ITBO20090241A1 - THERMOPLASTIC POLYURETHANE SOFT AND TRANSPARENT POLIETER, WITH HIGH ABRASION RESISTANCE, AND RELATIVE PREPARATION PROCESS. - Google Patents
THERMOPLASTIC POLYURETHANE SOFT AND TRANSPARENT POLIETER, WITH HIGH ABRASION RESISTANCE, AND RELATIVE PREPARATION PROCESS. Download PDFInfo
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- ITBO20090241A1 ITBO20090241A1 IT000241A ITBO20090241A ITBO20090241A1 IT BO20090241 A1 ITBO20090241 A1 IT BO20090241A1 IT 000241 A IT000241 A IT 000241A IT BO20090241 A ITBO20090241 A IT BO20090241A IT BO20090241 A1 ITBO20090241 A1 IT BO20090241A1
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- Italy
- Prior art keywords
- thermoplastic polyurethane
- tpu
- butene
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- percentage
- Prior art date
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- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims description 61
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims description 58
- 238000002360 preparation method Methods 0.000 title claims description 13
- 238000005299 abrasion Methods 0.000 title claims description 7
- 229920005862 polyol Polymers 0.000 claims description 23
- 150000003077 polyols Chemical class 0.000 claims description 22
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 125000005442 diisocyanate group Chemical group 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 10
- -1 aliphatic glycols Chemical class 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000005062 Polybutadiene Substances 0.000 claims description 8
- 239000004014 plasticizer Substances 0.000 claims description 8
- 229920002857 polybutadiene Polymers 0.000 claims description 8
- 239000004970 Chain extender Substances 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 5
- 150000002334 glycols Chemical class 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 3
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 claims description 3
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 5
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- NNIPDXPTJYIMKW-UHFFFAOYSA-N iron tin Chemical compound [Fe].[Sn] NNIPDXPTJYIMKW-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 238000003856 thermoforming Methods 0.000 claims 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 229940117927 ethylene oxide Drugs 0.000 description 4
- 235000019589 hardness Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- CWRORZJYSUFYHO-UHFFFAOYSA-N (3z)-3-diazobicyclo[2.2.2]octane Chemical compound C1CC2C(=[N+]=[N-])CC1CC2 CWRORZJYSUFYHO-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- KYIMHWNKQXQBDG-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCC Chemical compound N=C=O.N=C=O.CCCCCC KYIMHWNKQXQBDG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- DUFKCOQISQKSAV-UHFFFAOYSA-N Polypropylene glycol (m w 1,200-3,000) Chemical compound CC(O)COC(C)CO DUFKCOQISQKSAV-UHFFFAOYSA-N 0.000 description 1
- 229920013701 VORANOL™ Polymers 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 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 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical class OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0895—Manufacture of polymers by continuous processes
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- 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)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
DESCRIZIONE DESCRIPTION
annessa a domanda di brevetto per INVENZIONE INDUSTRIALE avente per titolo attached to a patent application for INDUSTRIAL INVENTION having the title
POLIURETANO TERMOPLASTICO POLIETERE MORBIDO E TRASPARENTE, CON ELEVATA RESISTENZA ALL'ABRA-SIONE, E RELATIVO PROCESSO DI PREPARAZIONE. THERMOPLASTIC POLYURETHANE SOFT AND TRANSPARENT POLYETHER, WITH HIGH RESISTANCE TO ABRA-SION, AND RELATED PREPARATION PROCESS.
Il presente trovato concerne un poliuretano termoplastico ed un relativo processo di preparazione impiegato per ottenerlo. The present invention relates to a thermoplastic polyurethane and a relative preparation process used to obtain it.
Il poliuretano termoplastico (TPU) è un elastomero industrialmente conosciuto, e attualmente utilizzato per una lunga serie di applicazioni. Il successo di questo materiale è dovuto alle elevate caratteristiche meccaniche unite alla sua lavorabilità come materiale termoplastico, e quindi, per semplice iniezione od estrusione. Thermoplastic polyurethane (TPU) is an industrially known elastomer, and currently used for a long series of applications. The success of this material is due to the high mechanical characteristics combined with its workability as a thermoplastic material, and therefore, by simple injection or extrusion.
Il poliuretano termoplastico TPU viene sintetizzato essenzialmente partendo da resine idrossiterminate (polioli) del tipo, ad esempio, di resine poliestere o polietere, da diisocianati organici e da dioli a corta catena (estensori di catena). TPU thermoplastic polyurethane is essentially synthesized starting from hydroxy-terminated resins (polyols) such as, for example, polyester or polyether resins, organic diisocyanates and short-chain diols (chain extenders).
Possono poi essere utilizzati una lunga serie di additivi utili a perfezionare il prodotto. A long series of additives can then be used to perfect the product.
Il processo industriale di preparazione normalmente usato è quello della cosiddetta "estrusione reattiva", secondo il quale i componenti vengono aggiunti nella bocca di un estrusore (normalmente un bivite corotante), all'interno del quale avviene poi la reazione chimica di allungamento . The industrial preparation process normally used is that of the so-called "reactive extrusion", according to which the components are added in the mouth of an extruder (normally a co-rotating twin screw), within which the chemical elongation reaction then takes place.
L'aggiunta dei componenti può essere fatta: con il metodo cosiddetto del "prepolimero" in cui 1'isocianato viene fatto più o meno reagire con il poliolo prima del suo inserimento nell'estrusore; oppure con il metodo denominato "one shot" in cui tutti i componenti vengono aggiunti nell'estrusore senza effettuare alcuna "prereazione". The addition of the components can be carried out: with the so-called "prepolymer" method in which the isocyanate is made to react more or less with the polyol before its insertion into the extruder; or with the method called "one shot" in which all the components are added to the extruder without performing any "pre-reaction".
Buona parte delle caratteristiche di base del TPU dipendono dal tipo di poliolo lineare scelto per la preparazione, ed esiste una lunga serie di polioli che sono applicati industrialmente allo scopo. Much of the basic characteristics of TPU depend on the type of linear polyol chosen for the preparation, and there is a long series of polyols that are industrially applied for the purpose.
Ad esempio, poliuretani termoplastici aventi elevate proprietà meccaniche e resistenza agli oli, vengono preparati da dioli poliestere, come ad esempio quelli ottenuti per condensazione di acido adipico e glicoli tipo l' 1-4 butandiolo. For example, thermoplastic polyurethanes having high mechanical properties and resistance to oils, are prepared from polyester diols, such as those obtained by condensation of adipic acid and glycols such as 1-4 butanediol.
Poliuretani termoplastici di questo tipo sono ampiamente utilizzati, ma soffrono molto della loro scarsa resistenza all'idrolisi e svantaggiosamente non possono essere utilizzati in applicazioni destinate ad impiego all'esterno o a contatto con acqua. Thermoplastic polyurethanes of this type are widely used, but suffer greatly from their poor resistance to hydrolysis and disadvantageously they cannot be used in applications intended for outdoor use or in contact with water.
Poliuretani termoplastici aventi invece elevata resistenza all'idrolisi e bassa densità, vengono invece preparati da polioli tipo polietere, che in questo caso, normalmente, possono essere di due tipi: il PTMG (politetrametilen glicole) e dei PPG/PEG (polipropilenglicoli/polietilenglicoli) . Thermoplastic polyurethanes with high resistance to hydrolysis and low density, on the other hand, are prepared from polyether-like polyols, which in this case can normally be of two types: PTMG (polytetramethylene glycol) and PPG / PEG (polypropylene glycols / polyethylene glycols) .
Nel primo caso (PTMG) industrialmente si producono poliuretani (TPU) in modo relativamente agevole e si riesce a mantenere per essi caratteristiche meccaniche ottimali, simili agli esteri. In the first case (PTMG) polyurethanes (TPU) are produced industrially in a relatively easy way and it is possible to maintain optimal mechanical characteristics for them, similar to esters.
I polioli PPG/PEG vengono ottenuti per polimerizzazione di ossido di etilene (EO) e di ossido di propilene(PO) e vengono utilizzati in moltissime applicazioni compreso il poliuretano (raramente nel termoplastico, TPU). PPG / PEG polyols are obtained by polymerization of ethylene oxide (EO) and propylene oxide (PO) and are used in many applications including polyurethane (rarely in thermoplastic, TPU).
Esiste una vasta gamma di polioli di questo tipo, prodotti con varie modalità di preparazione, che essenzialmente si distinguono tra loro per la diversa percentuale media di etilen-ossido nella catena e per la funzionalità dei gruppi ossidrili terminali della catena, che possono essere o meno di tipo "primario". I polioli da EO/PO sono facilmente reperibili e ad un costo relativamente contenuto e pertanto molto interesse è stato rivolto negli anni a questo tipo di materiale. I TPU ottenuti da polioli EO/PO tuttavia presentano numerosi svantaggi, i principali dei quali sono rappresentati da scarse caratteristiche meccaniche e in particolare da una bassa resistenza all'abrasione. Ulteriori svantaggi posseduti da tali materiali sono rappresentati dal fatto: di essere molto sensibili alle alte temperature e di implicare fasi di preparazione e trasformazione sempre molto difficoltose. There is a wide range of polyols of this type, produced with various methods of preparation, which essentially differ from each other for the different average percentage of ethylene-oxide in the chain and for the functionality of the terminal hydroxyl groups of the chain, which may or may not be of "primary" type. Polyols from EO / PO are readily available and at a relatively low cost and therefore much interest has been directed over the years to this type of material. TPUs obtained from EO / PO polyols, however, have numerous disadvantages, the main of which are represented by poor mechanical characteristics and in particular by a low resistance to abrasion. Further disadvantages of these materials are represented by the fact: they are very sensitive to high temperatures and involve always very difficult stages of preparation and transformation.
Inoltre, i manufatti ottenuti con tali tipi di TPU sono notevolmente opachi alla luce. Questi problemi si evidenziamo maggiormente nei materiali più morbidi, ovvero aventi durezze inferiori a circa 80 Shore A. Furthermore, the products obtained with these types of TPU are remarkably opaque to light. These problems are more evident in softer materials, i.e. with hardnesses lower than about 80 Shore A.
Per ovviare a tali inconvenienti sono stati fatti molti tentativi, ma con scarsissime applicazioni industriali nel poliuretano termoplastico. Many attempts have been made to overcome these drawbacks, but with very few industrial applications in thermoplastic polyurethane.
Attualmente, nelle poche applicazioni in uso, i TPU sopraddetti vengono utilizzati in miscela con altri polioli (altri polieteri o poliesteri) in modo da ottenere dei TPU ibridi che possano avere delle caratteristiche in qualche modo soddisfacenti. Currently, in the few applications in use, the aforementioned TPUs are used in a mixture with other polyols (other polyethers or polyesters) in order to obtain hybrid TPUs which may have somehow satisfactory characteristics.
Ad oggi tuttavia il problema resta aperto. To date, however, the problem remains open.
Scopo del presente trovato è pertanto quello di ovviare a questi inconvenienti mediante la preparazione di un poliuretano termoplastico tipo polietere, formato da unità strutturali derivanti da polioli di ossido di etilene (EO) e polioli da ossido di propilene (PO), che superi gli inconvenienti della tecnica nota e che abbia caratteristiche specifiche di alto pregio funzionale ed estetico, ripetibili con carattere costante, e non altrimenti raggiungibili da analoghi poliuretani termoplastici (TPU) viceversa prodotti con modalità convenzionali. The purpose of the present invention is therefore to obviate these drawbacks by preparing a polyether-like thermoplastic polyurethane, formed by structural units deriving from polyols of ethylene oxide (EO) and polyols from propylene oxide (PO), which overcomes the drawbacks of the known art and which has specific characteristics of high functional and aesthetic value, repeatable with a constant character, and not otherwise achievable by similar thermoplastic polyurethanes (TPU), vice versa produced with conventional methods.
Le caratteristiche tecniche del trovato, secondo i suddetti scopi, sono chiaramente riscontrabili dal contenuto delle rivendicazioni sotto riportate, ed i vantaggi dello stesso risulteranno maggiormente evidenti nella descrizione dettagliata che segue. The technical characteristics of the invention, according to the aforementioned purposes, can be clearly seen from the content of the claims reported below, and the advantages thereof will become more evident in the detailed description that follows.
La presente invenzione concerne un poliuretano termoplastico (TPU) che viene prodotto per estrusione reattiva di: The present invention relates to a thermoplastic polyurethane (TPU) which is produced by reactive extrusion of:
a) un poliolo o una miscela di polioli polietere da ossido di etilene (EO) e/o da ossido di propilene (PO) aventi peso molecolare medio da 500 a 6000 Dalton. I singoli polioli della miscela possono essere basati completamente su PO, oppure da PO cappato EO, oppure su copolimeri di EO e PO. I poliolo o la miscela devono avere una percentuale media di unità EO tra il 3 e il 60% (preferibilmente tra il 5 e il 30%) e una percentuale media di ossidrili primari tra il 20 e il 90% (preferibilmente tra il 30 e il 60%). a) a polyol or a mixture of polyether polyols from ethylene oxide (EO) and / or propylene oxide (PO) having an average molecular weight from 500 to 6000 Dalton. The single polyols of the mixture can be based completely on PO, or on PO capped EO, or on copolymers of EO and PO. The polyols or the mixture must have an average percentage of EO units between 3 and 60% (preferably between 5 and 30%) and an average percentage of primary hydroxyls between 20 and 90% (preferably between 30 and 60%).
b) un diisocianato o una miscela di diisocianati. Possono essere usati diisocianati alifatici o aromatici. I diisocianati sono commercialmente disponibili e comprendono: 4-4' diisocianato difenil metano (MDI); toluene 2-4 diisocianato (TDI); toluene 2-6 diisocianato (TDI); metilene bis (4 cicloesilisocianato) (H12 MDI); 3- isocianato metil-3,5,5-trimetil cicloesil isocianato (IPDI); 1,6 esano diisocianato (HDI); naftalene 1-5 diisocianato (NDI); isoforone diisocianato. Il diisocianato preferito è il 4-41 diisocianato difenil metano (MDI). b) a diisocyanate or a mixture of diisocyanates. Aliphatic or aromatic diisocyanates can be used. Diisocyanates are commercially available and include: 4-4 'diisocyanate diphenyl methane (MDI); toluene 2-4 diisocyanate (TDI); toluene 2-6 diisocyanate (TDI); methylene bis (4 cyclohexylisocyanate) (H12 MDI); 3- isocyanate methyl-3,5,5-trimethyl cyclohexyl isocyanate (IPDI); 1.6 hexane diisocyanate (HDI); naphthalene 1-5 diisocyanate (NDI); isophorone diisocyanate. The preferred diisocyanate is 4-41 diisocyanate diphenyl methane (MDI).
c) un allungatore di catena o una miscela di allungatori di catena. Come "allungatore" possono essere usati glicoli o diammine aventi peso molecolare inferiore a 400 Dalton, di tipo alifatico o aromatico. Preferiti ai fini della presente invenzione sono glicoli aventi da 2 a 6 atomi di carbonio, come ad esempio l'etandiolo, 1,3 butandiolo, 1,6 esandiolo, 1,5 pentandiolo o anche glicoli di alchil etere quali il dietilenglicole o il dipropilen glicole. c) a chain extender or a mixture of chain extenders. Glycols or diamines having a molecular weight lower than 400 Dalton, of the aliphatic or aromatic type, can be used as "extender". Preferred for the purposes of the present invention are glycols having from 2 to 6 carbon atoms, such as ethanediol, 1.3 butanediol, 1.6 hexanediol, 1.5 pentanediol or even alkyl ether glycols such as diethylene glycol or dipropylene glycol.
Con aggiunta di: With the addition of:
d) un polibutadiene liquido capace di rendere ottimale la resistenza all'abrasione, in una percentuale compresa tra lo 0,1 e il 10%, avente peso molecolare compreso tra 1000 e 10000 e comprendente unità 1,2-butene, 2,3-trans butene e 2,3-cis butene. Preferibilmente il suddetto polibutadiene viene utilizzato in una percentuale compresa tra lo 1 e il 46%, e la percentuale di 1,2 butene è inferiore al 50%, e il contenuto di 2,3-cis butene è maggiore del 2,3-trans butene. d) a liquid polybutadiene capable of optimizing abrasion resistance, in a percentage between 0.1 and 10%, having a molecular weight between 1000 and 10000 and comprising 1,2-butene, 2,3- trans butene and 2,3-cis butene. Preferably the aforesaid polybutadiene is used in a percentage ranging from 1 to 46%, and the percentage of 1.2 butene is less than 50%, and the content of 2,3-cis butene is greater than 2,3-trans butene.
Preferibilmente la estrusione reattiva viene condotta con il metodo del prepolimero, ovvero con un sistema in cui i componenti a) e b) vengono aggiunti in un reattore di "prepolimerizzazione" continuo o discontinuo, all'interno del quale gli ossidrili del componente a) vengano fatti reagire con il diisocianato fino ad una conversione superiore al 80%. Il componente c) viene aggiunto nell'estrusore, in una fase successiva a quella di prepolimerizzazione. Preferably the reactive extrusion is carried out with the prepolymer method, i.e. with a system in which components a) and b) are added in a continuous or discontinuous "prepolymerization" reactor, inside which the hydroxyls of component a) are made react with the diisocyanate up to a conversion higher than 80%. Component c) is added to the extruder, in a step subsequent to the prepolymerization step.
Il componente d) può essere aggiunto in una qualsiasi fase della preparazione del poliuretano termoplastico oggetto della presente invenzione o, in alternativa, in una successiva fase di "riestrusione" del polimero precedentemente ottenuto senza l'aggiunta dell'additivo. Preferibilmente il componente d) viene aggiunto durante la fase di preparazione del TPU, in un punto qualsiasi dell'estrusore o nel reattore di prepolimerizzazione. Per diminuire la durezza del poliuretano termoplastico e per migliorarne la lavorabilità, si possono, o meno, usare dei plastificanti o miscele di detti plastificanti. Idonei possono essere i plastificanti disponibili commercialmente come ad esempio i fosfati, gli ftalati, i dibenzoati, gli adipati, i sebacati, ecc. Il plastificante può essere aggiunto in una qualsiasi fase della preparazione del poliuretano termoplastico oggetto della presente invenzione o, in alternativa, in una successiva fase di "riestrusione" del polimero precedentemente ottenuto senza l'aggiunta dell'additivo. Ai fini della presente invenzione è preferibile l'aggiunta di una percentuale compresa tra il 5% e il 30% di un plastificante tipo DPG (dipropilen glicole dibenzoato), fatta durante la fase di estrusione reattiva del TPU, in un punto qualsiasi dell'estrusore o nel reattore di prepolimerizzazione. Component d) can be added in any step of the preparation of the thermoplastic polyurethane object of the present invention or, alternatively, in a subsequent "re-extrusion" step of the polymer previously obtained without adding the additive. Preferably the component d) is added during the TPU preparation step, at any point of the extruder or in the prepolymerization reactor. To decrease the hardness of the thermoplastic polyurethane and to improve its workability, it is possible, or not, to use plasticizers or mixtures of said plasticizers. Suitable are commercially available plasticizers such as phosphates, phthalates, dibenzoates, adipates, sebacates, etc. The plasticizer can be added in any step of the preparation of the thermoplastic polyurethane object of the present invention or, alternatively, in a subsequent "re-extrusion" step of the polymer previously obtained without adding the additive. For the purposes of the present invention it is preferable to add a percentage between 5% and 30% of a plasticizer such as DPG (dipropylene glycol dibenzoate), made during the reactive extrusion step of the TPU, at any point of the extruder. or in the prepolymerization reactor.
I componenti di reazione, opzionalmente in presenza di catalizzatori, sostanze ausiliari e/o additivi, vengono fatti reagire in quantità tali che il rapporto equivalente tra gruppi isocianato e la somma dei gruppi reattivi con 1'isocianato sia compresa tra lo 0,95:1 e 1,10:1. The reaction components, optionally in the presence of catalysts, auxiliary substances and / or additives, are reacted in such quantities that the equivalent ratio between isocyanate groups and the sum of the reactive groups with the isocyanate is between 0.95: 1 and 1.10: 1.
Catalizzatori idonei sono quelli capaci dì accelerare la reazione chimica dei gruppi isocianato: sono comprese le ammine terziarie tra cui la trietilammina, il diazobiciclo- (2,2,2)-ottano e simili, così come sono compresi i composti metallo organici del titanio, del ferro, dello stagno, o ancora i sali di stagno dialchilici con acidi carbossilici alitatici. Suitable catalysts are those capable of accelerating the chemical reaction of isocyanate groups: including tertiary amines including triethylamine, diazobicyclo- (2,2,2) -octane and the like, as well as the organic metal compounds of titanium, iron, tin, or dialkyl tin salts with alitatic carboxylic acids.
Oltre ai catalizzatori possono anche essere aggiunte sostanze ausiliarie o additivi, quali ad esempio: lubrificanti, stabilizzatori all'idrolisi, alla luce e al calore, agenti antifiamma, coloranti, riempitivi, rinforzanti, ecc. In addition to the catalysts, auxiliary substances or additives can also be added, such as for example: lubricants, hydrolysis, light and heat stabilizers, flame retardants, dyes, fillers, reinforcers, etc.
In ulteriore aggiunta possono essere incorporati altri polimeri termoplastici, come ad esempio i policarbonati, ABS (acrilonitrile butadiene stirene copolimero), SAN, SBS (stirene butadiene stirene copolimero), ÈVA , ecc. In further addition, other thermoplastic polymers can be incorporated, such as for example polycarbonates, ABS (acrylonitrile butadiene styrene copolymer), SAN, SBS (styrene butadiene styrene copolymer), ÈVA, etc.
Il TPU della presente invenzione può essere utilizzato per l'ottenimento di manufatti o prodotti secondo le normali tecniche di trasformazione. Può essere quindi lavorato per stampaggio ad iniezione, estrusione, stampaggio a compressione, ecc. The TPU of the present invention can be used to obtain manufactured articles or products according to normal transformation techniques. It can then be processed by injection molding, extrusion, compression molding, etc.
Sorprendentemente è stata scoperta la possibilità di avere un TPU trasparente con durezza inferiore a 75 Shore A, resistente allo scivolamento e avente resistenza all'abrasione (secondo norma DIN 53516 o ISO 4649) inferiore a 100 mm3, con un densità tipica del polietere (inferiore a 1,15 gr/cm3), tale poliuretano termoplastico (TPU) essendo trasformabile con le normali tecniche utilizzate per il poliuretano termoplastico convenzionale . Surprisingly it was discovered the possibility of having a transparent TPU with a hardness lower than 75 Shore A, slip resistant and with abrasion resistance (according to DIN 53516 or ISO 4649) lower than 100 mm3, with a typical density of polyether (lower at 1.15 gr / cm3), this thermoplastic polyurethane (TPU) being transformable with the normal techniques used for conventional thermoplastic polyurethane.
Un ESEMPIO di preparazione del prodotto e del relativo procedimento è il seguente. An EXAMPLE of preparation of the product and of the relative procedure is the following.
In un reattore viene preparato un prepolimero con la seguente composizione: MDI (Isonate 125M prodotto da Dow) 30%, Poliol 1 (Voranol P1010 da Dow) 35%, Poliol 2 (Voranol EP1900 da Dow) 35%. A prepolymer is prepared in a reactor with the following composition: MDI (Isonate 125M produced by Dow) 30%, Polyol 1 (Voranol P1010 by Dow) 35%, Polyol 2 (Voranol EP1900 by Dow) 35%.
Il prepolimero così ottenuto tramite un processo in continuo, viene premiscelato con un preparato comprendente 1-4 Butandiolo 99% e di diazobiclo-(2,2,2)-ottano 1%. La miscela viene colata in continuo all'interno in un estrusore bivite corotante. Le portate dei due componenti vengono regolate in modo tale che il rapporto stechiometrico isocianato/ossidrile (NCO/OH)sia di 1,02. Le temperature dell'estrusore vengono mantenute tra 150 e 180°C. Durante l'estrusione viene aggiunto del polibutadiene liquido con una portata tale da avere una percentuale del 3% sul totale. Alla fine dell'estrusore, il polimero fuso viene tagliato in granuli con idoneo sistema. The prepolymer thus obtained through a continuous process is premixed with a preparation comprising 1-4 Butanediol 99% and diazobyclo- (2,2,2) -octane 1%. The mixture is continuously poured into a co-rotating twin-screw extruder. The flow rates of the two components are adjusted in such a way that the stoichiometric isocyanate / hydroxyl (NCO / OH) ratio is 1.02. The temperatures of the extruder are maintained between 150 and 180 ° C. During the extrusion liquid polybutadiene is added with a flow rate such as to have a percentage of 3% of the total. At the end of the extruder, the melted polymer is cut into granules with a suitable system.
Dopo l'essiccazione, utilizzando una normale macchina di stampaggio ad iniezione, i granuli vengono fusi (temperature di parete di 190-210°C) iniettati all'interno di uno stampo campione. Dopo 60 secondi il pezzo viene rimosso dallo stampo e viene caratterizzato con i risultati di seguito indicati: After drying, using a normal injection molding machine, the granules are melted (wall temperatures of 190-210 ° C) injected into a sample mold. After 60 seconds the piece is removed from the mold and is characterized with the following results:
Densità: 1,08 g/cc Density: 1.08 g / cc
Durezza: 65 Shore A Hardness: 65 Shore A
Carico di rottura: 14 Mpa Breaking load: 14 Mpa
Allungamento a rottura: 700% Elongation at break: 700%
Resistenza a lacerazione: 55 N/mm Tear strength: 55 N / mm
Abrasione (DIN 53516): 80 mm<3>Abrasion (DIN 53516): 80 mm <3>
Il trovato così concepito è suscettibile di evidente applicazione industriale; può essere altresì oggetto di numerose modifiche e varianti tutte rientranti nell'ambito del concetto inventivo; tutti i dettagli possono essere sostituiti, inoltre, da elementi tecnicamente equivalenti. The invention thus conceived is susceptible of evident industrial application; it can also be subject to numerous modifications and variations, all of which are within the scope of the inventive concept; all the details can also be replaced by technically equivalent elements.
Claims (24)
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| Application Number | Priority Date | Filing Date | Title |
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| IT000241A ITBO20090241A1 (en) | 2009-04-15 | 2009-04-15 | THERMOPLASTIC POLYURETHANE SOFT AND TRANSPARENT POLIETER, WITH HIGH ABRASION RESISTANCE, AND RELATIVE PREPARATION PROCESS. |
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| IT000241A ITBO20090241A1 (en) | 2009-04-15 | 2009-04-15 | THERMOPLASTIC POLYURETHANE SOFT AND TRANSPARENT POLIETER, WITH HIGH ABRASION RESISTANCE, AND RELATIVE PREPARATION PROCESS. |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3983094A (en) * | 1975-09-11 | 1976-09-28 | Uniroyal, Inc. | Thermally stable polyurethane elastomers produced from poly(oxypropylene)-poly(oxyethylene)glycols of high oxyethylene group content |
| EP0118171A2 (en) * | 1983-03-04 | 1984-09-12 | Arco Chemical Technology, Inc. | Production of polyurethane-forming components having free-isocyanate or hydroxy groups |
| US5510054A (en) * | 1995-06-29 | 1996-04-23 | Dow Italia S.P.A. | Polyurethane elastomer and foam exhibiting improved abrasion resistance |
| WO2009017868A1 (en) * | 2007-07-27 | 2009-02-05 | Dow Global Technologies Inc. | Compositions of thermoplastic polyurethane (tpu), polybutadiene and polydiene-based tpu |
-
2009
- 2009-04-15 IT IT000241A patent/ITBO20090241A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3983094A (en) * | 1975-09-11 | 1976-09-28 | Uniroyal, Inc. | Thermally stable polyurethane elastomers produced from poly(oxypropylene)-poly(oxyethylene)glycols of high oxyethylene group content |
| EP0118171A2 (en) * | 1983-03-04 | 1984-09-12 | Arco Chemical Technology, Inc. | Production of polyurethane-forming components having free-isocyanate or hydroxy groups |
| US5510054A (en) * | 1995-06-29 | 1996-04-23 | Dow Italia S.P.A. | Polyurethane elastomer and foam exhibiting improved abrasion resistance |
| WO2009017868A1 (en) * | 2007-07-27 | 2009-02-05 | Dow Global Technologies Inc. | Compositions of thermoplastic polyurethane (tpu), polybutadiene and polydiene-based tpu |
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