US20090149586A1 - Primary pvc plasticizers derived from vegetable oils, process for obtaining primary pvc plasticizers derived from vegetable oils and plasticized pvc composition - Google Patents

Primary pvc plasticizers derived from vegetable oils, process for obtaining primary pvc plasticizers derived from vegetable oils and plasticized pvc composition Download PDF

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Publication number
US20090149586A1
US20090149586A1 US12/331,092 US33109208A US2009149586A1 US 20090149586 A1 US20090149586 A1 US 20090149586A1 US 33109208 A US33109208 A US 33109208A US 2009149586 A1 US2009149586 A1 US 2009149586A1
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Prior art keywords
pvc
vegetable oils
epoxidized
oil
primary
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Abandoned
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Jacyr Vianna De Quadros Junior
Jose Augusto De Carvalho
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Nexoleum Bioderivados Ltda
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Nexoleum Bioderivados Ltda
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Classifications

    • 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
    • C08K5/04—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
    • C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • 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
    • C08K5/0016—Plasticisers
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/006—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by oxidation

Definitions

  • Polyvinyl chloride is a polymer well known for its wide range of industrial applications. Its natural rigidity, due to its molecular structure, requires the use of some additives to increase the range of useful applications. These compositions are commonly known as PVC compounds.
  • plasticized PVC compounds present high flexibility and are used in films, wire and cable insulation, packaging, hoses, toys, etc.
  • Plasticized PVC compounds are obtained by the addition, in different levels, of additives known as plasticizers, to provide the desired flexibility.
  • Plasticizers are, in general, high boiling point liquids with average molecular weight (between 300 and 600), linear or cyclic carbon chains (14 to 40 carbons) that, when added to the PVC resin allow for movement between the PVC molecules promoting flexibility to the final compound.
  • phthalates obtained from petroleum. In addition to being dependent on the fluctuations of petroleum prices, phthalates are suspect of having adverse effects on human health.
  • Epoxidized soybean oil was proposed as a primary plasticizer.
  • its low compatibility with PVC limited its use to small quantities, keeping it from completely replacing phthalates as a primary plasticizer.
  • Patent GB934689 describes the preparation of esters with high oxirane index (8,5 to 12,33) from vegetable oils with high linolenic acid contents (such as linseed oil) and high iodine index (175 to 200), that are transesterified with lower alcohols and subsequently epoxidized.
  • esters obtained from pentaeritritol, trimelitic acid, ethylene glycol, propylene glycol and interesterified linseed oil
  • plasticizers present the drawback of having larger molecular weight and much higher cost when compared to phthalates.
  • Others obtained from methanol still have a price dependency on petroleum.
  • the proposed esters are composed by mixtures of esters with oxirane indexes greater than 8.
  • the other types of esters have been used as primary plasticizers for PVC only in laboratory tests, indicating the difficulty in obtaining an additive that is both technically and economically viable.
  • the objective of the present invention is to obtain technically and economically viable alternatives of primary plasticizers for PVC compounds derived exclusively from renewable sources (vegetable oils, sugar cane ethanol and sugar cane isoamylic alcohol) that are completely compatible with the PVC resin.
  • the invention developed compositions of plasticizers obtained from the complete transesterification and epoxidation of vegetable oils, henceforth called epoxidized bioesters.
  • Complete transesterification and epoxidation occur when the reactions achieve a minimum of 99% conversion.
  • This invention differs from the state of the art by providing epoxidized bioester plasticizers, presenting low linolenic acid content, and oxirane indexes below 8.
  • the epoxidized bioesters are obtained by the transesterification reaction of vegetable oils with mono-alcohols derived from sugar cane, such as ethanol and isoamylic alcohol, and subsequent epoxidation.
  • Vegetable oils are composed by triglycerides that contain glycerin molecules attached to three saturated, mono-unsaturated, di-unsaturated and tri-unsaturated acids such as palmitic, oleic, linoleic, and linolenic acids, among others. These fatty acids vary also in regards to the size of the carbon chain, presenting 14 to 18 carbon atoms for the oils referred in this invention.
  • the transesterification reaction of vegetable oils is employed to separate these fatty acids from the glycerin molecule and bond them to other alcohol molecules, providing superior properties when compared to those of the triglyceride.
  • the transesterification reaction results in the formation of different esters (depending on the type of alcohol used), with a common alcohol termination. This wide range of ester varieties increases the possibilities of compatibility with PVC, in addition to allowing different properties in the plasticized PVC.
  • the epoxidation process introduces an atom of oxygen in the double bonds of the fatty acid carbon chain, forming an oxirane ring that makes the ester more polar and thus more compatible with the PVC resin.
  • the greater the number of double bonds in the original ester the greater the number of oxirane rings formed, and therefore increased compatibility with PVC.
  • the substitution of the double bonds by the oxirane ring in the fatty acid chains increases the chemical and thermal stability of the resulting molecule.
  • the compatibility of the epoxidized bioesters with the PVC resin depends on the unsaturation of the original esters and the level of epoxidation of the double bonds.
  • the bioesters of this invention present compatibility with PVC even when the resulting oxirane index is below 8, which is not foreseen in the current state of the art.
  • the bioesters are obtained by the transesterification of a mixture of vegetable oils or one vegetable oil, such as soybean oil, with ethanol. After obtained, the bioesters are epoxidized.
  • the vegetable oils are chosen among the oils with an iodine index between 120 and 170, such as soybean oil, corn oil, linseed oil, sunflower oil, or a mixture thereof.
  • the refined soybean oil reacts with anhydrous ethanol in the presence of sodium ethoxide based catalysts, in the molar proportion oil:alcohol of 1:10 to 1:30 and temperatures between 80° C. and 120° C.
  • the glycerin formed in the reaction is separated and the soybean oil ethyl ester is obtained (ethyl soyate) with a high degree of purity.
  • the new ester is then submitted to the epoxidation reaction, where the double bonds of the esters are broken in the presence of free oxygen under specific temperature and mixing condition to form the oxirane rings.
  • Another embodiment is the production of bioesters from the transesterification of a mixture of vegetable oils or one vegetable oil, with iodine index between 120 and 170 such as soybean oil, with isoamylic alcohol.
  • the isoamylic alcohol is obtained from the residue of sugar cane based ethanol production (also known as fusel oil).
  • the bioesters are epoxidized.
  • the vegetable oils are chosen among the oils with an iodine index between 120 and 170, such as soybean oil, corn oil, linseed oil, sunflower oil, or a mixture thereof.
  • TRANSESTERIFICATION REACTION First, 35 g of sodium hydroxide 99% (NaOH) are added to 200 ml of anhydrous ethanol, forming sodium ethoxide in a stoichiometric quantity considering the sodium hydroxide amount, with excess ethanol.
  • 1 liter of soybean oil is pre-heated to 60° C.
  • the 200 ml of sodium/ethanol mixture plus an additional 300 ml of ethanol are added to the reactor.
  • the stirring and temperature are maintained constant for 90 minutes.
  • the reaction forms glycerin, soybean oil acids ethyl ester and excess ethanol and sodium ethoxide.
  • the stirring and heating are turned off and the whole mixture is transferred to a separation funnel.
  • the glycerin accumulated in the bottom is removed, leaving only the ester in the funnel.
  • the ester is washed with water, adding 1 liter of water to the mixture, intense agitation without heating and subsequent decanting for 3 to 6 hours (depending on the speed of separation) until the two phases present a clear interface.
  • the washing procedure is repeated with until the bottom phase is clear after decanting.
  • the ester is then dried at 40° C. for 2 to 4 hours until the material is clear and presents no cloudiness.
  • EPOXIDATION REACTION In a reactor with mechanical stirring, temperature control and reflux condenser, 500 g of the ethyl ester is added and the temperature is elevated to 80° C. Formic acid is added and the mixture is kept at constant agitation. Slowly (for 45 minutes or more) 184 g of hydrogen peroxide 50% is added, controlling the temperature at 90° C. After the addition of the hydrogen peroxide, the system is maintained at 80° for 4 hours. At the end of the reaction, the water phase is separated from the oil phase in a separation funnel. The oil phase contains the epoxidized ester and the formic acid.
  • the final product obtained is the epoxidized ethyl ester of a mixture of soybean oil acids (epoxidized ethyl soyate), which is a viscous transparent liquid slightly yellow and with a faint odor similar in characteristic to the original soybean oil used.
  • the epoxidized ethyl ester presents an oxirane index between 4 and 8, linear molecular chain with an average (20 carbon atoms) and lower average molecular weight (about 340) when compared to the epoxidized soybean oil (900).
  • R preferably selected randomly from the epoxidized oleic, linoleic and linolenic acids.
  • TRANSESTERIFICATION REACTION Initially, 35 g of sodium hydroxide 99% are added to 200 ml of isoamylic alcohol, forming sodium isoamyloxide in a stoichiometric quantity related to the sodium hydroxide, with excess isoamylic alcohol.
  • 1 liter of soybean oil is preheated to 80° C. and the previously prepared alcohol and sodium hydroxide are added to the reactor, with an additional 1600 ml of isoamylic alcohol. The stirring and temperature are maintained constant for 120 minutes. The reaction produces glycerin, isoamyl ester of soybean oil fatty acids, excess of non-reacted isoamylic alcohol, and sodium isoamyloxide.
  • the stirring and heating are turned off and the entire mixture is transferred to separation funnel.
  • decanting the glycerin is removed from the funnel, leaving only the ester.
  • the isoamyl ester is then washed with water, adding 1 liter of water at 70° C. to the mixture, intense stirring and subsequent decanting for 3 to 6 hours (depending on the speed of separation) until a clear interface appears.
  • the aqueous phase is removed from the funnel and the wash is repeated until the material in the aqueous phase is clear.
  • the ester is dried by heating at 70° C., for 2 to 4 hours until the material becomes totally clear, without cloudiness.
  • EPOXIDATION REACTION In a reactor with mechanical stirring, temperature control and reflux condenser, 500 g of the isoamyl ester is added and the temperature is elevated to 80° C. 60 g of formic acid (91%) is added and the mixture is kept at a constant agitation. Slowly (along 45 minutes or more) 178 g of hydrogen peroxide (50%) is added, controlling the temperature at 90° C. After the addition of the hydrogen peroxide, the system is maintained at 80° for 4 hours. At the end of the reaction, the water phase is separated from the oil phase in a separation funnel. The oil phase contains the epoxidized ester and the formic acid.
  • the wash of the oil phase is processed according to the procedure described for the wash of the ethyl ester after the transesterification, although the water needs to be preheated to 50° C. and the wash procedure shall be repeated until all the formic acid has been eliminated.
  • the finished product presents an oxirane index above 4.5, acidity below 5 mg KOH/g, characteristic odor, and slight yellow color.
  • the final product obtained is the epoxidized isoamyl ester (epoxidized isoamyl soyate) of a mixture of soybean oil acids, which is a viscous transparent liquid slightly yellow and with a faint odor similar in characteristic to the original soybean oil used.
  • the epoxidized isoamyl soyate presents an oxirane index between 4 and 8, linear molecular chain with average (23 carbon atoms) and lower average molecular weight (380) when compared to the epoxidized soybean oil.
  • plasticizers of epoxidized isoamyl soyate present the followinq formula:
  • R is preferably selected randomly from the epoxidized oleic, linoleic, and linolenic acid groups.
  • plasticized PVC is obtained by mixing i) 100 parts (weight/weight) of at least one type of PVC resin; ii) 1 to 200 parts (weight/weight) of plasticizer, which consists of epoxidized bioesters with an oxirane index below 8; the mixture is then homogenized and later extruded.
  • the plasticizer is made from vegetable oils completely transesterified with ethanol and later epoxidized, such as the esters of the type epoxidized ethyl soyate.
  • the plasticizer is made from vegetable oils completely transesterified with isoamylic alcohol and later epoxidized, such as the esters of the type epoxidized isoamyl soyate.
  • the plasticizer is made from a mixture of epoxidized ethanol and isoamylic alcohol bioesters, such as epoxidized ethyl soyate and epoxidized isoamyl soyate.
  • the plasticized PVC is therefore free of phthalate plasticizers. It is important to point out that the plasticizers composed of epoxidized bioesters of ethanol and/or isoamylic alcohol provide some property improvements to the plasticized PVC, improvements not foreseen in the state of the art, such as greater flexibility, greater resistance to UV light degradation, better physical properties at low temperatures, better mixture efficiency (salvation) of the PVC resin and better resistance to aliphatic solvents extraction.
  • PVC compounds plasticized with the objects of this invention present superiority in all these properties when compared to plasticized PVC prepared with plasticizers revealed by the state of the art while keeping the same proportion of plasticizer/PVC resin.
  • the epoxidized isoamyl soyate When compared to the epoxidized ethyl soyate, the epoxidized isoamyl soyate has a heavier and longer carbon chain, allowing for its use in applications requiring greater permanence over time.
  • plasticizers of this invention work out the inconveniencies described in the state of the art, presenting the following additional advantages:

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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US12/331,092 2007-12-10 2008-12-09 Primary pvc plasticizers derived from vegetable oils, process for obtaining primary pvc plasticizers derived from vegetable oils and plasticized pvc composition Abandoned US20090149586A1 (en)

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BRPI0705621-4 2007-12-10
BRPI0705621-4A BRPI0705621B1 (pt) 2007-12-10 2007-12-10 Composição plastificte de pvc

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US14/148,312 Active 2029-07-31 US9303140B2 (en) 2007-12-10 2014-01-06 Primary PVC plasticizers derived from vegetable oils, process for obtaining primary PVC plasticizers derived from vegetable oils and plasticized PVC composition
US14/223,090 Active 2029-04-23 US9388292B2 (en) 2007-12-10 2014-03-24 Primary PVC plasticizers derived from vegetable oils, process for obtaining primary PVC plasticizers derived from vegetable oils and plasticized PVC composition

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US14/223,090 Active 2029-04-23 US9388292B2 (en) 2007-12-10 2014-03-24 Primary PVC plasticizers derived from vegetable oils, process for obtaining primary PVC plasticizers derived from vegetable oils and plasticized PVC composition

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US (3) US20090149586A1 (es)
EP (2) EP2070977B1 (es)
BR (1) BRPI0705621B1 (es)
CY (1) CY1116883T1 (es)
DK (2) DK2960282T3 (es)
ES (2) ES2555781T3 (es)
PT (2) PT2070977E (es)
SI (1) SI2070977T1 (es)
TR (1) TR201906236T4 (es)

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WO2012019073A1 (en) * 2010-08-06 2012-02-09 Arkema Inc. Epoxidized composition and methods for making the same
US20120181057A1 (en) * 2009-09-30 2012-07-19 Chaudhary Bharat I Acetylate Glycerin Esters and Their Blends with Epoxidized Fatty Acid Esters
US8557139B2 (en) 2008-02-15 2013-10-15 Dow Global Technologies Llc Replacement plasticizer system for phthalate-plasticized formulations
US8697787B2 (en) 2009-09-30 2014-04-15 Dow Global Technologies Llc Flexible PVC compositions made with plasticizers derived from renewable sources
US8703849B2 (en) 2010-01-22 2014-04-22 Archer Daniels Midland Company Processes for making high purity renewable source-based plasticizers and products made therefrom
US8802988B2 (en) 2009-09-30 2014-08-12 Dow Global Technologies Llc Acetylated derivatives of castor oil and their blends with epoxidized fatty acid esters
US8859654B2 (en) 2009-09-30 2014-10-14 Dow Global Technologies Llc Heat stabilized polymeric composition with epoxidized fatty acid ester plasticizer
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WO2015173608A1 (en) * 2014-05-13 2015-11-19 Magink Comércio De Imagem Gráfica Ltda -Me Dispersion of homopolymer of vinyl chloride
US9228155B2 (en) 2010-07-28 2016-01-05 Dow Global Technologies Llc Plasticizers made from oil extracted from microorganisms and polar polymeric compositions comprising the same
US9394425B2 (en) 2012-06-22 2016-07-19 Dow Global Technologies Llc Acetylated polyol hydroxystearate plasticizers and plasticized polymeric compositions
US9422418B2 (en) 2009-09-30 2016-08-23 Dow Global Technologies Llc Acetylated monoglyceride of 12-hydroxystearic acid and blends with epoxidized fatty acid esters
US9499681B2 (en) 2012-11-12 2016-11-22 Dow Global Technologies Llc Epoxidized fatty acid alkyl ester plasticizers and methods for making epoxidized fatty acid alkyl ester plasticizers
US9593091B2 (en) 2012-11-12 2017-03-14 Dow Global Technologies Llc Methods for making epoxidized fatty acid alkyl esters
CN106519081A (zh) * 2016-09-22 2017-03-22 深圳立山环保材料有限公司 一种环氧类增塑剂及其制备方法
US9850366B2 (en) 2012-10-18 2017-12-26 Dow Global Technologies Llc Epdxidized fatty acid alkyl ester plasticizers and methods for making epdxidized fatty acid alkyl ester plasticizers
US10077355B2 (en) 2012-02-08 2018-09-18 Dow Global Technologies Llc Plasticizer compositions and methods for making plasticizer compositions
US10100172B2 (en) 2012-06-26 2018-10-16 Dow Global Technologies Llc Plasticizers and plasticized polymeric compositions
CN108863987A (zh) * 2018-07-25 2018-11-23 浙江工业大学 一种利用表面活性剂强化油脂环氧化的生产方法
US10398625B2 (en) 2013-03-13 2019-09-03 Fenwal, Inc. Medical containers with terephthalate plasticizer for storing red blood cell products
US10407559B2 (en) * 2014-03-27 2019-09-10 New Japan Chemical Co., Ltd. Plasticizer for vinyl chloride resin containing non-phthalate ester and vinyl chloride resin composition containing such plasticizer
CN110804029A (zh) * 2019-11-08 2020-02-18 浙江工业大学 一种环氧类增塑剂及其制备方法
US11160728B2 (en) 2014-02-20 2021-11-02 Fresenius Kabi Deutschland Gmbh Medical containers and system components with non-DEHP plasticizers for storing red blood cell products, plasma and platelets
CN113817226A (zh) * 2021-10-12 2021-12-21 南京工业大学 一种高分子复合材料添加剂及其应用

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EP2738774A1 (en) 2012-11-30 2014-06-04 Borealis AG A cable construction
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EP2924063A1 (de) * 2014-03-28 2015-09-30 LANXESS Deutschland GmbH Weichmacherzusammensetzung
SI24879A (sl) 2014-11-06 2016-05-31 Eurel D.O.O. Postopek za izdelavo oplaščenih vodilnih cevi, ki ne bodo vsebovale ftalatov, in oplaščene vodilne cevi narejene po tem postopku
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US20140221538A1 (en) 2014-08-07
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