Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
  • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
  • C10M105/32—Esters
  • C10M105/36—Esters of polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
  • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
  • C08J3/212—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase and solid additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C08J2327/06—Homopolymers or copolymers of vinyl chloride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
  • C08K2003/265—Calcium, strontium or barium carbonate
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/36—Release agents or mold release agents

Definitions

• the present invention relates to additives which have inner lubrication characteristics for use in plastic sector.
• the present invention particularly relates to an inner lubricant additive which is for use in PVC applications and which does not include phthalate.
• PVC is substantially viscose in molten form, and is inclined to adhere to metal components of processing equipment. This problem can be overcome by using lubricants.
• the basic function of lubricants in rigid PVC (rPVC) and other polymers is to decrease inner and external friction.
• rPVC rigid PVC
• advantages like easiness in flow, reduction in degradation probability of polymer, increase in production ratio, reduction in abrasion of equipment, less energy consumption are obtained.
• Lubricants are essentially classified as inner or external. Even though both types of lubricants are mixed with PVC polymer, they realize different functions. External lubricants do not substantially dissolve in PVC. They migrate to the polymer surface when they are in molten form. They cover the metal surface of the process equipment and decrease friction on the surface and provide external lubrication. In this case, bonding force between the polymer and the lubricant is weak.
• Inner lubricants are mostly dissolved in PVC. During process, inner lubricants function as included at molecular level to the movement of PVC chains. For an inner lubricant, the desired effect provides regulation of the polymer chains such that the polymer chains can be guided towards the flow direction. Thus, sliding tension between polymer molecules is decreased by the inner lubricant, and, therefore, molten viscosity and temperature increase are decreasing.
• Dissolvability of the lubricant is essentially determined by molecular structure of polymer and by the polarity thereof. A complete dissolvability is not desired because of the risk of fragmenting of polymer between the lubricant and the polymer.
• lubricant classes at a substantially wide range for rigid PVC, most of them are considered as wax or soap.
• the five main chemical classes are as follows: Amides; hydrocarbon waxes; oil acid esters; oil acids; metallic soaps.
• ester lubricants used in various rPVC formulations: Simple esters, glycerol esters, poly-glycerol esters, montan esters, partial esters of multi-functional alcohols, completely esterificated esters of multi-functional alcohols. Except montan esters, these esters are made of various alcohols and oil acids. These lubricants are essentially named as oil acid esters. Esters are essentially versatile and the characteristics thereof can change as inner or outer lubricant by means of increasing carbon chain length and esterification degree. Therefore, lubrication characteristics of an ester can be adapted for specific applications.
• the material being whether inner or outer lubricant is depending on the joining ability of the material with rPVC, adhesion durations and the effects on the molten viscosity.
• the inner lubricants shall not seriously affect adhesion durations but shall decrease the molten viscosity.
• the external lubricants shall affect on the adhesion duration but shall not substantially decrease the melting viscosity.
• the effect of lubricant systems on processing can be measured in laboratory scale extruders and injection molding machines.
• Hard PVC can be processed in various equipments like extruders (both single screwed and double screwed), calendering machines and injection molding machines.
• the lubricant system must be balanced in terms of the requirements of processing and end usage characteristic. While single screw extruders need inner and outer lubricant balance, double screw extruders, calenders and injection molding machines need more external lubricant. Lubricant systems are not only balanced for the processing equipment, at the same time, the lubricants affect the necessary end usage characteristics in a favorable manner. A formulation optimized completely provides high output amount, low waste ratios, high quality finished products and necessary physical characteristics. Insufficient or excessive amount of lubricant leads to decrease of the processing efficiency or can even stop processing. A balanced lubricant system (the correct amounts of both the inner and outer lubricants) provides control on thermal stability durations, output ratio, blooming, transparency and physical characteristics.
• plastic products are used frequently in daily lives of all people in both developed and developing countries.
• Such plastic products comprise additives added intentionally for developing and improving the technical and industrial characteristics of end products.
• these additives are phthalic acid esters used in various products.
• Plastic additives connected physically to plastic products can easily move to the surface through the polymer, moreover, they can leave the polymer and thus, they can be released to the environment.
• phthalates easily enter the environment by means of leakage, displacement and volatility during production and during usage and after disposal of the products. Phthalates have various damages for human health. For instance, high doses of phthalate change hormone levels and lead to birth faults, breast cancer, and lung and renal failures.
• the present invention relates to an inner lubricant additive, a process for preparing said inner lubricant additive, a PVC composition including said inner lubricant additive and a process for preparing said PVC composition, for meeting the abovementioned requirements and for eliminating the abovementioned disadvantages and for bringing new advantages to the related technical field.
• the primary object of the present invention is to obtain an inner lubricant additive which does not include chemical substances like distearyl phthalate which gives damage to human health or to the environment.
• the object of the present invention is to obtain an additive which has function as inner lubricant in rigid PVC process.
• Another object of the present invention is to obtain an inner lubricant additive which increases processability performance of PVC compositions.
• the present invention is an inner lubricant additive for use in shaping plastics, and it comprises distearyl adipat.
• said inner lubricant additive essentially does not include phthalate.
• said distearyl adipat is obtained by entering stearyl alcohol and adipic acid to esterification reaction.
• the stochiometric proportion of stearyl alcohol and adipic acid in esterification reaction is 2-2.5:1 .
• the present invention is a process for preparation of an inner lubricant additive for use in shaping plastics, and said process comprises the step of entering stearyl alcohol and adipic acid to esterification reaction.
• said process essentially does not include entering of an alcohol and phthalic anhydrite to esterification reaction.
• the stochiometric proportion of stearyl alcohol and adipic acid in esterification reaction is 2-2.5:1 .
• said esterification reaction is realized in the presence of acid catalyst.
• said process comprises the step of grinding and powdering of distearyl adipat mixture obtained as a result of esterification reaction.
• said process comprises the step of adding at least one agglomeration preventing additive to the distearyl adipat mixture, obtained as a result of esterification reaction, before grinding.
• the present invention is a method for production of an inner lubricant additive for use in shaping plastics, said method comprising the steps of:
• the present invention is a PVC composition and it comprises distearyl adipat as the inner lubricant.
• said PVC composition essentially does not include phthalate.
• said distearyl adipat is obtained by entering stearyl alcohol and adipic acid to esterification reaction.
• the stochiometric proportion of stearyl alcohol and adipic acid in esterification reaction is 2-2.5:1 .
• the present invention is a process for preparation of a PVC composition comprising at least one inner lubricant, and comprises the step of entering stearyl alcohol and adipic acid to esterification reaction.
• said process essentially does not include the step of entering an alcohol and phthalic anhydrite to esterification reaction.
• the stochiometric proportion of stearyl alcohol and adipic acid in esterification reaction is 2-2.5:1.
• said esterification reaction is realized in the presence of acid catalyst.
• said process comprises the step of grinding and powdering of distearyl adipat mixture obtained as a result of esterification reaction.
• said process comprises the step of adding at least one agglomeration preventing additive to the distearyl adipat mixture, obtained as a result of esterification reaction, before grinding.
• the present invention is a method for production of a PVC composition comprising at least one inner lubricant, said method comprising the steps of:
• an inner lubricant additive including distearyl adipat
• the inner lubricant additive means an additive which decreases friction between polymer-polymer, polymer-metal or polymer-filler.
• the present invention describes an inner lubricant additive for use in shaping plastics.
• Said inner lubricant additive comprises distearyl adipat.
• the chemical structure of distearyl adipat is shown by Figure 1.
• Distearyl adipat is preferably obtained by means of esterification reaction of stearyl alcohol and adipic acid in the presence of acid catalyst.
• Esterification reaction can be realized by using a known method by a person who is skilled in the known state of the art.
• the desired distearyl adipat is obtained by means of esterification of stearyl alcohol and adipic acid with proportion of 2-2.5:1 , preferably proportions of 2:1 or 2.5:1.
• the inner lubricant additive essentially does not include a phthalate including distearyl phthalate.
• a new inner additive is presented which does not comprise phthalate, in other words, which does not comprise chemical substances which give damage to human health or to the environment.
• said additive has the same PVC processing performance when compared with the alternatives including phthalate or increases this performance and provides improvements in gelling time and torque values and does not lead to color deteriorations.
• phthalate is obtained by means of esterification reaction of an alcohol component, for instance, methanol, ethanol, penta-eritritol, tris-methylol-propane (TMP), sorbitol, glycerol, diglycerol, poly-glycerol or and phthalic anhydrite which gives damages to human health and to the environment.
• an alcohol component for instance, methanol, ethanol, penta-eritritol, tris-methylol-propane (TMP), sorbitol, glycerol, diglycerol, poly-glycerol or and phthalic anhydrite which gives damages to human health and to the environment.
• TMP tris-methylol-propane
• sorbitol glycerol
• diglycerol diglycerol
• poly-glycerol or and phthalic anhydrite which gives damages to human health and to the environment.
• adipic acid which is a dicarbox
• the statement “does not essentially include phthalate” means that the inner lubricant additive does not include any phthalate or that the inner lubricant additive comprises phthalate at a low level which does not give damage to human health or to environment. It is considered that phthalate with proportion of 0.1% by total weight does not give damage to human health and environment health. Accordingly, in the present invention, the statement “does not essentially include phthalate” has been used in the meaning of “including phthalate with proportion between 0% and 0.1% by total weight”. Said phthalate can be distearyl phthalate. The chemical structure of distearyl phthalate is shown by Figure 2.
• the present invention describes a process for preparation of an inner lubricant additive for use in shaping plastics.
• Said process comprises the step of entering stearyl alcohol and adipic acid to esterification reaction. It has been found that distearyl adipat, obtained by means of said esterification reaction, has inner lubricant characteristics particularly in PVC compositions and has the same PVC processing performance when compared with phthalates or increases this performance.
• said process essentially does not include the step of entering stearyl alcohol and phthalic anhydrite to esterification reaction.
• the statement “essentially does not include the step of entering stearyl alcohol and phthalic anhydrite to esterification reaction” means that the inner lubricant additive, obtained by means of said process, does not include any phthalate or comprises low level of phthalate which does not give damage to human health or to environment. It is evaluated that phthalate, which has proportions lower than 0.1% by total weight, does not give damage to human and environment health. Accordingly, in the present invention, the statement “does not essentially include phthalate” has been used in the meaning of including phthalate at a proportion between 0% and 0.1% by total weight.
• the proportion of stearyl alcohol and adipic acid is equal to 2-2.5:1 , preferably equal to 2:1 or 2.5:1 .
• Esterification is preferably realized in the presence of acid catalyst.
• the subject matter process moreover can comprise the step of grinding of distearyl adipat mixture obtained as a result of esterification reaction and turning said distearyl adipat mixture into a form with powder, flake or lentil size.
• At least one agglomeration preventing additive can be added before grinding to the distearyl adipat mixture obtained as a result of esterification reaction.
• the agglomeration preventing additive is added into the reaction medium during cooling preferably after the esterification reaction is completed.
• the agglomeration preventing additives are inert organic or inorganic compounds which decrease probability of attraction between particles in some products (food, drug, dye, cosmetic, etc.) which are in powder form and which prevent adhesion and which provide fluidity of products which are in powder form or which have tiny particles and which prevent agglomeration probabilities.
• Such materials are called “agglomeration preventing agent”, “adhesion preventing agent”, “free flow agent” or “drying agent” in the literature. Said materials, which cover the particles with a thin layer, increase the distance between the particles and prevent the electrostatic attraction between the oppositely charged particles and prevent adhesion of particles to each other.
• the agglomeration preventing additives which can be used in the present invention, are materials already used at important proportions as stabilizer or filler in plastic, particularly in PVC compositions. Since said agglomeration preventing additives are used in plastic formulations, they are useful in turning the inner lubricant additive into powder form and prevent caking and petrification, and the additional usage of said filling materials or stabilizers during processing of a plastic material is prevented. Fillers are materials which cheapen the product and which provide toughness.
• the fillers which can be used as the agglomeration preventing additive which is compliant to the present invention there are calcium stearate, magnesium stearate, calcite (calcium carbonate) and talc (magnesium hydro-silicate) without limitation with these.
• the stabilizers which can be used as the agglomeration preventing additive which is compliant to the present invention there are calcium-based stabilizers, organo-tin-based stabilizers, metal stabilizers.
• the grinding systems which can be used in the subject matter process there are mill types like razor grinding mills, geared grinding mills and sprayed cooling systems without limitation.
• the present invention moreover describes a method for production of an inner lubricant additive for use in shaping plastics.
• Said method comprises the steps of: i) obtaining distearyl adipat; ii) obtaining at least one agglomeration preventing additive; iii) turning said agglomeration preventing additive into a mixture by means of distearyl adipat; and iv) grinding the mixture obtained in the step iii) and turning the mixture into powder form.
• inner lubricant additives are used in polymer shaping processes which show plastic characteristic.
• Said inner lubricant additive is particularly suitable for shaping polyvinyl chloride (PVC) like rigid PVC, polymers with chlorine like poly-vinylidene chloride, and the copolymers which are the derivative thereof.
• said inner lubricant additive can be used as process additive for engineering plastics, as mold separator and in processing PMMA (Poly(methyl)methacrylate).
• the subject matter inner lubricant additive can be added to plastic, for instance, to hard or soft PVC mixtures with changing proportions.
• the subject matter inner lubricant additive is added to the plastic material, which is to be processed, before processing.
• the amount of the added inner lubricant additive depends on the plastic material to be processed and the processing type.
• the present invention describes a PVC composition which comprises distearyl adipat as inner lubricant and PVC polymer.
• PVC composition comprises inner lubricant additive with proportion between 0.2% and 0.6% by total weight. By using these proportions, the desired physical and mechanical characteristics in the end product are obtained.
• PVC composition can comprise other additives like stabilizers (for instance, lead salts, calcium-zinc), fillers (for instance, calcium carbonate), dyes (for instance, titanium dioxide), process adjuvant agents (for instance, acrylic-based adjuvant agents), impact additives (for instance, chlorinated PE, methyl-butadiene-sitren and acrylonitrile-butadiene-sitren).
• stabilizers for instance, lead salts, calcium-zinc
• fillers for instance, calcium carbonate
• dyes for instance, titanium dioxide
• process adjuvant agents for instance, acrylic-based adjuvant agents
• impact additives for instance, chlorinated PE, methyl-butadiene-sitren and acrylonitrile-butadiene-sitren.
• PVC composition does not include distearyl phthalate.
• PVC composition essentially does not include a phthalate including distearyl phthalate.
• a new PVC composition which does not include phthalate is presented as the inner lubricant. It has been found that the subject matter PVC composition has the same PVC processing performance when compared with alternatives comprising phthalate or increases this performance. During processing, the power (torque value) applied by the device decreases and the color of the end product is not affected unfavorably.
• Table 1 Content of the composition with phthalate
• Table 2 Content of the composition with adipat
• Congo red test This test method aims at determining thermal stability of a PVC compound when said PVC compounds are processed at a high temperature. The method can be applied to all PVC compounds, copolymers and products dependent on these. A test sample of PVC material is heated to a specific temperature which is normally between 180-200 e C. The duration which passes for the degradation of the material because of hydrogen chloride is determined by a color change on Congo red test paper.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Emergency Medicine (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Lubricants (AREA)

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• 2021
  • 2021-06-09 TR TR2021/009462A patent/TR202109462A2/tr unknown
• 2022
  • 2022-06-06 EP EP22820693.4A patent/EP4204489A4/de not_active Withdrawn

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