TR201816394A2 - NEW COMPOSITIONS WITH PLASTIC AND INTERIOR SLIDING PROPERTIES - Google Patents

Abstract

The present invention relates to a lubricant composition for use in shaping tires. Said lubricant composition comprises adipic acid, pentaerythritol and oleic acid or ester mixture obtained from the esterification of the mixture of oleic acid and linoleic acid as the second component in combination with isodecyl stearate as the first component.

Description

TECHNICAL FIELD The present invention is used in the plastics industry, especially in PVC applications. New performance-enhanced slider with internal and external slider features for relates to compositions.

KNOWN STATE OF THE TECHNIQUE Like all polymers, PVC is made up of long chain molecules. These are melt However, it is highly viscous and will not adhere to the metal components of the processing equipment. tends. This problem can be overcome by using sliders. rigid The main function of lubricants in PVC (rPVC) and other polymers, internal and external is to reduce friction. Thus, ease of flowing at lower temperatures, decrease in degradation tendency, increase in production rate, wear of equipment advantages such as reduction and less energy consumption are obtained.

Sliders are generally classified as internal or external. of the slider Solubility is generally determined by the molecular structure and polarity of the polymer. determines. Due to the possibility of polymer decomposition between the lubricant and the polymer. A complete resolution is not desirable. Both types of lubricant with PVC polymer Although it is mixed, it functions differently. However, most sliders are both external It also has internal slider combinations.

Outer lubricants are largely insoluble in PVC. Migrate to the polymer surface in the molten state They become slippery on the metal surface of the process equipment and they show. In this case, the bond strength between polymer and lubricant is weak. is happening. The lubricant coats the metal surface of the processing equipment and It provides tooth slider by reducing the friction on its surface.

Internal lubricants are mostly soluble in PVC. PVC chains during the process They work by being involved in its movement at the molecular level and function as internal sliders. sees. The desired effect for an internal lubricant is that the polymer chains themselves flow. is to ensure that they can be arranged in such a way that they can be oriented towards its direction. So inside shear stress between polymer molecules is reduced by the slider, therefore, melt viscosity and temperature rise decrease.

Because commercial-scale equipment is very costly to operate, new The effects of an improved lubricant system on the properties of the rPVC compound, rheometers, dynamic two-cylinder mills, small-scale molding machines and can be measured using laboratory-scale equipment such as extruders.

Whether a material has an internal or external slider, the material can be combined with rPVC. ability, adhesion times and effects on melt viscosity. Inner Lubricants do not significantly affect adhesion times, but do not affect melt viscosity. is lowering. The shifters have an effect on the adhesion time, but they do not significantly reduce the melt viscosity. These features are a torque It can be measured in a rheometer and a dynamic two-roll mill. rPVC extruders (both single and twin screw), calendering machines and injection molding It can be processed in a wide variety of equipment such as machines.

The slider system in terms of processing and end-use feature requirements needs to be balanced. Single screw extruders balance inner and outer slider twin screw extruders, calenders and injection molders are more Requires more discs. Slider prompts for processing equipment only not balanced, but the sliders also provide the necessary end-use features. affects positively. A fully optimized formulation, high throughput, low residue rates, high quality finished products and required physical provides features. Insufficient or excessive amount of lubricant may affect processing efficiency. causes it to decrease or may even stop processing. A balanced slider system (both correct amounts of both inner and outer slider), thermal stability times, output rate, It provides control over flowering, transparency and physical properties. Although there is a fairly wide range of slider classes for rPVC, most is thought of as wax or soap. The five main chemical classes are: amides; hydrocarbon waxes; fatty acid esters; fatty acids; metallic soaps. There are many types of ester lubricants used in various rPVC formulations: simple esters, glycerol esters, polyglycerol esters, montane esters, multifunctional partial esters of alcohols, fully esterified esters of polyfunctional alcohols.

With the exception of montane esters, these esters are made from various alcohols and fatty acids. This Lubricants are often referred to as fatty acid esters. Esters are generally very It is directional and with increasing carbon chain length and degree of esterification, its properties change. or shifter. Therefore, the 'lubricity' properties of an ester can be adapted for specific applications.

In the state of the art, there are documents describing the various lubricant mixes. takes. One of them, in the application numbered US 95,286, is a document for PVC applications. The slider system is explained. Ester and/or oil in the said lubricant system acid-fatty alcohol ester, and optionally with a mixture of esters and/or another ester A multi-component lubricant system containing metal soap is disclosed. Promise In order to obtain the desired 'Features' with the slider system in question, each component must be careful selection and determination of optimum amounts for each component is complex. requires a preparatory step.

Monoesters of highly saturated fatty acids are colorless, odorless, crystalline solids.

These are the esters that show the most internal lubricant function. The most common glycerol monostearate (GMS). GMS is a mostly "internal" system with some "external" features. it is a slider. Increasing the degree of esterification increases the tooth slip properties. is increasing. The most common fatty acid used as a lubricant for rPVC is palmitic (16 carbon chain length) and stearic (18 carbon chain length) acids. These In addition to some internal slider features, they are also good external sliders. Most Their major disadvantage is their low volatility. As rPVC processing becomes more complex, proportions increase and parts become more well-balanced slider with good interior and exterior properties as it gets complex systems become more critical. This is usually two or mix of sliders that feature more internal and external sliders requires. Examples of these are paraffin / oxidized polyethylene / calcium stearate, oxidized polyethylene / fatty acid ester, fatty acid ester mixture, paraffin / amide etc. can be given.

Especially in the production of PVC films by the calendering process, the hot film There is a problem of sticking to mechanical parts and cylinders. this situation movie causes physical deformations on the product and the product is of the desired quality. it doesn't come out.

Isotridecyl stearate product, known by the abbreviation G-4O and having internal slipping feature, is the only Although this situation decreases slightly when used alone, it does not disappear completely and affect the visual and physical performance of the final product. Mixtures of transparent, amorphous and microcrystalline polyamides, copolyamides and polyamides is explained. Particularly preferred lubricants include isotridecyl stearate (Loxiol G-4O ®) is also included.

Although the internal slippery properties of the system when isotridesyl stearate is used, Although it is sufficient, while the processed product is coming out of the mold, it is necessary to pass through the screw or especially the film. adhesion and therefore the final product while passing over the cooling cylinders for deformation problems can be seen in the product, and plate-out problems may also occur.

The internal slider's feature alone is insufficient at this point.

As a result, due to the above-mentioned negativities and existing solutions It is necessary to make an improvement in the relevant technical field due to the inadequacy of the is locked.

BRIEF DESCRIPTION OF THE INVENTION The present invention fulfills the above-mentioned requirements, has all the disadvantages plastic, which eliminates and brings some additional advantages, especially PVC applications. relates to a slider composition suitable for

The primary aim of the invention is to produce a slider that has both internal and external slider properties. is to provide a slippery composition.

It is an object of the invention to reduce friction on the surface of the processing equipment and is to provide a slider composition with distinctive 'feature'.

Another object of the invention is a slider that eliminates the sticking problem. to provide composition.

Another object of the invention is to use a tool that enables improved torque values to be achieved. is to provide a slippery composition.

A similar object of the invention is lower power (Ampere) ratings for the extruder and A slider that allows higher gloss values to be reached. to provide composition.

Another object of the invention is that the film can pass through cooling cylinders without adhesion, By avoiding the deformation problem in the product, high quality products can be obtained. is to provide a lubricant composition that allows

Another object of the invention is to provide a slider to achieve production efficiency. to provide composition.

Another object of the invention is to use more than one additive separately. is to provide a lubricant composition that prevents

In order to fulfill the above-described purposes, the present invention is Describes a slider composition for use in shaping, said lubricant composition with isodecyl stearate as the first component adipic acid, pentaerythritol and oleic acid as the second component in combination, or ester mixture obtained from the esterification of oleic acid and Iinoleic acid mixture contains.

The present invention is also used as a lubricant for forming plastics. describes a method for producing a 'lubricating composition' for method; i- providing isodecyl stearate as the first component; ii- as a second component adipic acid, pentaerythritol and oleic acid or oleic acid and to be made; and iii- adding the said first component to the second component at the determined rates contains the steps.

The present invention is also used as a lubricant for forming plastics. Isodecyl stearate is obtained by esterification of stearic acid with isodecyl alcohol. followed by pentaerythritol with oleic acid or oleic acid and The present invention also describes a plastic product, said plastic 'product'. adipic acid, pentaerythritol and oleic acid in combination with isodecyl stearate, or ester mixture obtained from the esterification of oleic acid and Iinoleic acid mixture Contains a lubricant composition.

The structural and characteristic features of the invention and all its advantages are detailed below. will be more clearly understood by the explanation and therefore the evaluation This detailed explanation should also be taken into account.

DETAILED DESCRIPTION OF THE INVENTION In this detailed description, the preferred slider compositions of the invention are described. structuring, only for a better understanding of the subject and no It is explained in a way that does not have a restrictive effect.

The performance of the present invention plastic, especially for polyvinyl chloride (PVC) applications describes a new augmented slider composition. Invention subject slider composition two components, a first component and a second component includes: Component 1: Ester of stearic acid and isodecyl alcohol, and Component 2: Adipic acid, pentaerythritol and oleic acid or oleic acid and Iinoleic acid ester mixtures from the mixture slider in current reference; polymer-polymer, metal-metal, polymer-metal, filler-filler or an additive that reduces the friction between the polymer-filler. is coming.

Unexpected combination of the subject of the invention with Component 1 and Component 2 when used, the processing equipment is better than when using Component 1 alone. tooth slider and mold covering the metal surface and reducing the friction on the surface It has been found that it provides distinctive features and the adhesion problem is eliminated. This In this way, lower torque values, lower power (Amps) for the extruder values and higher gloss values have been reached. present invention Thanks to this, the film can pass through adhesion in the cooling cylinders, Obtaining high quality products by avoiding the deformation problem. can be achieved. Due to the falling torque, more material is loaded into the system. production efficiency has been achieved. In addition, in the product output per unit time (output) A synergistic increase was also detected.

In addition, thanks to the present invention, more than one additive can be separated separately. use is prevented. In this way, such as logistics, warehousing, purchasing It is an undeniable position in terms of both material and labor power and time. benefit is achieved.

According to the present invention, the first component; obtained from the ester of stearic acid and isodecyl alcohol. It consists of isodecyl stearate. The structure of isodecyl stearate is as follows Formula I The second component according to the present invention; i) adipic acid, ii) pentaerythritol and iii) oleic acid, or It consists of ester mixtures obtained from a mixture of oleic acid and linoleic acid. is coming. In other words, the second component pentaerythritol adipate oleate/oleate and linoleate The mixture consists of complex esters. used in the current reference as the complex esters of pentaerythritol adipate oleate/oleate and linoleate mixture; i) adipic acid, ii) pentaerythritol and iii) oleic acid or a mixture of oleic acid and linoleic acid means ester mixtures.

Formulas of compounds that make up these esters (i, when ii-oleic acid and iii) shown below.

Pentaerythritol Oleic Acid Adlplk Acid Formula I Formula II Formula III The weight of the first and second components included in the slider composition of the invention. ratios are important for the composition in question to have the desired properties. offers. Pentaerythritol adipate oleate/oleate contained in the composition of the invention and the proportion of linoleate blend complex esters accounts for 30% by weight of the total blend. The chemistry of the mixture and the technical properties of the final product are negatively affected. can be affected.

In a preferred embodiment of the invention, the lubricant composition is by total weight pentaerythritol adipate contains oleatloleate and Iinoleate mixture complex esters.

In a more preferred embodiment of the invention, the lubricant composition is 70% to 90% by weight isodecyl stearate and 10% to 30% by total weight of pentaerythritol It contains adipate oleate/oleate and Iinoleate mixture complex esters.

The targeted acid number of the lubricant composition of the invention is 51 mgKOH/g.

The total amount of complex esters of pentaerythritol adipate oleate/oleate and Iinoleate mixture When the weight ratio exceeds 30%, the acid number exceeds the target value. is coming out.

In another preferred embodiment of the invention, the slider composition is the first component. adipic acid as the second component in combination with isodecyl stearate as ester mixture obtained from the esterification of pentaerythritol and oleic acid wherein the first component is 70 to 90% by weight, the second the proportion by total weight of the component is 10 to 30% and the acidity of the said composition the number is 1 mg KOH/g or less.

In the current application, the “acid number” is used to neutralize one gram of the chemical. means the mass, in milligrams, of potassium hydroxide required. Acid The number gives the amount of carboxylic acid groups in solution.

In the present application, the "hydroxyl number" is a gram containing free hydroxyl groups. to neutralize the acetic acid taken up during an acetylation of the chemical means the mass, in milligrams, of potassium hydroxide required.

Known esterification methods of component (A) isodecyl stearate according to the present invention can be achieved by realizing it. For example, stearic acid isodecyl alcohol and acid esterifies in the presence of a catalyst. Starting materials in different mole ratios can be used. For example, preference is given to obtaining 'products with desired properties'. The ratio of stearic acid to zizodecyl alcohol can be 1:1,07. The ratio of isodecyl alcohol When it is below 1.07, the reaction is not complete. over 1.07l When isodecyl alcohol is added, there is a problem in removing excess alcohol and The hydroxyl number is also higher than desired.

Preferred hydroxyl number for isodecyl stearate according to the invention is 55 mgKOH/g, acid number and 51 mgKOH/g.

In the isodecyl stearate solution obtained according to the invention preferably free carboxyl and/or the hydroxyl group is essentially absent.

Second component pentaerythritol adipate oleate/oleate and Iinoleate mixture complex adipic acid used as starting material in esters: pentaerythritol: 0leic The ratio of acid/oleic and Iinoleic acid mixture may vary. For example, The preferred ratio to obtain products with desired & properties is 0.78:1:2.22.

In addition, adipic acid-zoleic acid is maintained by keeping pentaerythritol constant according to the product with the desired viscosity. acid/oleic and linoleic acid mixture ratio can be changed Other preferred has a direct effect on the viscosity of said second component. desired viscosity its value is optimized by changing the mole ratios mentioned.

When using oleic acid as the monocarboxylic acid, the preferred adipic acid is zoleic acid The ratio of pentaerythritol:Oleic acid is 0.35:O.45:1.

According to the invention, pentaerythritol adipate oleate/oleate and Iinoleate mixture for complex esters the preferred hydroxyl number is 520 mgKOH/g and the acid number is 515 mgKOH/g.

Pentaerythritol adipate stearate/oleate complex ester mixture obtained according to the invention The free hydroxyl group is essentially absent.

Second component pentaerythritol adipate oleate/oleate and linoleate mixture according to the present invention complex esters are obtained by performing esterification methods known in the literature. can be achieved. For example, a mixture of oleic acid/oleic acid and Iinoleic acid with pentaerythritol Partial ester is obtained by esterification. One or more of the resulting products It has a free hydroxyl group. The later mentioned free hydroxyl groups are reacted with adipic acid. According to another method, `first Some of the hydroxyl groups of pentaerythritol are esterified with adipic acid, then The remaining free hydroxyl groups of the partial ester obtained are oleic acid/oleic acid and Iinoleic acid. reacted with the acid mixture.

Pentaerythritol adipate oleate/oleate and Iinoleate mixture to obtain complex ester mixture The starting materials can be used in different mole ratios.

In another preferred embodiment of the invention, pentaerythritol adipate oleate/oleate and esterification of pentaerythritol followed by esterification of the resulting product with adipic acid It is obtained by two-stage esterification.

In another preferred embodiment of the invention, pentaerythritol adipate oleate/oleate and is obtained through

In the literature, esterification reactions in synthesis steps are generally 200- It is seen that it is carried out at 210°C and for very long periods. Meet Isodecyl stearate and pentaerythritol adipate oleate synthesized within the scope of synthesis of complex esters at much lower temperatures (at 135°C and 170°C) and in short periods (10 hours and 7 hours). used in the reaction The type and amount of catalyst can change the reaction time and temperature.

In order for the reaction to reach equilibrium in a short time, strong inorganic sulfuric acid and hydrochloric acid are used. Best according to current invention p-toluenesulfonic acid catalysis, which enables the balance to be reached more quickly and is preferred.

The lubricant composition according to the invention is specific to the product of the first component isodecyl stearate. ratios of pentaerythritol adipate oleate/oleate and Iinoleate mixture complex esters. obtained by adding In addition, the invention includes physical properties of the first and second components. Instead of being mixed as a chemical, it can be mixed in the reaction medium. can be prepared. The preparation of the slider composition subject to the invention in this way In the case of 'for example, isodecyl stearate synthesis in the first step is followed by the environment' Pentaerythritol and oleic acid or a mixture of oleic acid and Iinoleic acid can be added.

The slider compositions, which are the subject of the invention, obtained in different proportions, are plastic, 'For example, It can be added to hard or soft PVC mixtures in varying proportions. This For this reason, the first component and the second component in the molten state in the desired ratios. must be compatible with each other. Thus, homogeneous mixtures are obtained. can be achieved. The lubricant compositions of the invention are the plastics to be processed. It is used by adding to the material before processing. Slider to be added The amount of composition depends on the plastic material to be processed and the type of processing.

Preferably, the plastic product mentioned is 0.2 to 0.6% by total weight of lubricant. contains composition.

Also, if the user wants to get increased scrolling values, If it finds too much, control the amount of the relevant mixture in the final product. and with this amount, it has a slippery effect obtained with a single product and a better achieve a visual quality.

As an example of PVC `products' for which the lubricant composition of the invention will be used. window profiles, automobile seat skins, floor coverings, wallpapers, shoes bases, electrical cables, various packages can be given.

Thanks to the inventive slider composition, for example, PVC material can be applied in the mold. residence time is reduced. This means that the PVC material is high in the system. It provides less exposure to heat. Thus, the thermal degradation rate is further reduced compared to the previously applied system and its 'life is longer'. it is long. At the same time, thanks to the increased tooth slider feature, the equipment is also The possibility of damage is minimized and the service life is extended.

In particular, reducing the thermal degradation of PVC affects the light fastness of the final product. (light fastness) makes a positive contribution. For example, the end product is a window profile. on the other hand, the window profile remains without yellowing for a longer period of time. because the material The less and short time it is exposed to heat while it is being produced, the thermal and thermal effects of the final product. mechanical strength is higher.

The fact that the sliding feature has been improved is also possible, such as extruder screw and sleeve. components last longer, extruder screw cleaning is less frequent has a positive contribution to the need.

After the lubricant composition is homogeneously distributed in the plastic, The shaping can be done in one of the ways known in the literature.

EXAMPLES Isodecyl stearate (A) obtained from isodecyl alcohol and stearic acid according to the present invention and ester mixtures (B) obtained from adipic acid, pentaerythritol and oleic acid, and the preparation of their inventive combinations is in the examples below is explained.

Synthesis of Isodecyl stearate ester (1 Component): One nitrogen inlet, one mechanical stirrer inlet, one thermometer inlet and vacuum outlet alcohol and added as catalyst. Heat It was set at 140°C. After a reaction time of about 10 hours, the acid count is checked. was done. After falling below 1 mg KOH/gr, vacuum was applied and under vacuum for 4 hours. Excess alcohol was removed. The reaction medium was cooled to 30°C. 48% NaOH and The medium was neutralized with deionized water. To remove the remaining water inside the product the reactor was heated to 100°C and vacuum was applied for about 2 hours. The environment is cooled and The isodecyl stearate product was obtained.

For the product obtained; acid number: 0.21 mg KOH/gr, saponification number: 141 mg KOH/g, Viscosity 19.2 mPa.s, density: 0.857 g/cms.

Synthesis of pentaerythritol adipate oleate complex ester (Component 2): One nitrogen inlet, one mechanical stirrer inlet, one thermometer inlet and vacuum outlet and 0.645 9 PTSA was added as catalyst. The temperature was set to 170°C. formed juice A light vacuum was applied to remove it. The reaction is in this way, the acid number is 1 mg. It continued until it fell below KOH/gr. Then the vacuum was cut off and the temperature was done. The temperature was set back to 170°C and the water formed during the reaction was slightly removed from the environment by applying vacuum. Acid number below 12 mg KOH/gr The reaction is complete, the medium is cooled and pentaerythritol adipate oleate complex ester viscose product was obtained.

For the product obtained; saponification number: 277 mg KOH/gr, Viscosity: 3000 mPa.s, Preparation of the mix Pentaerythritol adipate oleate is added to the obtained isodecyl stearate product at certain rates. was done. The slipperiness effect of the mixture obtained in different proportions is laboratory scale measured in the extruder. Prepared standard PVC mixture as specified below products are added and the data obtained are presented in the table: Formulation 100 phr PVC, 10 phr Calcite, 2 phr Lmpact Modifier, 5.5 phr Stabilizer Package Extruder Göttfert, 30 rpm, 25 mm die Sample No. 1 2 3 4 5 Isodecyl Stearate Isodecyl Stearate .

Any Just and 10% and 20% zode .V? /030 . . . . . . Pentaerythritol Property slider Izodecyl Pentaerythritol Pentaerythritol Name at Oleate Stearate Adipate Oleate Adipate Oleate p (reference) used together used used has been used Adhesion to the roller and surface adhesion and adhesion Consequence problems surface not observed, not observed, not observed, observed problems. surface surface surface observed suitable suitable suitable suitable As can be seen in the table, the mixture product subject to the invention is never used under all conditions. unexpected situation compared to the use case or isodecyl stearate alone. somehow gave better results.

It has also been observed that the slipperiness and output increase with lower torque.

The results also show that the power used (power, Ampere) has a slippery effect. indicates that it decreases with an increase. Thus, the addition of the inventive combination It has also been found that it provides an electrical and financial gain.

The last 3,4 and 5, which includes the combination of all these advantages, namely the sirabulus issue. It was observed that the gloss level of the products increased by 3-6 units. This This situation also provides an advantage on the basis of the end product.

As a result of the studies, mixtures containing the combination of the invention are synergistic. As a result, it gave a better technical and end product performance in all ratios.

Claims (18)

REQUESTS . A lubricant composition for use in the shaping of plastics, containing as components a mixture of esters obtained from the esterification of adipic acid, pentaerythritol and oleic acid or a mixture of oleic acid and Iinoleic acid. . The lubricant composition according to claim 1, wherein the first component is 70 to 90% by weight and the second component is 10 to 30% by total weight. Lubricant composition according to claim 1 or 2, wherein said composition has an acid number of 1 mg KOH/g or less. . Lubricant composition according to claims 1 to 3, wherein said first component isodecyl stearate acid number is 1 mg KOH/g or less. . Lubricant composition according to claims 1 to 4, wherein said first component isodecyl stearate has a hydroxyl number of 5 mg KOH/g or less. . Lubricant composition according to claims 1 to 5, wherein said first component isodecyl stearate is obtained by esterification of stearic acid with isodecyl alcohol under an acid catalysis, where the molar ratio of stearic acid:isodecyl alcohol is 1:1.07. . The lubricant composition according to claims 1 to 6, wherein said second component ester mixture has an acid number of 15 mg KOH/g or less. . The lubricant composition according to claims 1 to 7, wherein said second component ester mixture has a hydroxyl number of 20 mg KOH/g or less. . Lubricating composition according to any one of the preceding claims, wherein the molar ratio of adipic acid : pentaerythritol : oleic acid/oleic acid and Iinoleic acid mixture is selected. 10. Lubricant composition according to claim 9, wherein the molar ratio of adipic acid: pentaerythritol: oleic acid/oleic acid and Iinoleic acid mixture is 0.78:1:2.22. The lubricant composition according to any one of the preceding claims, wherein said second component is an ester mixture obtained from the esterification of adipic acid, pentaerythritol and oleic acid. 12. A method for producing a 'lubricating composition' for use as a lubricant in shaping plastics, wherein i- providing isodecyl stearate as the first component; ii- and taking adipic acid, pentaerythritol and oleic acid or oleic acid as the second component; and iii- adding said first component to the second component at determined rates. 13. The method according to claim 11, wherein said second component is an ester mixture obtained from the esterification of adipic acid, pentaerythritol and oleic acid. 14. It is a method for producing a lubricant composition to be used as a lubricant in the shaping of plastics. It includes the step of obtaining isodecyl stearate by esterification of stearic acid with isodecyl alcohol, followed by the addition of pentaerythritol and oleic acid or a mixture of oleic acid and Iinoleic acid to the reaction medium. 15. The method according to claim 14, comprising the step of adding oleic acid to the reaction medium. 16. It is a plastics product, characterized in that it contains a lubricant composition comprising adipic acid, pentaerythritol and oleic acid in combination with isodecyl stearate or an ester mixture obtained from the esterification of a mixture of oleic acid and Iinoleic acid. 17. The plastic product according to claim 16, comprising between 0.2% and 0.6% by total weight of the lubricant composition. 18. Plastic product according to claim 16 or 17, said plastic product being PVC