 30-50 rpm After reaching the desired temperature, the mixture is unloaded and cooled at 20-25 ° C. The dry-blend mixture is extruded at a pressure of 35-40 MPa at a temperature of 110-200 ° C for 5-7 minutes using a 150mm x 150mm x 2.3mm or 232mm x 155 x 2.2mm mold and then cooled.

Below is the production of PVC by preparing PVC paste, i.e. Execution 2 Execution 2

PVC and plasticizer are placed in the mortar in a mass ratio of (10-12): (12-15), then they are pounded until a homogeneous mass is obtained for about 8 hours. In the next stage, the whole is deaerated in a vacuum dryer at a pressure of 6-8 hPa and a temperature of 20-30°C for about 48 hours.

The properties of the obtained PVC material with the addition of a plasticizer constituting the present invention were tested. In the conducted tests, it was found that the obtained parameters are extremely favorable.

In particular, the reduction of global migration to aqueous model fluids (including acetic acid solution, ethyl alcohol solution) and to isooctane (substitution test) by complete immersion according to the standards of the PN-EN 1186 series) due to the larger molecule of the compound according to the invention in relation to the commonly polymers used, e.g. from the group of phthalates. The obtained PVC material with the addition of a plasticizer from examples 1-8 also shows comparable properties to currently used plasticizers, i.e. from the group of phthalates. The compared parameters were: tensile strength, yield strength, relative elongation at break, tear strength, Shore A or D hardness, resistivity, DMA shear test, determination of the glass transition temperature.

Claims (5)

Patent claims 1. Polyether ester polymer surfactant with a molecular weight of 1000 to 3000 g/mol, a copolymer of succinic acid, monohydroxy alcohol and polyoxypropylenediol (Rokopol D450) and a compound with the formula: Where: Ri is a monohydroxy alcohol residue selected from 2-ethylhexyl or caprylic, capric, lauryl, myristyl, cetyl or stearyl, isostearyl or elaidine or oleic or linoleic or elaidolinol, linolenic, ricinoleic, arachidyl, behenyl or erucyl alcohols. n - is a natural number from the range 2-4, p - is a natural number from the range 5-6. 2. A polymeric surfactant according to claim The compound of claim 1, which is a compound selected from: - a copolymer of succinic acid, lauryl alcohol and polyoxypropylene diol (Rokopol D450), with the average molecular weight of this copolymer being 1836 g/mol, - a copolymer of succinic acid, 2-ethylhexyl or caprylic alcohol and polyoxypropylenediol (Rokopol D450), the average molecular weight of this copolymer being 1780 g/mol, - a copolymer of succinic acid, capric alcohol and polyoxypropylene diol (Rokopol D450), with the average molecular weight of this copolymer being 1808 g/mol, - a copolymer of succinic acid, myristyl alcohol and polyoxypropylenediol (Rokopol D450), with the average molecular weight of this copolymer being 1864 g/mol, - a copolymer of succinic acid, cetyl alcohol and polyoxypropylene diol (Rokopol D450), with the average molecular weight of this copolymer being 1892 g/mol, - a copolymer of succinic acid, stearyl alcohol and polyoxypropylenediol (Rokopol D450), with the average molecular weight of this copolymer being 1920 g/mol, - a copolymer of succinic acid, arachidyl alcohol and polyoxypropylenediol (Rokopol D450), the average molecular weight of this copolymer being 1948 g/mol, or - a copolymer of succinic acid, behenyl alcohol and polyoxypropylene diol (Rokopol D450), the average molecular weight of this copolymer being 1976 g/mol. 3. The use of a polymeric surfactant as defined in claim 1. 1-2 as a plasticizer, especially for the production of plastics or paints. 4. Use according to claim 3, characterized in that the varnish produced is a nail polish. 5. Use according to claim The process of claim 3, characterized in that the plastic produced is a poly(lactic acid) or poly(vinyl chloride) material.