WO2014100862A1 - Composition de polypropylène et son utilisation, pièce de polypropylène, combinaison d'additifs et résine de polypropylène - Google Patents

Composition de polypropylène et son utilisation, pièce de polypropylène, combinaison d'additifs et résine de polypropylène Download PDF

Info

Publication number
WO2014100862A1
WO2014100862A1 PCT/BR2012/000529 BR2012000529W WO2014100862A1 WO 2014100862 A1 WO2014100862 A1 WO 2014100862A1 BR 2012000529 W BR2012000529 W BR 2012000529W WO 2014100862 A1 WO2014100862 A1 WO 2014100862A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition according
agent
polypropylene
resin
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/BR2012/000529
Other languages
English (en)
Portuguese (pt)
Inventor
Alexandre Di Pintor DA LUZ
Marcelo FARAH
Alessandro Cauduro LIMA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Braskem SA
Original Assignee
Braskem SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Braskem SA filed Critical Braskem SA
Priority to PCT/BR2012/000529 priority Critical patent/WO2014100862A1/fr
Priority to ARP130104963A priority patent/AR094226A1/es
Publication of WO2014100862A1 publication Critical patent/WO2014100862A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/002—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix

Definitions

  • the present invention relates to a polypropylene composition
  • a polypropylene composition comprising a combination of additives that act as infrared, nucleation and antiblock absorbing agents in order to optimize and increase the energy efficiency of the thermoforming process by increasing production cycling and reducing the waste of defective generated parts.
  • thermoforming process is widely used in the manufacture of rigid packaging and disposable items as it is an economically viable process for the production of low complexity and high volume parts, since such parts require low forming pressures and low cost molds.
  • accuracy and quality of workpiece finishing is directly related to the balance between heat and pressure during the molding process.
  • thermoforming can be understood as a technique of converting thermoplastic sheets into energy absorbing molded articles which in turn turns into temperature increases and can be assisted by plug and / or vacuum.
  • thermoplastic plates are heated to the most appropriate softening and / or crystalline melting temperature and subsequently molded onto or under a mold. Thermoformed parts can be cut to eliminate unnecessary edges, can also be decorated and / or converted into differently shaped products for different applications.
  • thermoforming process can be subdivided into five main stages, namely: preheating, heating zones, forming stage, cooling and cutting, and can be applied to different types of thermoplastic resins, such as: polypropylene (PP) , high impact polystyrene (HIPS), polystyrene (PS), acrylonitrile butadiene styrene polymer (ABS), vinyl polychloride (PVC) and ethylene polyterephthalate (PET), each type of material requiring parameter adjustments for best product and process performance is achieved, having a direct correlation with the molecular structure of the polymer.
  • PP polypropylene
  • HIPS high impact polystyrene
  • PS polystyrene
  • ABS acrylonitrile butadiene styrene polymer
  • PVVC vinyl polychloride
  • PET ethylene polyterephthalate
  • the preheating stage is only required for resins that have low energy absorption in the next stage (heating), as is the case with PP which in turn has the need for larger heating zones to reach the molding temperature. due to its lower absorption power. For this reason, the preheating stage, especially when using PP resins, is treated as a critical point for productivity in the thermoforming process.
  • Thermoplastic resins exhibit different behaviors during the preheating stage, and for resins with higher energy absorption, the number of heating zones in the thermoforming process can be reduced and / or optimized compared to resins with lower absorption. power.
  • thermoforming machines feature accurate plate temperature control in the heating zones and, through the use of servo motors, provide increased productivity with reduced energy consumption. It is common for thermoforming machines to use ceramic or quartz lamps in their furnaces as infrared (IR) emitting bodies, with greater intensity in the near infrared region, to heat the thermoplastic plates. Quartz lamps are very efficient and recommended for high temperatures because they do not deteriorate quickly; However, such lamps have a higher price in the market.
  • IR infrared
  • thermoforming resins used in thermoforming are generally transparent to infrared irradiation and can therefore be doped with IR absorbers to increase absorption efficiency.
  • Absorbers are typically polar, with groups -OH, -COOH or -NH2.
  • Hydrated inorganics such as hydrous magnesium hydroxide may be used up to 20% by weight to provide polyolefins with some additional absorbance.
  • Carbon black can also be used as an IR absorber, but has an undesirable effect on resin coloration, even in small amounts such as 1 to 10 ppm.
  • the softened or molten polymer is molded in the mold cavity, with or without the assistance of plugs and / or vacuum, and subsequently cooled and removed from the mold usually with the aid of extracting pins and / or pressurized air. At this time the deformation of the original plate occurs to copy the mold details.
  • the cooling stage of the resin to non-flow temperature, at which the resin copies the mold and maintains its geometry, is considered another critical point for productivity in the thermoforming process, as lagging resin crystallization can make it difficult to demould and keep the workpiece attached to the mold.
  • nucleating and clarifying agents to increase productivity, as they increase both the temperature and the crystallization kinetics of polymers, making the resins to reach their non-flow temperature and consequently higher system productivity.
  • accessories such as air blowers, mist and mold cooling are also used to accelerate and homogenize parts on both sides. The demoulding occurs by crystallization of the resin and consequent contraction. Thus, the parts may come loose from the mold cavity and be expelled naturally or by blowing air, for example.
  • release and anti-slip at the cutting stage is common in polymeric films and PP parts for injection cycle gain, and even to ensure both proper unwinding and maintaining a stable sliding force on films.
  • US Patent 4869938 describes the use of hydrogenated petroleum resins for blister packs (which may contain ethylene and butene in PP) with silica particles with particle size smaller than 5 ⁇ for the purpose of improving PP extrusion performance. and the mechanical properties.
  • hydrogenated resins to increase extrusion processability is a complication of the system as it requires values above 5% to significantly improve.
  • US 5961914 deals with the addition of sorbitols to improve processability, especially the more homogeneous shrinkage of thermoformed parts.
  • the invention demonstrates considerable gains in crystallization temperature with the possibility of accelerating the process as it allows demolding at higher temperatures.
  • the technique described in this document does not present process gains regarding the difficulty of heating the plates, nor the possibility of lower kneading index or problems generated when demolding.
  • US 7470727 deals with the use of silica gel and polymer crystallization nucleating agents as a means of preventing agglomeration formation within the dosage systems.
  • This solution encompasses a 10 to 30% mixture of silica with nucleating agents to improve system fluidability.
  • concentration of nucleating agents cited is at most 500 ppm
  • the range of silica added in this system is 50 to 150 ppm. ppm, too low to properly interfere with the radiation absorption process.
  • this silica concentration is too low to act on the part demolding step.
  • US 7303795 describes the use of metal salts to improve the infrared absorption characteristic of PP resins.
  • the presence of salts generates radiation absorption points that can increase the resins absorption level, accelerating the heating process as a whole.
  • these salts in addition to being unusual for PP (metal salts can generate color) applications, can accelerate resin degradation.
  • WO2006 / 001024 describes the use of dehydrated clays and minerals in PP resins for better infrared absorption and use in agricultural greenhouse films. Said document relates particle size to increased infrared absorption in order to retain more heat within planting systems without losing the transparency of polyethylene and / or ethylene vinyl acetate (EVA) films, thereby increasing productivity. agricultural. In this case, therefore, the technology involves the final application and not the improvement of the thermoforming process steps with PP.
  • EVA ethylene vinyl acetate
  • the present invention provides a combination of agents that optimizes and increases the energy efficiency of the thermoforming process, not only improving crystallization kinetics, radiation absorption and ease of demolding, but also increasing the cycling of the thermoforming. reducing waste from defective generated parts
  • the present invention is directed to a polypropylene composition comprising at least one infrared absorbing agent, at least one nucleating agent and at least one antiblocking agent.
  • the present invention is also directed to the use of the polypropylene composition for application in thermoforming, Injection Strecht Blow Molding or any process wherein at least one reheating step is provided for molding.
  • Another object of the present invention is to obtain a combination of additives for the preparation of the polypropylene composition.
  • Another object of the present invention is to obtain a polypropylene resin wherein the polypropylene is selected from homopolymers, random copolymers and etherophasic copolymers, and has a melt index between 0.1 and 20 g / 10min.
  • Figure 1 Representation of anti-blocking agents in plastic films.
  • FIG. 2 Schematic representation of the infrared absorption efficiency measuring equipment.
  • Figure 4 Variation of opacity and calculated derivative of silica samples of different natures at 120 ° C.
  • Figure 5 Calculated derivatives for different nucleating agents and infrared absorption agent for a melt flow rate polypropylene 2 g / 10min.
  • the present invention demonstrates the additive capacity of PP for thermoforming processes by synergizing at least one IR absorbing agent, a nucleating agent and a demolding aid.
  • the purpose of the IR absorption agent is to allow the temperature reduction of the plate heating furnaces in the thermoforming, reducing the energy consumption for this step.
  • the nucleating agent has the function of reducing the time for formation and improving the cutting of the pieces.
  • the release agent helps parts to be extracted more easily without kneading or retention in the mold cavity.
  • Additives are known to impart specific properties to plastics, improving their performance.
  • the inventors of the present patent application studied and tested the thermoforming stages in the presence of a combination of specific additives and concluded that the distribution of such additives on the surface of a PP resin prevents intense adhesion between the wall of the same and the wall of the mold with vacuum, thus facilitating the demolding of the part.
  • non-adherence allows air to enter more quickly between the cavity and the molded part, aiding in its extraction. In the end product this can result in easier separation between two pieces (as in the case of disposable cups, for example), making it an economically attractive process for the consumer.
  • thermoforming agents of the present invention comprises the following additive composition:
  • At least one antiblocking agent or demolding agent.
  • the additive composition disclosed in the present invention is present in a PP resin in an amount ranging from 300 to 2500 ppm by weight, based on the mass of the final resin composition.
  • the PP used in the present invention is preferably selected from the group comprising IF (melt index) homopolymers from 0.1 to 20 g / 10min, random copolymers (selected from the group comprising ethylene comonomers and / or one or more alpha -olefins of 4 to 12 carbon atoms, added in contents of 0,1 to 6% and IF between 0,1 to 20 g / 10min), or heterophasic copolymers (selected from the group comprising ethylene comonomers and / or a or more alpha-olefins of 4 to 12 carbon atoms in the matrix phase with contents of 0.1 to 6%, and rubber phase with ethylene and / or one or more alpha-olefin in fraction of 1 to 40% by weight and Final IF (0.1 to 20 g / 10 min), and / or mixture thereof.
  • IF melt index
  • the IR absorbing agent used in the present invention is preferably selected from the group comprising mineral fillers and organic compounds.
  • Mineral fillers are preferably selected from silicas, hydrotalcites, calcium carbonates, micas, kaolin, clays, carbon black, talc, zeolites, diatomaceous earth, among other mineral fillers, metal salts and mixtures thereof, and the fillers may be have different particle sizes and distributions.
  • the organic compounds are preferably selected from the group which comprises aromatic ring rich organic compounds and other functional groups capable of improving the infrared absorption of the PP resin. The choice of filler must be made so that the transparency of the PP resin is maintained at least 65% on 1 mm plates.
  • the contents may range from 250 to 5000 ppm for absorbers, more specifically between 400 and 2500 ppm, except for carbon black which may be in the range of 1 to 15 ppm, more specifically between 3 and 10 ppm.
  • the desired size of absorbing agent is 100 to 5000 nm average particle size, except for carbon black where the order should be 20 to 100 nm.
  • the crystallizing nucleating agent used in the present invention is preferably selected from the group comprising organic and inorganic compounds, such as talc, sodium benzoate, sorbite salts thereof, bicyclo (2,2,1) heptane dicarboxylate salts, phosphates, triphenythiazine, gamma-quinacridone, N N'-dicyclohexylterephthalamide, and mixture of calcium stearate with pimelic acid or suberic acid or a mixture of two or more thereof. These agents and mixtures thereof may be present in the range of 200 to 2000 ppm, more specifically between 250 and 000 ppm.
  • organic and inorganic compounds such as talc, sodium benzoate, sorbite salts thereof, bicyclo (2,2,1) heptane dicarboxylate salts, phosphates, triphenythiazine, gamma-quinacridone, N N'-dicyclohexylterephthalamide, and mixture of
  • the antiblocking agent used in the present invention is selected from the group comprising inorganic compounds such as silicas (natural and synthetic), talc, calcium carbonate, diatomaceous earth, kaolin, glass beads, mica or a mixture of two or more thereof, and organic compounds such as bisamides, primary and secondary amides, organic and metallic stearates, polyethylene fluoride (PTFE), silicones, among others, or a mixture of two or more thereof. These agents may be present in the fraction from 100 to 2000 ppm, more specifically between 300 and 1000 ppm.
  • the desired particle size of the demoulding agents is from 3 to 10 microns average particle size.
  • At least two additives present in the composition consist of the same substance.
  • the agents of the composition are chosen such that there is at least one substance acting as at least two agents.
  • an absorbing agent and an antiblocking agent may act not only on infrared absorption and / or demolding, but also on nucleation of the product.
  • the sum of effects and their synergies can give PP resin a higher thermoforming profile than pure products, maintaining the same level of transparency and showing significant economic and competitive advancement.
  • the combination of at least two IR absorbing agents is used in the composition disclosed in the present invention.
  • At least one infrared absorber exerts the function of antiblocking agent; or at least one infrared absorbing agent performs the function of nucleating agent; or at least one nucleating agent performs the function of antiblocking agent; or at least one nucleating agent performs the function of infrared absorber; or at least one anti-blocking agent performs the function of infrared absorber; or at least one antiblocking agent performs the function of nucleating agent.
  • the PP resin comprising the additive composition disclosed in the present invention may be applied in thermoforming processes, Injection Strecht Blow Molding (ISBM), or any process wherein at least one reheating step is provided for molding.
  • ISBM Injection Strecht Blow Molding
  • the PP resin is applied in thermoforming processes.
  • the PP resin comprising the additive composition disclosed in the present invention has infrared absorption properties of at least 1 in the derivative at a temperature of 120 ° C (and at least 10% greater than pure polymer) with opacity. less than 65% on 1 mm specimens, with productivity at least 5% above the reference (pure polymer) and / or loss ratios less than 30% from the reference and / or reduction in total energy consumption of at least 3 % by weight of processed resin.
  • the IR lamp (1) generates radiation that collides with the thermal insulation plate (3).
  • this plate there is an opening (4) through which part of the radiation strikes an injected polymer sample (5) and causes heating.
  • An IR sensor (6) positioned in the shade of the lamp (1), focused on the polymer sample face (5), captures the temperature values of the opposite face of the sample (5), at a distance determined by a ruler (2). ) control, generating a heating profile. Temperature values between 100 and 140 ° C were analyzed and the resulting curve derivative at 120 ° C was used as heat absorption efficiency criteria.
  • the lamp was set at a temperature of 500 ° C and the distance to the insulating stand was 145 mm.
  • the demolding step was evaluated using DSC (Differential Scaning Calorimetry) curves, where the samples are heated to 200 ° C and cooled to 10 ° C / min and the crystallization temperature (Tc) is determined. The higher the Tc, the higher the possible demoulding temperature.
  • the analysis of resistance to demolding was done by measuring the sliding between COF plates (coefficient of friction), considering that the sample with lower coefficients will present easier demolding and, consequently, less tendency to kneading and retention in the cavities.
  • the resins used in the present invention were commercial IF 2 and 3 g / 10min PP resins, usual for the cup and jar thermoforming segments. The following nomenclature helps to understand the coding of samples:
  • the derivative value indicates the local heating rate of the sample and is interpreted as the absorption efficiency.
  • Small (fine) mineral fillers tend to have a higher derivative value at lower temperatures and performance decreases with increasing temperature.
  • the increase in filler contents also leads to an increase in the derivative, but two facts lead to a limitation of the content: increased opacity, as in the case of excess silica, and excessive yellowing of silica and calcium carbonate.
  • the best content will be determined by obtaining higher values of the derivative in the entire analysis range, according to the methodology. It is relevant to point out that Some properties are affected by absorbers, and in the case of PP applications the transparency appeal is relevant and should be weighed in choosing the appropriate content / composition for the application. For silica we have the efficiency and opacity behavior presented in Figure 4.
  • the use of fine particles is more efficient than larger particles due to the area of IR absorbers exposed to radiation.
  • the particle may have ADe and AAIR effect, as in the case of ordinary silica, but more than one AAIR or ADe may be made to obtain the most suitable processing gain value.
  • the mixture of common silica, colloidal silica and fine carbonate for maximum performance in all temperature and performance ranges.
  • Example 02 Composite effect of IR and nucleating absorbers.
  • compositions with only ANu and AAIR are shown, and the results obtained are illustrated in Figure 5.
  • Example 03 Synergistic effect of ANu, AAIR and ADe on practical thermoforming results.
  • silica played two roles: ADe and AAIR, but the use of specific component is interesting and desirable since in Example 1 common silica was not the best absorber.
  • the optimized product will also have gains in the easy removal of one cup from the other by actuating the bulb. ADe.
  • composition in the presence of ADe and ANu, generated a plate with lower coefficient of friction, facilitating two important effects:
  • formulation optimization demonstrates that there is a need for at least one AAIR, at least one ANu and at least one ADe.
  • the use of thinner loading is also desirable as it allows for the possibility of a better optical characteristic added to a product of greater final appeal.
  • Combining more than one AAIR is also desirable, as it can improve absorption at different temperatures, according to curve-based analyzes between 100 and 140 ° C, specifically at 120 ° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de polypropylène et son utilisation pour application en thermoformage, comprenant au moins un agent d'absorption d'infrarouge, au moins un agent de nucléation, et au moins un agent anti-blocage pour optimiser et augmenter l'efficacité énergétique du procédé de thermoformage, améliorant le cycle de production et réduisant les pertes associées aux pièces produites avec des défauts. La présente invention concerne également une pièce et une résine de polypropylène, ainsi qu'une combinaison d'additifs évitant une adhésion intense entre la paroi de la résine et la paroi du moule sous vide, facilitant ainsi le démoulage de la pièce.
PCT/BR2012/000529 2012-12-26 2012-12-26 Composition de polypropylène et son utilisation, pièce de polypropylène, combinaison d'additifs et résine de polypropylène Ceased WO2014100862A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/BR2012/000529 WO2014100862A1 (fr) 2012-12-26 2012-12-26 Composition de polypropylène et son utilisation, pièce de polypropylène, combinaison d'additifs et résine de polypropylène
ARP130104963A AR094226A1 (es) 2012-12-26 2013-12-20 Composicion de polipropileno y su uso, pieza de polipropileno, combinacion de aditivos y resina de polipropileno

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/BR2012/000529 WO2014100862A1 (fr) 2012-12-26 2012-12-26 Composition de polypropylène et son utilisation, pièce de polypropylène, combinaison d'additifs et résine de polypropylène

Publications (1)

Publication Number Publication Date
WO2014100862A1 true WO2014100862A1 (fr) 2014-07-03

Family

ID=51019577

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/BR2012/000529 Ceased WO2014100862A1 (fr) 2012-12-26 2012-12-26 Composition de polypropylène et son utilisation, pièce de polypropylène, combinaison d'additifs et résine de polypropylène

Country Status (2)

Country Link
AR (1) AR094226A1 (fr)
WO (1) WO2014100862A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110003571A (zh) * 2019-04-29 2019-07-12 金旸（厦门）新材料科技有限公司 一种高疏水低气味阻燃聚丙烯复合材料及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5961914A (en) * 1996-05-03 1999-10-05 Milliken & Company Method of thermoforming polyolefin resin
WO2004083294A1 (fr) * 2003-03-13 2004-09-30 Invista Technologies S.A.R.L. Moulage de polypropylene a caracteristiques de postcombustion ameliorees
EP1921059A2 (fr) * 2001-03-24 2008-05-14 Milliken&Company Articles thermoplastiques hautement nucléés

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5961914A (en) * 1996-05-03 1999-10-05 Milliken & Company Method of thermoforming polyolefin resin
EP1921059A2 (fr) * 2001-03-24 2008-05-14 Milliken&Company Articles thermoplastiques hautement nucléés
WO2004083294A1 (fr) * 2003-03-13 2004-09-30 Invista Technologies S.A.R.L. Moulage de polypropylene a caracteristiques de postcombustion ameliorees

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SILVIO MANRICH, PROCESSAMENTO DE TERMOPLÁSTICOS/ROSCA UNICA/EXTRUSÃO&MATIZES/INJEGDO/MOLDES, 2005, pages 240 - 242 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110003571A (zh) * 2019-04-29 2019-07-12 金旸（厦门）新材料科技有限公司 一种高疏水低气味阻燃聚丙烯复合材料及其制备方法
CN110003571B (zh) * 2019-04-29 2021-04-20 金旸（厦门）新材料科技有限公司 一种高疏水低气味阻燃聚丙烯复合材料及其制备方法

Also Published As

Publication number Publication date
AR094226A1 (es) 2015-07-22

Similar Documents

Publication Publication Date Title
ES2295384T3 (es) Metodo para producir articulos de poli(acido lactico) semicristalino.
EP2822992B1 (fr) Composition essentiellement d'origine biologique, thermoformable et conteneurs formés de celle-ci
JPS5962660A (ja) 熱成形部分結晶ポリエステル製品の製造方法
JPH02286725A (ja) 軽量ポリエステル物品
KR102641627B1 (ko) 첨가제 조성물, 및 이를 사용한 중합체 조성물의 제조 방법
ES2877607T3 (es) Composición de resina de poliéster y procedimiento para la fabricación de un artículo de vajilla de alta densidad
ATE234184T1 (de) Verfahren zum herstellen von kunststoffschaumgegenständen mit niedriger dichte
US20040026827A1 (en) Method for the fabrication of crystallizable resins and articles therefrom
US9815964B2 (en) Polyester composition for extrusion blow molded containers with improved aging and drop performance
WO2014100862A1 (fr) Composition de polypropylène et son utilisation, pièce de polypropylène, combinaison d'additifs et résine de polypropylène
JP2014159134A (ja) 耐熱食品容器及びその製造方法
ES2818375T3 (es) Fabricación de artículos a base de polilactida por rotomoldeo
EP3222405A1 (fr) Procédé de fabrication d'un récipient résistant à la chaleur
BRPI0708939A2 (pt) recipiente, processo para preparar um recipiente, processo para preparar uma prÉ-forma micro-celular, e recipiente plÁstico possuindo uma estrutura espumada
CA2697228A1 (fr) Procede pour preparer un contenant ayant une paroi en mousse
BR112017016628B1 (pt) Método para a produção de partes pequenas de plástico de parede delgada, e, parte pequena de plástico de parede delgada
CN1989191A (zh) 基于聚酯的热塑性组合物及其制备方法和由这些组合物获得的中空体
IT202100022292A1 (it) Processo per la produzione di contenitori in PET e rPET ad elevata barriera e cristallinità con tecnologia monostadio standard di iniezione-stiro-soffiaggio
CN1925969A (zh) 具有发泡器壁的容器
WO2012121960A1 (fr) Procédé pour la préparation d'un article en mousse d'acide polylactique résistant à la chaleur
BR112021012232A2 (pt) Artigo modelado e método para produzir o mesmo
CA3214026A1 (fr) Compositions de polymere de polypropylene et articles fabriques a partir de celles-ci
BR112021012232B1 (pt) Método para produzir um artigo modelado
AU2020300261A1 (en) Polymer nanocomposite comprising a melt mixture of virgin pet and recycled pet with clay; method for preparing the nanocomposite; and use thereof in the manufacture of mouldable objects or films, including packages, containers and fibres, among others
JPS59164118A (ja) ポリプロピレン製二軸延伸ボトルの製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12890738

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12890738

Country of ref document: EP

Kind code of ref document: A1