DK2315784T3 - Fremgangsmåde til syntese af funktionaliserede poly(1,3-alkadiener) og anvendelse deraf til fremstilling af slagfaste vinylaromatiske polymerer - Google Patents

Fremgangsmåde til syntese af funktionaliserede poly(1,3-alkadiener) og anvendelse deraf til fremstilling af slagfaste vinylaromatiske polymerer Download PDF

Info

Publication number
DK2315784T3
DK2315784T3 DK09777874.0T DK09777874T DK2315784T3 DK 2315784 T3 DK2315784 T3 DK 2315784T3 DK 09777874 T DK09777874 T DK 09777874T DK 2315784 T3 DK2315784 T3 DK 2315784T3
Authority
DK
Denmark
Prior art keywords
vinyl aromatic
polymerization
mixture
solvent
elastomer
Prior art date
Application number
DK09777874.0T
Other languages
English (en)
Inventor
Gian Tommaso Viola
Leonardo Chiezzi
Original Assignee
Versalis Spa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Versalis Spa filed Critical Versalis Spa
Application granted granted Critical
Publication of DK2315784T3 publication Critical patent/DK2315784T3/da

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
    • C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
    • 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
    • C08F2/00—Processes of polymerisation
    • 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
    • C08F212/08—Styrene
    • 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
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • 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
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • 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
    • C08L51/04—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 rubbers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (9)

1. Fremgangsmåde til syntese af funktionaliserede poly(l,3-alkadiener) der omfatter anionisk polymerisering af mindst en monomer af en 1,3-alkadien, i tilstedeværelsen af organisk lithium og et lavt-kogende ikke-polært opløsningsmiddel og effektuering af kæde-termineringsfasen af polymeren baseret på 1,3-alkadien, ved afslutningen af polymeriseringen, ved tilsætning til polymeriseringsblandingen, afen bromalkan, hvor alkanen indeholder fra 1 til 12 carbonatomer, efterfulgt af tilsætningen af et produkt indeholdende et stabilt nitroxyradikal, kendetegnet ved at -NO*-gruppen er opløselig i det ikke-polære opløsningsmiddel.
2. Fremgangsmåde ifølge krav 1, hvor 1,3-alkadienen er butadien.
3. Fremgangsmåde ifølge krav 1 eller 2, hvor det organiske lithium er lithiumbutyl.
4. Fremgangsmåde ifølge krav 1, 2 eller 3, hvor bromalkanen er 1-bromoktan.
5. Fremgangsmåde ifølge et hvilket som helst af de foregående krav, hvor produktet indeholdende et stabilt nitroxyradikal, kendetegnet ved at -NO-gruppen er valgt fra dem med den almene formel (II)
(II) hvor grupperne RI, R2, R5 og R6, er de samme eller forskellige, er lineære eller forgrenede alkylradikaler, substitueret eller ikke-substitueret indeholdende fra 1 til 20 carbonatomer eller alkylaromatiske radikaler, hvor alkylgruppen indeholder fra 1 til 4 carbonatomer mens grupperne R3 og R4, er de samme eller forskellige, er lig med RI, R2, R5 og R6 eller R3-CNC-R4 tilhører en cyklisk struktur, for eksempel med 4 eller 5 carbonatomer, eventuelt kondenseret med en aromatisk ring eller med en mættet ring indeholdende fra 3 til 20 carbonatomer.
6. Funktionaliserede poly(l,3-alkadiener) opnåelige ifølge fremgangsmåden ifølge et hvilket som helst af de foregående krav.
7. Fremgangsmåde til fremstilling af vinylaromatiske (co)polymerer podet på en umættet elastomer på en kontrolleret måde, omfattende: a. at opløse en elastomer funktionaliseret med brom-alkaner og nitroxyradikaler opløselige i ikke-polære opløsningsmidler, som beskrevet i krav 6, i en væskefase bestående af en blanding af vinylaromatiske monomer(er)/polymeriseringsopløsningsmiddel i et vægtforhold på fra 60/40 til 100/0, fortrinsvis fra 60/40 til 90/10; b. at tilføre mindst en radikalinitiator til blandingen, indeholdende den funktionaliserede elastomer i opløsning, og polymisering af den dermed opnåede blanding ved en temperatur der er højere end eller lig med 120°C; c. at genvinde den vinylaromatiske (co)polymer opnået ved afslutningen af polymeriseringen og at underkaste den devolatilisering under vakuum til genvinding af opløsningsmidlet og ikke-reageret monomer(er); og d. at genbruge opløsningsmiddel-/monomer(er)blandingen, der stammer fra devolatilisering, til trin (a).
8. Fremgangsmåde ifølge krav 7, hvor de vinylaromatiske monomerer er styren og/eller a-methylstyren.
9. Slagfast vinylaromatisk (co)polymer omfattende en kontinuerlig fase, i det væsentlige bestående af en matrix indeholdende mindst 50 vægtprocent afen vinylaromatisk monomer, og en dispergeret fase i det væsentlige bestående af 1 til 25 vægtprocent, i forhold til det samlede indhold, afen funktionaliseret elastomer med partikler med en "kerneskals-" morfologi med en gennemsnitsdiameter på fra 0,1 til 1 pm, opnåelig ifølge fremgangsmåden ifølge et hvilket som helst af kravene 7 eller 8.
DK09777874.0T 2008-08-20 2009-08-07 Fremgangsmåde til syntese af funktionaliserede poly(1,3-alkadiener) og anvendelse deraf til fremstilling af slagfaste vinylaromatiske polymerer DK2315784T3 (da)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI2008A001524A IT1391109B1 (it) 2008-08-20 2008-08-20 Procedimento per la sintesi di poli(1,3-alcadieni) funzionalizzati e loro impiego nella preparazione di polimeri vinilaromatici ad alta resistenza all'urto
PCT/EP2009/005893 WO2010020374A1 (en) 2008-08-20 2009-08-07 Process for the synthesis of functionalized poly(1,3-alkadienes) and use thereof in the preparation of high impact vinyl aromatic polymers

Publications (1)

Publication Number Publication Date
DK2315784T3 true DK2315784T3 (da) 2017-02-27

Family

ID=40802003

Family Applications (1)

Application Number Title Priority Date Filing Date
DK09777874.0T DK2315784T3 (da) 2008-08-20 2009-08-07 Fremgangsmåde til syntese af funktionaliserede poly(1,3-alkadiener) og anvendelse deraf til fremstilling af slagfaste vinylaromatiske polymerer

Country Status (13)

Country Link
US (1) US9029479B2 (da)
EP (1) EP2315784B1 (da)
JP (1) JP5642677B2 (da)
CN (1) CN102164968B (da)
BR (1) BRPI0917857B1 (da)
DK (1) DK2315784T3 (da)
ES (1) ES2616517T3 (da)
HU (1) HUE033188T2 (da)
IT (1) IT1391109B1 (da)
PL (1) PL2315784T3 (da)
PT (1) PT2315784T (da)
RU (1) RU2493174C2 (da)
WO (1) WO2010020374A1 (da)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20121018A1 (it) 2012-06-12 2013-12-13 Versalis Spa Procedimento per la preparazione di copolimeri elastomerici funzionalizzati e ramificati e loro impiego in composizioni elastomeriche vulcanizzabili
TWI674295B (zh) * 2015-08-20 2019-10-11 日商日本瑞翁股份有限公司 含腈基之共聚橡膠、交聯性橡膠組合物及橡膠交聯物
US10882940B2 (en) 2016-04-29 2021-01-05 Sabic Global Technologies B.V. Process for the production of copolymers
RU2666724C1 (ru) * 2018-05-15 2018-09-12 Публичное Акционерное Общество "Нижнекамскнефтехим" Способ получения полимеров бутадиена или сополимеров бутадиена со стиролом с низким содержанием 1,2-звеньев в бутадиеновой части
TW202330677A (zh) 2021-12-10 2023-08-01 義大利商佛沙里斯股份有限公司 橡膠強化的乙烯芳香族(共)聚合物及其製備方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2730241B1 (fr) * 1995-02-07 1997-02-28 Atofina Procede de fabrication d'une composition comprenant un polymere vinylaromatique et un caoutchouc par polymerisation en presence d'un radical libre stable
IT1274361B (it) * 1995-02-16 1997-07-17 Enichem Spa Procedimento per la preparazione di copolimeri vinilaromatici rinforzati con gomma
HU220138B (hu) * 1996-03-29 2001-11-28 The Dow Chemical Co. Szabadgyökös tömbpolimerizálási eljárás kaucsukkal módosított polimerek vinil-aromás monomerekből való előállítására
FR2768739B1 (fr) * 1997-09-19 2004-08-06 Atochem Elf Sa Polymere vinylaromatique choc obtenu a partir d'un caoutchouc porteur d'un groupement generateur d'un radical libre stable
IT1318479B1 (it) * 2000-04-20 2003-08-25 Enichem Spa Procedimento per la preparazione di gomme sbr con miglioratalavorabilita' e minore resistenza al rotolamento.
ITMI20031420A1 (it) * 2003-07-11 2005-01-12 Polimeri Europa Spa Polimeri vinilaromatici rinforzati con gomma
ITMI20040752A1 (it) * 2004-04-16 2004-07-16 Polimeri Europa Spa Procedimento per la preparazione di co polimeri vinilaromatici aggraffati su elastometro in modo controllato
US7125934B1 (en) 2005-06-28 2006-10-24 The Goodyear Tire & Rubber Company Functionalization of living rubbery polymers with nitrones
JP4286300B2 (ja) * 2007-04-16 2009-06-24 横浜ゴム株式会社 変性ポリマー
KR20090130070A (ko) * 2007-04-18 2009-12-17 다우 글로벌 테크놀로지스 인크. 설파닐실란 관능화 탄성중합체성 중합체를 포함하는 개선된 모노비닐리덴 방향족 중합체

Also Published As

Publication number Publication date
ES2616517T3 (es) 2017-06-13
WO2010020374A1 (en) 2010-02-25
HUE033188T2 (hu) 2017-11-28
BRPI0917857B1 (pt) 2019-01-02
RU2493174C2 (ru) 2013-09-20
ITMI20081524A1 (it) 2010-02-21
JP2012500310A (ja) 2012-01-05
CN102164968B (zh) 2013-04-17
CN102164968A (zh) 2011-08-24
PT2315784T (pt) 2017-02-28
IT1391109B1 (it) 2011-11-18
RU2011107115A (ru) 2012-09-27
BRPI0917857A2 (pt) 2015-11-24
PL2315784T3 (pl) 2017-06-30
EP2315784A1 (en) 2011-05-04
US9029479B2 (en) 2015-05-12
EP2315784B1 (en) 2016-11-23
US20110207884A1 (en) 2011-08-25
JP5642677B2 (ja) 2014-12-17

Similar Documents

Publication Publication Date Title
US7754817B2 (en) Low temperature initiators for improving the rubber phase volume of HIPS formulations
DK2315784T3 (da) Fremgangsmåde til syntese af funktionaliserede poly(1,3-alkadiener) og anvendelse deraf til fremstilling af slagfaste vinylaromatiske polymerer
EP2142575A1 (en) Process for the production of a (co) polymer composition by mediated free radical chain growth polymerization
Hanifpour et al. Poly1‐hexene: New impact modifier in HIPS technology
US7514516B2 (en) Measurement and preparation of branched vinyl polymers
WO2004106428A2 (en) Optimizing polystyrene in the presence of additives
EP2358773B1 (en) Rubber-reinforced vinyl aromatic (co)polymer, having an optimum balance of physico-mechanical properties and a high gloss
MX2011001876A (es) Proceso para la sintesis de poli(1,3-alcadienos)funcionalizados y el uso de los mismos en la preparacion de polimeros aromaticos de vinilo de alto impacto.
TWI518099B (zh) A method for achieving high rubber efficiency in a high impact polystyrene reactor
US20050113525A1 (en) Use of tetrafunctional initiators to improve the rubber phase volume of HIPS
WO2023105386A1 (en) Rubber-reinforced vinylaromatic (co)polymers and process for the preparation thereof
Uriel et al. Study on two different dithiobenzoates effectiveness in bulk RAFT polymerization of β-myrcene
JP2008520752A (ja) Ｈｉｐｓのゴム相容積を改善するための四官能性開始剤の使用
CN106867127A (zh) 热可塑性树脂组成物及其所形成的成型品
WO2006054995A1 (en) Use of tetrafunctional initiators to improve the rubber phase volume of hips