ITSA990005A1 - PROPYLENE-BASED COPOLYMERS CONTAINING STYRENE UNITS - Google Patents
PROPYLENE-BASED COPOLYMERS CONTAINING STYRENE UNITSInfo
- Publication number
- ITSA990005A1 ITSA990005A1 IT1999SA000005A ITSA990005A ITSA990005A1 IT SA990005 A1 ITSA990005 A1 IT SA990005A1 IT 1999SA000005 A IT1999SA000005 A IT 1999SA000005A IT SA990005 A ITSA990005 A IT SA990005A IT SA990005 A1 ITSA990005 A1 IT SA990005A1
- Authority
- IT
- Italy
- Prior art keywords
- atom
- copolymers
- propylene
- units
- styrene
- Prior art date
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims description 35
- 229920001577 copolymer Polymers 0.000 title claims description 20
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 22
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 15
- 239000005977 Ethylene Substances 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 150000003440 styrenes Chemical class 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000003780 insertion Methods 0.000 claims description 3
- 230000037431 insertion Effects 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 125000004437 phosphorous atom Chemical group 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000002685 polymerization catalyst Substances 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- -1 polypropylene Polymers 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920006301 statistical copolymer Polymers 0.000 description 4
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910007928 ZrCl2 Inorganic materials 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229920001580 isotactic polymer Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Description
DESCRIZIONE DESCRIPTION
a corredo di una domanda di brevetto per invenzione industriale dal titolo: accompanying a patent application for industrial invention entitled:
COPOLIMERI A BASE DI PROPILENE CONTENENTI UNITÀ STIRENICHE PROPYLENE-BASED COPOLYMERS CONTAINING STYRENE UNITS
L’invenzione presentata riguarda copolimeri statistici a base di propilene contenenti unità stireniche. The invention presented concerns propylene-based statistical copolymers containing styrenic units.
E’ ben noto che le materie plastiche, a base di polipropilene isotattico sono tra le più interessanti da un punto di vista tecnologico. Infatti, esse non solo sono concorrenziali da un punto di vista economico, ma sono anche adattabili alle più svariate applicazioni a seguito di opportune modifiche chimiche o fisiche. It is well known that plastics, based on isotactic polypropylene are among the most interesting from a technological point of view. In fact, they are not only competitive from an economic point of view, but are also adaptable to the most varied applications following appropriate chemical or physical modifications.
Il tipo di modifica chimica più comunemente utilizzato industrialmente è la copolimerizzazione statistica con piccole quantità di comonomero, generalmente etilene oppure butene, che consente di ottenere materiali che, rispetto al polipropilene isotattico, presentano una più bassa temperatura di fusione (sfruttata soprattutto per la realizzazione di strati termo-saldabili in film), una minore rigidità, una maggiore resistenza all’urto alle basse temperature ed una più elevata trasparenza. Tutte le sopra citate variazioni di proprietà fìsiche rispetto al’omopolimero sono collegate con i più bassi gradi di cristallinità ed alle più ridotte dimensioni dei cristalliti associati alla presenza di unità comonomeriche. The type of chemical modification most commonly used industrially is the statistical copolymerization with small quantities of comonomer, generally ethylene or butene, which allows to obtain materials which, compared to isotactic polypropylene, have a lower melting temperature (mainly used for the production of heat-sealable film layers), lower stiffness, greater impact resistance at low temperatures and higher transparency. All the aforementioned variations in physical properties with respect to the homopolymer are related to the lower degrees of crystallinity and to the smaller dimensions of the crystallites associated with the presence of comonomer units.
Va notato che le unità etileniche e quelle buteniche presentano ingombri non molto differenti da quelle propileniche per cui, sebbene provochino una diminuzione dell’energia di impacchettamento, sono in parte incluse come difetti all’interno della fase cristallina. E’ ben noto che, in generale per materiali polimerici semicristallini, si ottiene una più efficiente diminuzione di cristallinità e di dimensioni dei cristalliti nel caso di unità comonomeriche di ingombro molto più elevato rispetto all’unità monomerica di base, cioè tali da dover essere necessariamente escluse dalla fase cristallina. It should be noted that the ethylene and butene units have dimensions that are not very different from the propylene ones so, although they cause a decrease in the packing energy, they are partly included as defects within the crystalline phase. It is well known that, in general for semi-crystalline polymeric materials, a more efficient decrease in crystallinity and crystallite size is obtained in the case of comonomer units having a much larger footprint than the basic monomer unit, i.e. such that they must necessarily be excluded from the crystalline phase.
A riguardo esiste tuttavia il problema che comonomeri ingombranti e di basso costo, quale ad esempio lo stirene, non sono facilmente copolimerizzabili con il propilene, in quanto in genere siti catalitici idonei per la polimerizzazione isotattica del propene non sono in grado di polimerizzare lo stirene e viceversa. Infatti, sistemi catalitici per la polimerizzazione di 1-alcheni a polimeri isotattici, quali ad esempio quelli a base di metalloceni e di metilallumossano, non sono in genere in grado di polimerizzare lo stirene. Anzi lo stirene tende ad agire come veleno per tali processi. Val la pena anche di notare che nel caso di catalizzatori eterogenei, tipicamente contenenti differenti tipi di siti catalitici, è possibile polimerizzare miscele dei due monomeri, ma si ottengono prevalentemente miscele dei due omopolimeri. In this regard, however, there is the problem that bulky and low-cost comonomers, such as styrene, are not easily copolymerizable with propylene, since generally suitable catalytic sites for the isotactic polymerization of propene are not able to polymerize styrene and vice versa. In fact, catalytic systems for the polymerization of 1-alkenes to isotactic polymers, such as for example those based on metallocenes and methylalumoxane, are generally unable to polymerize styrene. Indeed styrene tends to act as a poison for such processes. It is also worth noting that in the case of heterogeneous catalysts, typically containing different types of catalytic sites, it is possible to polymerize mixtures of the two monomers, but mainly mixtures of the two homopolymers are obtained.
Un altro inconveniente dei copolimeri statistici a base di propilene esistenti, ottenuti mediante catalizzatori eterogenei, è che la distribuzione delle unità comonomeriche non è omogenea tra le varie macromolecole, cosicché le frazioni con più elevato contenuto di comonomero sono facilmente estraibili con solventi. Ciò ovviamente costituisce un impedimento all’accettazione in applicazioni che prevedano contatto con cibi. Another drawback of existing propylene-based statistical copolymers, obtained by means of heterogeneous catalysts, is that the distribution of the comonomer units is not homogeneous among the various macromolecules, so that the fractions with a higher comonomer content are easily extractable with solvents. This obviously constitutes an impediment to acceptance in applications involving contact with food.
La presente invenzione riguarda nuovi copolimeri a base di polipropilene isotattico che presentano una distribuzione omogenea di unità strutturali del tipo: The present invention relates to new copolymers based on isotactic polypropylene which have a homogeneous distribution of structural units of the type:
dove R rappresenta un atomo dì idrogeno, un atomo di alogeno o un sostituente contenente atomi di carbonio, un atomo di ossigeno, un atomo di azoto, un atomo di zolfo, un atomo di fosforo o un atomo di silicio, ed n rappresenta un intero compreso tra 1 e 3. L’invenzione riguarda inoltre processi per l’ottenimento di tali copolimeri. where R represents a hydrogen atom, a halogen atom or a substituent containing carbon atoms, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom, and n represents an integer between 1 and 3. The invention also relates to processes for obtaining such copolymers.
L’invenzione si colloca nel campo tecnico-scientifico della chimica industriale, più in particolare nel settore della produzione dei materiali termoplastici. The invention is located in the technical-scientific field of industrial chemistry, more particularly in the sector of the production of thermoplastic materials.
DESCRIZIONE DETTAGLIATA DETAILED DESCRIPTION
Per l’ottenimento dei copolimeri descritti nel presente brevetto si possono utilizzare sistemi catalitici omogenei per la polimerizzazione per inserzione del propene, che portano ad omopolimero isotattico, quali To obtain the copolymers described in this patent, homogeneous catalytic systems can be used for the insertion polymerization of propene, which lead to isotactic homopolymer, such as
La copolimerizzazione di propilene e stirene viene condotta in presenza di piccole quantità di etilene. In particolare, la copolimerizzazione può essere condotta con concentrazioni di catalizzatori comprese tra 10<-8 >M e 10<'2 >M; di propilene tra 0.1 M e 7M; di stirene tra 10<-3>M e 9 M e concentrazione di etilene almeno dieci volte minore di quella del propilene; a temperature comprese nell’ intervallo -30°C ÷ 80°C. The copolymerization of propylene and styrene is carried out in the presence of small quantities of ethylene. In particular, the copolymerization can be carried out with catalyst concentrations ranging from 10 <-8> M and 10 <'2> M; of propylene between 0.1 M and 7M; of styrene between 10 <-3> M and 9 M and concentration of ethylene at least ten times lower than that of propylene; at temperatures between -30 ° C ÷ 80 ° C.
I copolimeri oggetto della presente invenzione sono caratterizzati dalla presenza di unità strutturali del tipo: The copolymers object of the present invention are characterized by the presence of structural units of the type:
quantificabili sulla base delle intensità di opportuni segnali in spettri di risonanza magnetica nucleare al <13>C. Ad esempio, nel caso di copolimeri del propene con lo stirene, tali unità strutturali sono evidenziate dalla presenza di segnali nella zona alifatica a 33.9 e 25.2 ppm (“chemical shifìs rispetto al tetrametilsilano, Figura 1) e la frazione molare di unità stireniche (Xs), pari alla frazione molare di unità etileniche connesse, può essere ottenuta mediante la relazione: quantifiable on the basis of the intensities of suitable signals in nuclear magnetic resonance spectra at <13> C. For example, in the case of copolymers of propene with styrene, these structural units are highlighted by the presence of signals in the aliphatic zone at 33.9 and 25.2 ppm ("chemical shifìs with respect to tetramethylsilane, Figure 1) and the molar fraction of styrene units (Xs ), equal to the molar fraction of connected ethylene units, can be obtained by means of the relation:
dove Ax sono intensità dei segnali presenti ad x ppm. where Ax are intensity of the signals present at x ppm.
La natura statistica del copolimero è testimoniata dalla non rilevabilità negli spettri <13>C NMR dei segnali a le 41 e 44 ÷ 46 ppm indicativi della presenza di blocchi polistirenici. The statistical nature of the copolymer is evidenced by the non-detectability in the <13> C NMR spectra of the signals at le 41 and 44 ÷ 46 ppm indicative of the presence of polystyrene blocks.
A seconda delle condizioni di polimerizzazione si ottengono copolimeri statistici di differenti composizioni e con gradi di polimerizzazione superiori a 10, in genere con masse molecolari medie in peso Mw comprese tra 3000 e 10<6>u.m.a. Depending on the polymerization conditions, statistical copolymers of different compositions and with polymerization degrees higher than 10 are obtained, generally with average molecular masses by weight Mw between 3000 and 10 <6> u.m.a.
E’ importante notare che eventuali copolimeri statistici del propilene con stirene o con stireni sostituiti, in assenza di unità etileniche associate, presenterebbero sostanziali aumenti della temperatura di transizione vetrosa (Tg) rispetto al'omopolimero approssimativamente regolati dalla relazione di Fox: It is important to note that any statistical copolymers of propylene with styrene or with substituted styrenes, in the absence of associated ethylene units, would show substantial increases in the glass transition temperature (Tg) compared to the homopolymer approximately regulated by the Fox relationship:
dove Wprop e Wstir sono le frazioni in peso dei due monomeri propilene e stirene (o stirene sostituito) e Tg prop e Tg stir sono le temperature di transizione vetrosa degli omopolimeri polipropilene e polistirene (o polistirene sostituito), rispettivamente. Dato che le temperature di transizione vetrosa dei polimeri stirenici sono molto più elevate di quella del polipropilene e le masse molecolari delle unità stireniche sono molto più elevate rispetto a quella dell’unità propilenica, si dovrebbero osservare anche sostanziali aumenti delle temperature di transizione vetrosa anche per bassi contenuti molari di unità stireniche, che renderebbero tali materiali inutilizzabili per applicazioni che prevedano basse temperature di esercizio. where Wprop and Wstir are the fractions by weight of the two monomers propylene and styrene (or substituted styrene) and Tg prop and Tg stir are the glass transition temperatures of the polypropylene and polystyrene (or substituted polystyrene) homopolymers, respectively. Since the glass transition temperatures of styrene polymers are much higher than that of polypropylene and the molecular masses of the styrene units are much higher than that of the propylene unit, substantial increases in glass transition temperatures should also be observed for low molar contents of styrene units, which would make these materials unsuitable for applications involving low operating temperatures.
Airopposto, i copolimeri oggetto della presente invenzione presentano una sostanziale invarianza della temperatura di transizione vetrosa rispetto al polipropilene isotattico. Ad esempio, nel caso di copolimeri contenenti unità stireniche ed etileniche associate, non si osservano incrementi della Tg rispetto al polipropilene isotattico superiori a 10 °C. Ad esempio, se la Tg viene misurata mediante calorimetria a scansione differenziale, condotta con una velocità di scansione di 10 K/min, il suo valore non supera 0°C. On the contrary, the copolymers object of the present invention show a substantial invariance of the glass transition temperature with respect to isotactic polypropylene. For example, in the case of copolymers containing associated styrene and ethylene units, no increases in Tg are observed with respect to isotactic polypropylene higher than 10 ° C. For example, if Tg is measured by differential scanning calorimetry, conducted with a scanning rate of 10 K / min, its value does not exceed 0 ° C.
I copolimeri ottenuti presentano inoltre una distribuzione omogenea dei comonomeri. La omogeneità di tale distribuzione è ad esempio evidenziata dal fatto che non è possibile separare i copolimeri ottenuti mediante estrazione con solventi in frazioni con valori di Xs che differiscono di piu’ del 30% rispetto al valore di Xs del campione non frazionato. The copolymers obtained also show a homogeneous distribution of the comonomers. The homogeneity of this distribution is highlighted, for example, by the fact that it is not possible to separate the copolymers obtained by extraction with solvents in fractions with values of Xs that differ by more than 30% compared to the value of Xs of the unfractionated sample.
A scopo illustrativo e non limitativo, vengono descritti di seguito tre esempi di processo e prodotto: For illustrative and non-limiting purposes, three process and product examples are described below:
Esempio 1 Example 1
In un pallone di vetro pyrex a tre colli da 100 mL termostatato a -25°C sono introdotti, in atmosfera d’azoto, nell’ordine: stirene (30 mL) e metilalumossano (MAO) (300 mg); rimosso l’azoto, la fase liquida viene saturata facendo gorgogliare a pressione atmosferica una miscela propilene/etilene (20/1 mol/mol), regolando il flusso a 0.3 L al minuto. In a 100 mL three-necked pyrex glass flask thermostated at -25 ° C, the following are introduced, in a nitrogen atmosphere, in order: styrene (30 mL) and methylalumoxane (MAO) (300 mg); removed the nitrogen, the liquid phase is saturated by bubbling a propylene / ethylene mixture (20/1 mol / mol) at atmospheric pressure, adjusting the flow to 0.3 L per minute.
Si fa partire la reazione iniettando nel pallone 3 mg di catalizzatore rac-Etilene-bis(1-indenil)ZrCl2 sciolti in 2 mL di toluene anidro. The reaction is started by injecting into the flask 3 mg of rac-Ethylene-bis (1-indenyl) ZrCl2 catalyst dissolved in 2 mL of anhydrous toluene.
Dopo 4 ore di reazione, il polimero prodotto e’ stato coagulato in 200 mL di etanolo acidificato con HC1, filtrato e seccato in stufa da vuoto. After 4 hours of reaction, the polymer produced was coagulated in 200 mL of ethanol acidified with HC1, filtered and dried in a vacuum oven.
La resa è di circa 120 mg. The yield is about 120 mg.
Dall’analisi <13>C NMR (figura 1) risulta che il polimero e’ composto dal 76% in moli di unita’ propileniche e dal 12% in moli di unita’ stireniche e 12% in moli di unita’ etileniche associate (Xs = 0.12). From the <13> C NMR analysis (figure 1) it results that the polymer is composed of 76% in moles of propylene units and 12% in moles of styrenic units and 12% in moles of associated ethylene units (Xs = 0.12).
Dall’analisi calorimetrica a scansione differenziale, condotta con una velocità di scansione di 10 K/min, risulta che il polimero è caratterizzato da una temperatura di fusione a 79°C (ΔHf = 10 J/g) e da una Tg≈ -9°C. From the differential scanning calorimetric analysis, carried out with a scanning speed of 10 K / min, it appears that the polymer is characterized by a melting temperature of 79 ° C (ΔHf = 10 J / g) and by a Tg≈ -9 ° C.
La massa molecolare media in peso misurata mediante cromatografia a permeazione di gel è di 3x 10<3 >u.m.a. The weight average molecular mass measured by gel permeation chromatography is 3x 10 <3> u.m.a.
Esempio 2 Example 2
11 sistema catalitico utilizzato, la procedura seguita e le condizioni di reazione sono identiche a quelle dell’esempio 1 fatta eccezione per le quantità di stirene (10 mL) e di toluene (20 mL) impiegate. The catalytic system used, the procedure followed and the reaction conditions are identical to those of example 1 except for the quantities of styrene (10 mL) and toluene (20 mL) used.
La resa e’ di circa 200 mg. The yield is about 200 mg.
Dall’analisi <13>C NMR risulta che il polimero e’ composto da 88% in moli di unita’ propileniche e dal 6 % in moli di unita’ stireniche RIVENDICAZIONI From the <13> C NMR analysis it appears that the polymer is composed of 88% by moles of propylene units and 6% by moles of styrenic units CLAIMS
1 Copolimeri a base di propilene con un contenuto molare di unità strutturali del tipo: 1 Copolymers based on propylene with a molar content of structural units of the type:
(dove R rappresenta un atomo di idrogeno, un atomo di alogeno o un sostituente contenente atomi di carbonio, un atomo di ossigeno, un atomo di azoto, un atomo di zolfo, un atomo di fosforo o un atomo di silicio, ed n rappresenta un intero compreso tra 1 e 3) compreso nell’intervallo 0.1-30%, e un grado di polimerizzazione non inferiore a 10. (where R represents a hydrogen atom, a halogen atom or a substituent containing carbon atoms, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom, and n represents a integer between 1 and 3) between 0.1-30%, and a degree of polymerization of not less than 10.
2. Copolimeri, come dalla rivendicazione 1, per cui le sequenze di unità propeniche sono prevalentemente isotattiche, con ammontare di diadi meso (m) superiore all’ 80%. 2. Copolymers, as per claim 1, for which the sequences of propenic units are predominantly isotactic, with an amount of meso dyad (m) greater than 80%.
3. Copolimeri, come nelle rivendicazioni 1 e 2, in cui R sia un atomo di idrogeno, un atomo di alogeno, un gruppo alchilico, un gruppo alcossilico o un gruppo solfonico. 3. Copolymers, as in claims 1 and 2, wherein R is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a sulphonic group.
4. Processi per l’ottenimento dei copolimeri, come descritti nelle rivendicazioni 1-3, che prevedano l’uso di catalizzatori di polimerizzazione per inserzione che sono in grado di omopolimerizzare il propene e di copolimerizzare lo stirene (o stireni sostituiti) con l’etilene. 4. Processes for obtaining copolymers, as described in claims 1-3, which provide for the use of insertion polymerization catalysts which are capable of homopolymerizing propene and copolymerizing styrene (or substituted styrenes) with ethylene.
e dal 6 % in moli di unita’ etileniche associate (Xs = 0.06). and 6% by moles of associated ethylene units (Xs = 0.06).
Dall’analisi calorimetrica a scansione differenziale (DSC) risulta che il polimero è caratterizzato da una temperatura di fusione a 103°C The differential scanning calorimetric analysis (DSC) shows that the polymer is characterized by a melting temperature of 103 ° C
Esempio 3 Example 3
La reazione e’ condotta a 0°C in una autoclave da 250 mL contenente 50 mL di toluene, 3.2 mL di stirene, 0.9 g di MAO e 9 mg dello stesso catalizzatore impiegato negli esempi 1 e 2, alimentando con una miscela gassosa di etilene/propilene (1/40 mol/mol) a 2 atmosfere. The reaction is carried out at 0 ° C in a 250 mL autoclave containing 50 mL of toluene, 3.2 mL of styrene, 0.9 g of MAO and 9 mg of the same catalyst used in examples 1 and 2, feeding with a gaseous mixture of ethylene / propylene (1/40 mol / mol) at 2 atmospheres.
La reazione e’ bloccata dopo un’ora e sono ottenuti circa 600 mg di prodotto (conversione < del 5% ). The reaction is stopped after one hour and approximately 600 mg of product are obtained (conversion <5%).
Dall’analisi dello spettro <13>C NMR risulta che il campione è caratterizzato da un contenuto in moli di unita’ stireniche del 3% (Xs =0.03), mentre il contenuto in moli di unita’ etileniche e’ del 7% ed è distribuito tra sequenze di unità etileniche contigue ad unita’ stireniche (3%) e sequenze di unità etileniche comprese tra unita’ propileniche From the analysis of the <13> C NMR spectrum it results that the sample is characterized by a content in moles of styrene units of 3% (Xs = 0.03), while the content in moles of ethylene units is 7% and is distributed between sequences of ethylene units contiguous to styrenic units (3%) and sequences of ethylene units comprised between propylene units
La temperatura di fusione del polimero e’ di The melting temperature of the polymer is
La distribuzione omogenea dei comonomeri è confermata da prove di estrazione con solventi idrocarburici: il polimero è completamente solubile in esano bollente ed è completamente insolubile in etere etilico bollente. The homogeneous distribution of the comonomers is confirmed by extraction tests with hydrocarbon solvents: the polymer is completely soluble in boiling hexane and completely insoluble in boiling ethyl ether.
Claims (4)
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT1999SA000005A ITSA990005A1 (en) | 1999-02-11 | 1999-02-11 | PROPYLENE-BASED COPOLYMERS CONTAINING STYRENE UNITS |
| KR1020007011224A KR20010042561A (en) | 1999-02-11 | 2000-02-10 | Propylene copolymers containing styrene units |
| CA002327781A CA2327781A1 (en) | 1999-02-11 | 2000-02-10 | Propylene copolymers containing styrene units |
| EP00910679A EP1071720A1 (en) | 1999-02-11 | 2000-02-10 | Propylene copolymers containing styrene units |
| JP2000598558A JP2002536514A (en) | 1999-02-11 | 2000-02-10 | Propylene copolymer containing styrene units |
| BR0004772-4A BR0004772A (en) | 1999-02-11 | 2000-02-10 | Propylene copolymers containing styrene units. |
| AU32807/00A AU3280700A (en) | 1999-02-11 | 2000-02-10 | Propylene copolymers containing styrene units |
| CN00800512A CN1300300A (en) | 1999-02-11 | 2000-02-10 | Propylene copolymers containing styrene units |
| PCT/EP2000/001219 WO2000047643A1 (en) | 1999-02-11 | 2000-02-10 | Propylene copolymers containing styrene units |
| NO20005101A NO20005101L (en) | 1999-02-11 | 2000-10-10 | Propylene copolymers containing styrene units |
| US10/068,361 US6617410B2 (en) | 1999-02-11 | 2002-02-06 | Propylene copolymers containing styrene units |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT1999SA000005A ITSA990005A1 (en) | 1999-02-11 | 1999-02-11 | PROPYLENE-BASED COPOLYMERS CONTAINING STYRENE UNITS |
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| Publication Number | Publication Date |
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| ITSA990005A1 true ITSA990005A1 (en) | 2000-08-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| IT1999SA000005A ITSA990005A1 (en) | 1999-02-11 | 1999-02-11 | PROPYLENE-BASED COPOLYMERS CONTAINING STYRENE UNITS |
Country Status (10)
| Country | Link |
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| EP (1) | EP1071720A1 (en) |
| JP (1) | JP2002536514A (en) |
| KR (1) | KR20010042561A (en) |
| CN (1) | CN1300300A (en) |
| AU (1) | AU3280700A (en) |
| BR (1) | BR0004772A (en) |
| CA (1) | CA2327781A1 (en) |
| IT (1) | ITSA990005A1 (en) |
| NO (1) | NO20005101L (en) |
| WO (1) | WO2000047643A1 (en) |
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| US7193024B2 (en) * | 2001-06-15 | 2007-03-20 | Dow Global Technology Inc. | Alpha-Olefin based branched polymer |
| FR2828198B1 (en) | 2001-07-31 | 2007-02-23 | Atofina | ISOTACTIC POLYPROPYLENE OBTAINED BY METALLOCENE GRAFT CATALYSIS |
| EP1866348B1 (en) | 2005-04-02 | 2011-08-24 | LG Chem. Ltd. | Method of producing styren polymers using high speed catalytic dispersion technology |
| CN106232646B (en) * | 2014-04-18 | 2018-11-20 | 日本A&L株式会社 | Graft copolymer and thermoplastic resin composition |
| CN116176018B (en) * | 2023-02-23 | 2023-11-14 | 河北海伟电子新材料科技股份有限公司 | Polypropylene capacitor film applied to electronic anti-monitoring tag and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2927566B2 (en) * | 1991-03-28 | 1999-07-28 | 出光興産株式会社 | Method for producing styrenic copolymer |
| US5543484A (en) * | 1994-11-18 | 1996-08-06 | The Penn State Research Foundation | α-olefin/para-alkylstyrene copolymers |
| EP0718323A3 (en) * | 1994-12-19 | 1998-01-14 | Sumitomo Chemical Company Limited | Ethylene type quaternary copolymer rubber |
| JP3489697B2 (en) * | 1995-04-04 | 2004-01-26 | 電気化学工業株式会社 | Propylene-aromatic vinyl compound copolymer and method for producing the same |
| DE19711339B4 (en) * | 1996-03-19 | 2008-09-11 | Denki Kagaku Kogyo K.K. | Copolymer of ethylene and aromatic vinyl compound, process for its preparation, molded articles thereof and composition comprising the copolymer |
| TW473503B (en) * | 1996-09-04 | 2002-01-21 | Dow Chemical Co | Substantially random interpolymer comprising Α-olefin/vinyl aromatic monomer and/or hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers, ethylene/styrene copolymer, and process for preparing Α-olefin/vinyl aromatic monomer interpoly |
| DE69820145T2 (en) * | 1997-04-17 | 2004-05-27 | Denki Kagaku Kogyo K.K. | Transition metal compound as a catalyst component for the polymerization, copolymer having stereoregularity from an aromatic vinyl compound and an olefin, and process for its production using the transition metal compound as a catalyst component |
-
1999
- 1999-02-11 IT IT1999SA000005A patent/ITSA990005A1/en unknown
-
2000
- 2000-02-10 BR BR0004772-4A patent/BR0004772A/en not_active IP Right Cessation
- 2000-02-10 CA CA002327781A patent/CA2327781A1/en not_active Abandoned
- 2000-02-10 AU AU32807/00A patent/AU3280700A/en not_active Abandoned
- 2000-02-10 JP JP2000598558A patent/JP2002536514A/en active Pending
- 2000-02-10 CN CN00800512A patent/CN1300300A/en active Pending
- 2000-02-10 EP EP00910679A patent/EP1071720A1/en not_active Withdrawn
- 2000-02-10 KR KR1020007011224A patent/KR20010042561A/en not_active Application Discontinuation
- 2000-02-10 WO PCT/EP2000/001219 patent/WO2000047643A1/en not_active Application Discontinuation
- 2000-10-10 NO NO20005101A patent/NO20005101L/en not_active Application Discontinuation
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| Publication number | Publication date |
|---|---|
| CA2327781A1 (en) | 2000-08-17 |
| KR20010042561A (en) | 2001-05-25 |
| BR0004772A (en) | 2000-11-21 |
| WO2000047643A1 (en) | 2000-08-17 |
| NO20005101D0 (en) | 2000-10-10 |
| CN1300300A (en) | 2001-06-20 |
| NO20005101L (en) | 2000-11-09 |
| JP2002536514A (en) | 2002-10-29 |
| EP1071720A1 (en) | 2001-01-31 |
| AU3280700A (en) | 2000-08-29 |
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