ITMC20080116A1 - THERMOPLASTIC ELASTOMERS WITH HIGH ENVIRONMENTAL COMPATIBILITY AND BIODEGRADABILITY. - Google Patents
THERMOPLASTIC ELASTOMERS WITH HIGH ENVIRONMENTAL COMPATIBILITY AND BIODEGRADABILITY. Download PDFInfo
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- ITMC20080116A1 ITMC20080116A1 ITMC20080116A ITMC20080116A1 IT MC20080116 A1 ITMC20080116 A1 IT MC20080116A1 IT MC20080116 A ITMC20080116 A IT MC20080116A IT MC20080116 A1 ITMC20080116 A1 IT MC20080116A1
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- Prior art keywords
- maleic anhydride
- block copolymer
- modified
- styrene
- thermoplastic elastomeric
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- 229920002725 thermoplastic elastomer Polymers 0.000 title description 6
- 230000007613 environmental effect Effects 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 claims description 38
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 25
- 229920006132 styrene block copolymer Polymers 0.000 claims description 22
- 235000013311 vegetables Nutrition 0.000 claims description 18
- 229920001169 thermoplastic Polymers 0.000 claims description 17
- 239000004416 thermosoftening plastic Substances 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 13
- -1 Styrene-Ethylene-Butylene-Styrene Chemical class 0.000 claims description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 10
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 10
- 229920002472 Starch Polymers 0.000 claims description 9
- 229920002678 cellulose Polymers 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 235000019698 starch Nutrition 0.000 claims description 9
- 241000196324 Embryophyta Species 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 229920001400 block copolymer Polymers 0.000 claims description 5
- 240000008042 Zea mays Species 0.000 claims description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 235000005822 corn Nutrition 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 2
- 241000018646 Pinus brutia Species 0.000 claims description 2
- 235000011613 Pinus brutia Nutrition 0.000 claims description 2
- 244000061456 Solanum tuberosum Species 0.000 claims description 2
- 235000002595 Solanum tuberosum Nutrition 0.000 claims description 2
- 235000021307 Triticum Nutrition 0.000 claims description 2
- 150000001336 alkenes Chemical group 0.000 claims description 2
- 235000009120 camo Nutrition 0.000 claims description 2
- 235000005607 chanvre indien Nutrition 0.000 claims description 2
- 239000011487 hemp Substances 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims 7
- 235000010980 cellulose Nutrition 0.000 claims 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 claims 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims 1
- 241000209140 Triticum Species 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 claims 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 claims 1
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 claims 1
- 229920002743 polystyrene-poly(ethylene-ethylene/propylene) block-polystyrene Polymers 0.000 claims 1
- 241000894007 species Species 0.000 claims 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims 1
- 229920006249 styrenic copolymer Polymers 0.000 claims 1
- 239000000047 product Substances 0.000 description 21
- 235000015112 vegetable and seed oil Nutrition 0.000 description 20
- 239000008158 vegetable oil Substances 0.000 description 19
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000004014 plasticizer Substances 0.000 description 7
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000001617 migratory effect Effects 0.000 description 3
- 239000012766 organic filler Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 2
- 229920002633 Kraton (polymer) Polymers 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 235000012438 extruded product Nutrition 0.000 description 2
- 239000012764 mineral filler Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000016571 aggressive behavior Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 231100000209 biodegradability test Toxicity 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003920 environmental process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/006—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions 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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
DESCRIZIONE DESCRIPTION
a corredo di una domanda di brevetto per invenzione industriale avente per titolo: accompanying a patent application for an industrial invention entitled:
“ELASTOMERI TERMOPLASTICI CON ELEVATA COMPATIBILITÀ AMBIENTALE E BIODEGRADABILITÀ” "THERMOPLASTIC ELASTOMERS WITH HIGH ENVIRONMENTAL COMPATIBILITY AND BIODEGRADABILITY"
TESTO DELLA DESCRIZIONE TEXT OF THE DESCRIPTION
La presente domanda di brevetto per invenzione ha per oggetto un gruppo di elastomeri termoplastici con elevata compatibilità ambientale e biodegradabilità. The present patent application for the invention relates to a group of thermoplastic elastomers with high environmental compatibility and biodegradability.
I copolimeri a blocchi SBS (Stirene-Butadiene-Stirene), SIS (Stirene-Isoprene-Stirene), SIBS (Stirene-Isoprene, Butadiene-Stirene) ed i suoi derivati idrogenati (SEBS, SEPS, SEEPS etc.), vengono usualmente plastificati con oli minerali di natura paraffinica con basso contenuto di prodotti aromatici. The block copolymers SBS (Styrene-Butadiene-Styrene), SIS (Styrene-Isoprene-Styrene), SIBS (Styrene-Isoprene, Butadiene-Styrene) and its hydrogenated derivatives (SEBS, SEPS, SEEPS etc.), are usually plasticized with paraffinic mineral oils with low content of aromatic products.
Negli ultimi anni sono stati sviluppati compounds in cui i plastificanti minerali sono stati sostituiti con prodotti di origine vegetale, quali gli oli estratti da una grande varietà di organismi vegetali, Soia, Mais, Lino etc., contribuendo così a risolvere i numerosi e gravi problemi posti dai plastificanti minerali, sia nel caso di contatto umano che nella biodegradabilità. In recent years, compounds have been developed in which mineral plasticizers have been replaced with products of vegetable origin, such as oils extracted from a large variety of plant organisms, soybeans, corn, flax etc., thus helping to solve the numerous and serious problems posed by mineral plasticizers, both in the case of human contact and in biodegradability.
La domanda di brevetto MC2007A000010, a nome della stessa richiedente, illustra ampiamente questo uso di oli vegetali, anche se limita la sua descrizione ai soli elastomeri termoplastici di natura stirenica, SBS, SEBS e similari, senza l’utilizzo di alcun prodotto compatibilizzante e senza l’addizione di prodotti solidi vegetali. Patent application MC2007A000010, in the name of the same applicant, amply illustrates this use of vegetable oils, even if it limits its description only to thermoplastic elastomers of styrenic nature, SBS, SEBS and similar, without the use of any compatibilizing product and without the addition of plant solids.
Saltuariamente sono stati osservati fenomeni di migrazioni di oli vegetali in superficie, eventi rari, ma pur sempre presenti, la cui responsabilità è da attribuire alla limitata compatibilità del blocco butadienico con l’olio vegetale. Occasionally, phenomena of migration of vegetable oils to the surface have been observed, rare but still present events, the responsibility of which is to be attributed to the limited compatibility of the butadiene block with vegetable oil.
Il brevetto EP 1 181 333, a nome BASF, descrive un procedimento che risolve il problema della compatibilità, tra olio vegetale e copolimero a blocchi stirenico con una modifica strutturale del blocco soft butadienico, per renderlo più polare e conseguentemente più compatibile con l’olio vegetale. Patent EP 1 181 333, in the name of BASF, describes a process that solves the problem of compatibility between vegetable oil and styrenic block copolymer with a structural modification of the soft butadiene block, to make it more polar and consequently more compatible with oil. vegetable.
La modifica, è realizzata nella fase di polimerizzazione del blocco butadienico con l’introduzione di una miscela di Stirene e Butadiene che produce un segmento di catena di composizione mista Butadiene Stirene al posto del solo Butadiene. The modification is carried out in the polymerization phase of the butadiene block with the introduction of a mixture of Styrene and Butadiene which produces a chain segment of mixed composition Butadiene Styrene instead of only Butadiene.
Questa modifica aumenta senz’altro la compatibilità, del blocco Stirene-Butadiene con l’olio vegetale, ma rende meno elastastico il copolimero a blocchi stirenico, con riduzione delle sue caratteristiche elastomeriche. This modification certainly increases the compatibility of the Styrene-Butadiene block with vegetable oil, but makes the styrene block copolymer less elastic, with a reduction in its elastomeric characteristics.
Alla luce di quando sopra descritto, si riduce sensibilmente la possibilità di introdurre prodotti solidi polimerici di natura vegetale, amidacea o cellulosica, in forma polvere o fibre, allo scopo di incrementare la caratteristica biodegradativa del compound, in quanto si renderebbe ancora più instabile il complesso copolimero a blocchi stirenico e olio vegetale. In the light of what has been described above, the possibility of introducing solid polymeric products of a vegetable, starchy or cellulosic nature, in powder or fiber form, is considerably reduced, in order to increase the biodegradative characteristic of the compound, as it would make the complex even more unstable. styrenic block copolymer and vegetable oil.
Questi prodotti solidi vegetali, si comportano essenzialmente, ma non esattamente, come le cariche minerali normalmente utilizzate in questa tipologia di materiali, quali ad esempio Carbonato di Calcio, Caolino, Talco etc., ma presentano il grande vantaggio di accrescere considerevolmente la caratteristica biodegradativa dei compounds. These solid vegetable products behave essentially, but not exactly, like the mineral fillers normally used in this type of materials, such as for example Calcium Carbonate, Kaolin, Talc etc., but have the great advantage of considerably increasing the biodegradative characteristic of compounds.
Gli amidi o le cellulose sono prodotti le cui superfici esterne di contatto con la matrice elastomerica sono molto polari, essenzialmente costituite da gruppi idrossilici, pertanto la compatibilità con i polimeri elastomerici basati su copolimeri a blocchi stirenici, i TPE-S, plastificati con gli oli vegetali, è sensibilmente ridotta. Starches or cellulose are products whose external contact surfaces with the elastomeric matrix are very polar, essentially consisting of hydroxyl groups, therefore compatibility with elastomeric polymers based on styrenic block copolymers, the TPE-S, plasticized with oils vegetable, is significantly reduced.
Il fenomeno della migrazione degli oli vegetali, utilizzati come plastificanti su compounds stirenici a blocchi, ha sino ad ora impedito l’uso di discrete quantità di solidi di origine vegetale in questi prodotti, riducendo la loro capacità biodegradativa. The phenomenon of the migration of vegetable oils, used as plasticizers on block styrenic compounds, has so far prevented the use of discrete quantities of solids of vegetable origin in these products, reducing their biodegradation capacity.
Scopo della presente invenzione è di eliminare gli inconvenienti della tecnica nota, fornendo elastomeri termoplastici con elevata compatibilità ambientale e biodegradabilità. The object of the present invention is to eliminate the drawbacks of the known art, providing thermoplastic elastomers with high environmental compatibility and biodegradability.
Altro scopo della presente invenzione è di fornire elastomeri termoplastici altamente compatibili con oli e cariche vegetali ed in particolare atti ad evitare la migrazione degli oli. Another object of the present invention is to provide thermoplastic elastomers highly compatible with vegetable oils and fillers and in particular suitable for avoiding the migration of oils.
Questi scopi sono raggiunti in accordo all’invenzione, con le caratteristiche elencate nell’annessa rivendicazione indipendente 1. These purposes are achieved in accordance with the invention, with the characteristics listed in the attached independent claim 1.
Realizzazioni vantaggiose appaiono dalle rivendicazioni dipendenti. Advantageous embodiments appear from the dependent claims.
Gli oli di semi di origine vegetale sono essenzialmente dei trigliceridi di acidi grassi saturi ed insaturi, pertanto in una catena molecolare di circa 50 atomi di carbonio sono presenti solo 3 gruppi esterei che conferiscono una limitata polarità chimica complessiva del prodotto. Seed oils of vegetable origin are essentially triglycerides of saturated and unsaturated fatty acids, therefore in a molecular chain of about 50 carbon atoms there are only 3 ester groups which give the product a limited overall chemical polarity.
Tale relativamente bassa polarità rende l’olio utilizzabile quale plastificante delle catene paraffiniche o paraffinicheolefiniche presenti tra i blocchi stirenici dei copolimeri a blocchi Stirene-Butadiene, o Stirene-Isoprene (o prodotti similari) con limitati problemi di migrazione sia in produzione che durante la vita dei manufatti. This relatively low polarity makes the oil usable as a plasticizer of the paraffinic or paraffinicolefinic chains present between the styrene blocks of the Styrene-Butadiene block copolymers, or Styrene-Isoprene (or similar products) with limited migration problems both in production and during life. of the artifacts.
Soprattutto non si evidenziano fenomeni di dissoluzione dei domini stirenici con riduzione delle caratteristiche elastomeriche complessive; infatti le prove meccaniche di trazione, allungamento e ritorno elastico, non hanno evidenziato differenze sostanziali nei riguardi dei compound prodotti con oli minerali. Above all, there are no phenomena of dissolution of the styrene domains with a reduction of the overall elastomeric characteristics; in fact, the mechanical tests of traction, elongation and elastic return did not show substantial differences with regard to compounds produced with mineral oils.
Prove di resistenza a temperatura, effettuate su provini posti a 55° di temperatura ed a –25° C non hanno evidenziato sostanziali anomalie di migrazione, verso la superficie esterna, dei prodotti oleosi, anche se sono stati rilevati sporadici fenomeni di scarso rilievo. Temperature resistance tests, carried out on specimens placed at a temperature of 55 ° and at –25 ° C, did not show substantial migration anomalies, towards the external surface, of the oily products, even if sporadic phenomena of little importance were detected.
La preparazione dei compounds basati sui copolimeri a blocchi stirenici plastificati con oli vegetali ed additivati con prodotti inerti di origine vegetale, quali amidi o cellulose, segue perfettamente la dinamica e la logica dei corrispondenti compounds prodotti con oli e cariche di origine minerali, ma l’inserimento di questi elementi contenenti elevate quantità di gruppi idrossilici superficiali, modifica sensibilmente le caratteristiche di equilibrio termodinamico del sistema rendendolo più instabile. The preparation of compounds based on styrenic block copolymers plasticized with vegetable oils and additives with inert products of vegetable origin, such as starch or cellulose, perfectly follows the dynamics and logic of the corresponding compounds produced with oils and fillers of mineral origin, but the insertion of these elements containing high quantities of surface hydroxyl groups, significantly modifies the thermodynamic equilibrium characteristics of the system, making it more unstable.
Questa instabilità si manifesta con un sensibile incremento di fenomeni migrativi degli oli vegetali verso la superfici dei prodotti, creando notevoli problemi di adesività verso i comuni collanti poliuretanici, conferendo, inoltre, una negativa sensazione visiva e tattile alla superficie del manufatto. This instability manifests itself with a significant increase in migratory phenomena of vegetable oils towards the surfaces of the products, creating considerable problems of adhesiveness towards common polyurethane glues, also giving a negative visual and tactile sensation to the surface of the product.
L’incremento della quantità totale di prodotti biodegradabili, di origine naturale, a valori superiori al 20-30%, aumenta la caratteristica biodegradativa del compound, ma nel contempo riduce la sua stabilità nei riguardi degli oli vegetali, con la conseguenza di esaltare fenomeni di separazione dell’olio verso la superficie, vanificando così lo sforzo ecologico complessivo che si desidera ottenere. The increase in the total quantity of biodegradable products, of natural origin, to values higher than 20-30%, increases the biodegradative characteristic of the compound, but at the same time reduces its stability with regard to vegetable oils, with the consequence of enhancing phenomena of separation of the oil towards the surface, thus nullifying the overall ecological effort that is to be obtained.
La richiedente ha sorprendentemente scoperto una famiglia di prodotti polimerici in grado di risolvere il problema della compatibilità dei copolimeri a blocchi stirenici, saturi ed insaturi, nei riguardi degli oli e cariche vegetali, quando questi prodotti vengono utilizzati in concentrazione totale, superiore al 20%. The Applicant has surprisingly discovered a family of polymeric products capable of solving the problem of the compatibility of saturated and unsaturated styrenic block copolymers, with regard to vegetable oils and fillers, when these products are used in a total concentration, higher than 20%.
I prodotti capaci di eliminare i fenomeni migratori degli oli vegetali e così incrementare la capacità biodegradativa dei compounds, quando vengono additivati ulteriormente con prodotti solidi di origine vegetale, sono i derivati maleici dei copolimeri a blocchi stirenici, SBS, SEBS, etc.. The products capable of eliminating the migratory phenomena of vegetable oils and thus increasing the biodegradative capacity of the compounds, when they are further added with solid products of vegetable origin, are the maleic derivatives of styrenic block copolymers, SBS, SEBS, etc ..
L’Anidride Maleica, inserita mediante reazioni di addizione, alla catena alifatica di detti copolimeri, che chiameremo S-B(ma)-S, S-EB(ma)-S, S-EP(ma)-S, etc., modifica la polarità del blocco alifatico di detti copolimeri rendendoli capaci di interagire contemporaneamente sia con le parti idrossiliche delle superfici amidacee o cellulosiche che con i gruppi esterei degli oli vegetali. Maleic anhydride, inserted through addition reactions, to the aliphatic chain of said copolymers, which we will call S-B (ma) -S, S-EB (ma) -S, S-EP (ma) -S, etc., modifies the polarity of the aliphatic block of said copolymers making them capable of interacting simultaneously both with the hydroxyl parts of the starchy or cellulosic surfaces and with the ester groups of vegetable oils.
I blocchi stirenici degli SB(ma)S o SEB(ma)S od altri similari, non sono interessati alla modifica prodotta dall’anidride maleica, rimanendo perfettamente compatibili con i blocchi stirenici del copolimero base SBS o SEBS od altro prodotto similare, rendendo così omogeneo il sistema ed evitando una separazione di fase che è alla base del fenomeno migratorio dell’olio vegetale. The styrene blocks of SB (ma) S or SEB (ma) S or other similar, are not interested in the modification produced by maleic anhydride, remaining perfectly compatible with the styrenic blocks of the SBS or SEBS copolymer base or other similar product, thus making homogeneous the system and avoiding a phase separation which is the basis of the migratory phenomenon of vegetable oil.
La preparazione dei derivati maleici di copolimeri SBS o SEBS è nota in letteratura e si effettua facendo reagire l’Anidride Maleica solida con i copolimeri a blocchi mediante intervento, in temperatura, di catalizzatori generatori di radicali. The preparation of maleic derivatives of SBS or SEBS copolymers is known in the literature and is carried out by reacting the solid Maleic Anhydride with the block copolymers by means of the intervention, at temperature, of radical generating catalysts.
La reazione avviene allo stato fuso in estrusore, alle condizioni di temperatura dipendenti dal catalizzatore utilizzato, cioè funzione della sua velocità di decomposizione alla condizione prescelta e della viscosità del copolimero base utilizzato. The reaction takes place in the molten state in the extruder, at the temperature conditions depending on the catalyst used, that is, a function of its decomposition rate at the chosen condition and of the viscosity of the base copolymer used.
In genere la quantità di Anidride Maleica legata nel copolimero a blocchi può oscillare tra 0,5% e 10%, preferibilmente una concentrazione Anidride Maleica tra 1% e 5% è sufficiente a risolvere il problema della compatibilità. Generally the quantity of Maleic Anhydride bound in the block copolymer can fluctuate between 0.5% and 10%, preferably a Maleic Anhydride concentration between 1% and 5% is sufficient to solve the compatibility problem.
Nel mercato esistono diversi copolimeri SBS od SEBS funzionalizzati con anidride maleica, prodotti da ditte quali Kraton, Kuraray, Hauser Polimeri, od altre ditte similari. On the market there are several SBS or SEBS copolymers functionalized with maleic anhydride, produced by companies such as Kraton, Kuraray, Hauser Polimeri, or other similar companies.
Il ogni caso, copolimero a blocchi stirenico, modificato con anidride maleica può comprendere una qualsiasi delle seguenti basi: SEBS (Stirene-Etilene-Butilene-Stirene), SEPS (Stirene-Etilene-Propilene-Stirene), SEP (Stirene-Etilene-Propilene), SEEPS (Stirene-Etilene-Etilene-Propilene-Stirene), SBS (Stirene-Butilene-Stirene), SIS (Stirene-Isoprene-Stirene) e anche un copolimero a blocchi stirenico avente una catena olefinica derivata da olefine dieniche da 4 a 10 atomi di carbonio, che viene modificata per reazione con anidride maleica. Each case, maleic anhydride modified styrene block copolymer may comprise any of the following bases: SEBS (Styrene-Ethylene-Butylene-Styrene), SEPS (Styrene-Ethylene-Propylene-Styrene), SEP (Styrene-Ethylene-Propylene ), SEEPS (Styrene-Ethylene-Ethylene-Propylene-Styrene), SBS (Styrene-Butylene-Styrene), SIS (Styrene-Isoprene-Styrene) and also a styrene block copolymer having an olefin chain derived from 4 to 10 carbon atoms, which is modified by reaction with maleic anhydride.
La preparazione del compound, ad alta biocompatibilità, prevede l’iniziale processo di assorbimento del plastificante sul polimero, l’aggiunta di cariche organiche tipo amidi o cellulose, del polimero modificato con Anidride Maleica, di vari altri additivi e pigmenti coloranti, infine l’estrusione con gli usuali macchinari da sempre usati per questa tipologia di materiali elastomerici. The preparation of the highly biocompatible compound involves the initial absorption process of the plasticizer on the polymer, the addition of organic fillers such as starches or cellulose, the polymer modified with Maleic Anhydride, various other additives and coloring pigments, finally the extrusion with the usual machinery that has always been used for this type of elastomeric materials.
La concentrazione del copolimero a blocchi stirenico nel compound elastomerico termoplastico è compresa tra 0,5% e 20%, preferibilmente tra 1% e 6%. The concentration of the styrenic block copolymer in the thermoplastic elastomeric compound is between 0.5% and 20%, preferably between 1% and 6%.
I prodotti solidi vegetali comprendono amidi e/o cellulose. Gli amidi possono provenire da svariate specie vegetali, quali grano, mais, patata, riso, etc. Le cellulose possono provenire da svariati organismi vegetali, quali cotone, lino, canapa, pino, paglia, etc. Plant solids include starches and / or cellulose. Starches can come from various plant species, such as wheat, corn, potato, rice, etc. Cellulose can come from various plant organisms, such as cotton, linen, hemp, pine, straw, etc.
I prodotti solidi vegetali possono essere in polveri o in fibre ed hanno una concentrazione che varia dallo 1% al 40%, preferibilmente tra 2% e 30% rispetto al compound finale. The vegetable solids can be in powders or fibers and have a concentration ranging from 1% to 40%, preferably between 2% and 30% with respect to the final compound.
Ulteriori caratteristiche dell’invenzione appariranno più chiare dalla descrizione di alcuni esempi che segue, fatta a titolo puramente esemplificativo e quindi non limitativo. Further features of the invention will become clearer from the description of some examples that follows, given purely by way of example and therefore not limiting.
ESEMPIO 1 EXAMPLE 1
Nella tabella sottostante vengono riportate le quantità di materiali utilizzate per produrre un primo Compound. The table below shows the quantities of materials used to produce a first Compound.
Tabella 1 Table 1
I materiali di tabella 1 sono stati miscelati ed estrusi. Il prodotto estruso è stato stampato in modo da ottenere dei provini che sono stati testatati. Il risultato dei test è riportato in Tabella 2. The materials of table 1 were mixed and extruded. The extruded product was molded in order to obtain specimens which were tested. The result of the tests is reported in Table 2.
Tabella 2 Table 2
ESEMPIO 2 EXAMPLE 2
Nella tabella sottostante vengono riportate le quantità di materiali utilizzate per produrre un secondo Compound. The table below shows the quantities of materials used to produce a second Compound.
Tabella 3 Table 3
I materiali di tabella 3 sono stati miscelati ed estrusi. Il prodotto estruso è stato stampato in modo da ottenere dei provini che sono stati testatati. Il risultato dei test è riportato in tabella 4. The materials of table 3 were mixed and extruded. The extruded product was molded in order to obtain specimens which were tested. The result of the tests is shown in table 4.
Tabella 4 Table 4
Nelle Tabelle 1 e 3: In Tables 1 and 3:
SOL T161 è un SBS radiale Prodotto dalla Polimeri Europa; e SOL T161 is a radial SBS produced by Polimeri Europa; And
FG-1901X è un SEB(ma)S con il 2% di Anidride Maleica prodotto dalla ditta Kraton. FG-1901X is a SEB (ma) S with 2% Maleic Anhydride produced by the company Kraton.
Le metodiche utilizzate nei test sono riportate nella tabella sottostante: The methods used in the tests are shown in the table below:
Tabella 5 Table 5
Paragonando i risultati di questi compounds, che utilizzano olio vegetale e cariche organiche di natura poli-idrati di carbonio, anche conosciuti come polisaccaridi (amidi e cellulose), con i corrispondenti prodotti ottenuti sostituendo l’olio vegetale con il plastificante minerale (olio parafinico e/o naftenico) e le cariche organiche polimeriche con le tradizionali cariche minerali (Calcio carbonato, Caolini, etc.), si ottengono risultati similari per quanto riguarda le caratteristiche fisiche. By comparing the results of these compounds, which use vegetable oil and organic fillers of the nature of carbon polyhydrates, also known as polysaccharides (starches and cellulose), with the corresponding products obtained by replacing the vegetable oil with the mineral plasticizer (parafinic oil and / or naphthenic) and the polymeric organic fillers with the traditional mineral fillers (Calcium carbonate, Kaolins, etc.), similar results are obtained as regards the physical characteristics.
La grande differenza di comportamento la si rileva nelle prove di biodegradabilità, dove il compound tradizionale non mostra segni evidenti di aggressione ne di batteri ne di funghi nell’arco di decenni, mentre il compound avente olio vegetale come plastificante mostra già evidenti segni di attacco a partire dal primo decennio. The great difference in behavior can be seen in the biodegradability tests, where the traditional compound does not show evident signs of aggression of bacteria or fungi over decades, while the compound having vegetable oil as plasticizer already shows evident signs of attack to starting from the first decade.
L’assenza di degradazione la si riscontra solo se il prodotto viene utilizzato in ambienti non molto umidi e caldi, in quanto temperatura e umidità sono i fattori principali che accellerano o ritardano il fenomeno biodegradativo. The absence of degradation is found only if the product is used in not very humid and hot environments, as temperature and humidity are the main factors that accelerate or delay the biodegradation phenomenon.
L’aggiunta ulteriore di prodotti vegetali, quali amidi o cellulose, al compound additivato con olio vegetale, accelera sensibilmente la velocità del processo aggressivo ambientale sul materiale, anticipandone sensibilmente la sua degradazione nel tempo. The further addition of vegetable products, such as starch or cellulose, to the compound with vegetable oil additives, significantly accelerates the speed of the aggressive environmental process on the material, significantly anticipating its degradation over time.
Alle presenti forme di realizzazione dell’invenzione possono essere apportate numerose variazioni e modifiche di dettaglio, alla portata di un tecnico del ramo, rientranti comunque entro l’ambito dell’invenzione espresso dalle rivendicazioni annesse. Numerous variations and detailed modifications can be made to the present embodiments of the invention, within the reach of a person skilled in the art, however falling within the scope of the invention expressed by the attached claims.
Claims (10)
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| ITMC20080116 ITMC20080116A1 (en) | 2008-06-17 | 2008-06-17 | THERMOPLASTIC ELASTOMERS WITH HIGH ENVIRONMENTAL COMPATIBILITY AND BIODEGRADABILITY. |
| PCT/EP2008/063037 WO2009152870A1 (en) | 2008-06-17 | 2008-09-29 | Thermoplastic elastomers with high environmental compatibility and biodegradability properties |
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| IT1399468B1 (en) | 2010-04-16 | 2013-04-19 | Tecnofilm Spa | BIODEGRADABLE POLYMERS AND COMPOUNDS. |
| EP2602282B1 (en) * | 2011-12-05 | 2014-10-29 | Mondi Gronau GmbH | Elastic film for the nappy area |
| US20140100311A1 (en) | 2012-10-08 | 2014-04-10 | Cerestech, Inc. | Thermoplastic elastomer compositions having biorenewable content |
| EP2904045B1 (en) | 2012-10-08 | 2018-09-19 | Teknor Apex Company | Thermoplastic elastomer compositions having biorenewable content |
| EP2759572A1 (en) | 2013-01-23 | 2014-07-30 | Teknor Apex Company | Thermoplastic elastomer compositions having biorenewable content |
| CN109912918A (en) * | 2019-02-26 | 2019-06-21 | 嘉兴市捷豪清洁用品有限公司 | A kind of modified thermoplastic rubber synthesising biological composite material and preparation method thereof |
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