WO2000058379A1 - Procede de preparation de polypropylenes fonctionnalises - Google Patents

Procede de preparation de polypropylenes fonctionnalises Download PDF

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Publication number
WO2000058379A1
WO2000058379A1 PCT/DE2000/000503 DE0000503W WO0058379A1 WO 2000058379 A1 WO2000058379 A1 WO 2000058379A1 DE 0000503 W DE0000503 W DE 0000503W WO 0058379 A1 WO0058379 A1 WO 0058379A1
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WO
WIPO (PCT)
Prior art keywords
reaction
polypropylene
acid
carried out
grafting
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Application number
PCT/DE2000/000503
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German (de)
English (en)
Inventor
Jochen Gerecke
Joachim Stude
Original Assignee
Kometa Kunststoff-Modifikatoren Und-Additiv Ag
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 Kometa Kunststoff-Modifikatoren Und-Additiv Ag filed Critical Kometa Kunststoff-Modifikatoren Und-Additiv Ag
Priority to EP00914038A priority Critical patent/EP1181322A1/fr
Priority to JP2000608671A priority patent/JP2002540267A/ja
Publication of WO2000058379A1 publication Critical patent/WO2000058379A1/fr

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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
    • 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
    • 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
    • C08F8/00—Chemical modification by after-treatment

Definitions

  • the invention relates to a process for the production of functionalized polypropylenes by means of reaction of low molecular weight compounds having functional groups with polypropylene under solid phase reaction conditions.
  • polypropylene with polar plastics, in particular polycondensates such as polyamides and saturated polyesters, and / or with the adhesion to mineral reinforcing materials such as e.g. B. glass fibers, is to improve the functionalization of polypropylene by means of monomeric compounds having functional groups.
  • Functionalized polypropylenes are produced by generating radical sites on the polypropylene main chain and linking low-molecular compounds with at least one carboxyl, acid anhydride, amine, hydroxyl, epoxy, silane or another functional group (US 3862265, US 3884451) , US 4003874, US 4146529, US 4578428; US 4003874, EP 0268486; US 4443584; US 4652326).
  • grafting processes in the polymer melt are particularly known (DE 2242324, DE 2326589, DE 2455); EP 0128775; US 3177269, US 3177270, US 3987123, US 4753937, US 4857254).
  • the functionalization in particular the maleiination of polypropylene in the solid phase at lower temperatures, generally between 60 and 125 ° C., using a radical initiator or optionally also ionizing radiation is known (EP 0519341, EP 0664305, DD 275159, DD 275160, DD 275161, US 5079302).
  • the disadvantage of these discontinuous solid phase grafting technologies is their low grafting efficiency and a high proportion of inhomogeneities in the graft product, in particular when using higher-boiling dicarboxylic acids / acid anhydrides, such as, for. B. fumaric acid, itaconic acid (a ⁇ hydrid) and preferably maleic anhydride (MSA).
  • higher-boiling dicarboxylic acids / acid anhydrides such as, for. B. fumaric acid, itaconic acid (a ⁇ hydrid) and preferably maleic anhydride (MSA).
  • a process for the production of functionalized polypropylenes by free radical grafting of low molecular weight, at least one carboxyl and / or one acid anhydride and / or one amide and / or one imide and / or one hydroxyl and / or one epoxy and / or or an amine and / or a silane group-containing compounds found on polypropylene which is characterized in that the reaction in the solid phase in the temperature range between 80 and 160 ° C, preferably between 125 and 150 ° C, with continuous addition of the reaction components and continuous Discharge of the reaction product is carried out.
  • the functionalization represents a chemical modification of the polypropylene, also referred to as a polymer substrate, by grafting functional compounds as Single molecule or as a polymerized or copolymerized chain on the backbone chain of the polymer substrate.
  • HPP propylene
  • RCP statistical copolymers with copolymerized ethylene and / or C 4 to C 12 olefin units of 0.1 to 8% by mass
  • HCP heterophasic copolymers with copolymerized ethylene and / or C 4 to C 2 olefin units of 8 to 40 mass%
  • M w weight average molecular weight
  • MFR melt flow rate
  • Suitable low-molecular functionalization agents are the monomers customary for the known graft copolymerizations with at least one carboxy, anhydride, hydroxyl, epoxy, amino, silane or other functionality.
  • Monocarboxylic acids in particular acrylic acid, methacrylic acid, crotonic acid and their higher molecular weight homologues
  • dicarboxylic acids or their anhydrides in particular maleic anhydride (MSA), fumaric acid, itaconic acid (anhydride) and their higher molecular weight homologs can preferably be used.
  • the selected hydroxyl and epoxy group-containing monomers include hydroxyalkyl methacrylates and in particular glycidyl methacrylate (GMA).
  • GMA glycidyl methacrylate
  • dimethylaminoalkyl methacrylates in particular and of the possible silane group-containing compounds preferably vinyltrialkoxysilanes or methacryloxyalkyltrialkoxysilanes can be used.
  • the functional monomers mentioned are also in the form of their mixtures with one another and / or with the addition of non-polar comonomers, in particular vinyl aromatics such as styrene and methylstyrene, and / or comonomers having a functional group of low reactivity, for example an ester group such as methyl methacrylate and acrylic acid esters of Ci to C ⁇ alcohols, in a composition between 10 - 99 mass% functional monomer (s) and 1 - 90 mass% comonomer (s) can be used. With this measure, the specific reaction conditions and especially the graft product properties can be influenced in a targeted manner.
  • non-polar comonomers in particular vinyl aromatics such as styrene and methylstyrene
  • comonomers having a functional group of low reactivity for example an ester group such as methyl methacrylate and acrylic acid esters of Ci to C ⁇ alcohols
  • the radical functionalization reaction is usually carried out using a known radical generator to ensure a sufficient degree of functionalization and a uniform grafting.
  • Peroxidic initiators or also organic diazo compounds with half-lives of 5 to 100 minutes in the temperature range of 80 to 160 ° C. are preferably used as thermally decomposing radical formers. Selected examples of this are:
  • Di (tert.butyl) peroxide Di (tert.butyl) peroxide, dilauroyl peroxide, dibenzoyl peroxide, didecanoyl peroxide, dicumyl peroxide, tert.butylperoxy-2-ethylhexanoate, tert.butylperoxy-3,3,5-trimethylhexanoate, tert.butylperoxyisobutyrate, tert.butiperacetate, tert.butyl peroxide 1,1-di (tert-butylperoxy) -3,3,5-trimethyl-cyclohexane, 1,1-di (tert-amylperoxy) cyclohexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne -3, 2,5-dimethyl-2,5-di (hydro-peroxy) hexane etc.
  • diazo compounds such as. B. 2,2'-azo-bis (isobutyronitrile), 2,2'-azo-bis (2-methyl-butyronitrile), etc.
  • B. 2,2'-azo-bis (isobutyronitrile), 2,2'-azo-bis (2-methyl-butyronitrile), etc. can be used as a radical generator.
  • a special variant of carboxylation is the use of functional peroxyesters, which on the one hand function as free radical formers and on the other hand can act as modifiers due to their carboxy functionality, so that a functional monomer can generally be dispensed with.
  • Peroxyesters which are preferably suitable are: tert-butiperiperoxymaleic acid, tert-amylperoxymaleic acid, tert-butyl-peroxy-acanoic acid, and optionally also tert-butyl- or tert-amylperoxy-succinic acid (EP 0474227, WO 95/11938).
  • the specific use of the initiator ie the choice with regard to its chemical structure / half-life and its concentration based on the polymer substrate mass, depends on the grafting conditions chosen, in particular the functionalization agent used and the reaction temperature, taking into account the specially used reaction device and the technological regime.
  • a temperature-controllable reactor equipped with a heatable kneading and mixing elements and conveying in the axial direction has proven to be a preferred embodiment.
  • An overall continuously operated plant for the production of the functionalized polypropylenes according to the invention consists, for example, of a premixer, intermediate container, horizontal stirring reactor, product discharge device and post-reactor as main units.
  • the process can preferably be carried out in three main process stages: in a first process stage, the reaction components [polymer substrate, monomer or monomer mixture, initiator] are mixed in a temperature-controlled mixer, preferably first the polymer substrate with the initiator and, after a nitrogen purge, the monomer (s) ) added, whereby - according to the mixer size coordinated with the reactor volume and reactor throughput - dispersion temperatures between 20 and 60 ° C and mixing times from 10 to 90 min are chosen.
  • the dispersed premix is then fed to a weighing funnel as an intermediate container in which nitrogen is advantageously passed through the bed.
  • the premix is fed via a metering screw or another metering device suitable for dry-fluid substances into the previously flushed with nitrogen and with the polymer substrate (according to start-up mode) or filled with a previous premixed reactor.
  • T R temperatures between 80 and 160 ° C and mean residence times (VWZ) between 5 and 120 min, preferably between 10 and 30 min, at no point in the reactor including the reactor nozzle for metering - and discharge device a monomer condensation can occur.
  • This basic requirement can be met by appropriate (additional) heating of these reactor parts.
  • the same applies to the product discharge, which, for. B. can be done in a nitrogen-flushed hatch or other discharge device.
  • a heated screw discharged "raw" graft product of unreacted monomers by means of nitrogen flushing at a temperature between 100 and 160 ° C. and a residence time between 10 and 60 min. At the same time, remaining initiator residues are completely degraded. if necessary after adding a stabilizer or stabilizer mixture known for polypropylene, cooled and classified The functionalized polypropylenes obtained in this way can be used without further processing steps for their intended use as a compatibilizer and / or coupling agent.
  • the advantage of the process according to the invention over the known processes of polypropylene functionalization in the melt and in the solid phase at temperatures between 60 and 125 ° C. is its high cost-effectiveness and the assurance of a high degree of grafting (mass of grafted polypropylene to the total mass of polypropylene). This can be attributed to the easy-to-use process control with a wider range of options regarding the degree of modification and the characteristic level of the functionalized polypropylenes.
  • the products according to the invention have a graft structure which is effective for melt phase products. rend on individual "attached" functional structure units, for example succinic anhydride units when using MSA.
  • a significant advantage over the melt grafting is the more targeted polymer backbone chain degradation corresponding to the desired narrower molecular weight distributions and / or higher melt flow indices.
  • the degree of functionalization i. that is, the concentration of grafted MA is determined after a 6-hour treatment of the residue with xylene / excess methanolic KOH in a defined amount by back-titration with methanolic HCl.
  • CPO Dicumyl peroxide
  • TBPM Butyl-peroxy-maleic acid
  • HPP MFR: 3 g / 10 min
  • example 5 RCP MFR: 1.9 g / 10 min
  • HPP MFR: 12 g / 10 min

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)

Abstract

Procédé de préparation de polypropylènes fonctionnalisés à l'aide d'une réaction de greffage radicalaire entre des liaisons contenant des groupes fonctionnels de faible poids moléculaire et des polypropylènes dans des conditions de réaction à phase solide. Ledit procédé est caractérisé en ce que le greffage de liaisons contenant des groupes fonctionnels sur du polypropylène s'effectue avec apport en continu des constituants de réaction ainsi qu'avec évacuation en continu du produit de réaction dans la plage de température située entre 80 et 160 DEG C. Par rapport aux procédés connus, l'avantage fondamental du procédé selon la présente invention réside dans son rendement économique élevé associé à la garantie simultanée d'un succès de greffage élevé. Dans les conditions de greffage selon la présente invention, la formation d'homopolymères ou plus précisément de copolymères non greffés est inexistante ou si minime qu'elle peut être ignorée, et les polypropylènes fonctionnalisés possèdent une structure greffée efficace.
PCT/DE2000/000503 1999-03-29 2000-02-23 Procede de preparation de polypropylenes fonctionnalises WO2000058379A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP00914038A EP1181322A1 (fr) 1999-03-29 2000-02-23 Procede de preparation de polypropylenes fonctionnalises
JP2000608671A JP2002540267A (ja) 1999-03-29 2000-02-23 官能化ポリプロピレンの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1999114146 DE19914146A1 (de) 1999-03-29 1999-03-29 Verfahren zur Herstellung funktionalisierter Polypropylene
DE19914146.0 1999-03-29

Publications (1)

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WO2000058379A1 true WO2000058379A1 (fr) 2000-10-05

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EP (1) EP1181322A1 (fr)
JP (1) JP2002540267A (fr)
DE (1) DE19914146A1 (fr)
WO (1) WO2000058379A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10123825A1 (de) * 2001-05-16 2002-11-28 Kometra Kunststoff Modifikatoren & Additiv Durch Maleinsäureanhydrid modifizierte Polypropylene und Verfahren zu ihrer Herstellung

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10213908A1 (de) * 2002-03-28 2003-10-09 Kometra Kunststoff Modifikatoren & Additiv Verfahren zur Herstellung von funktionalisierten syndiotaktischen Polystyrolen
ES2517291T3 (es) * 2002-11-26 2014-11-03 Byk Kometra Gmbh Copolímeros en bloque de estireno/olefina funcionalizados
DE102004016163A1 (de) * 2004-03-26 2005-10-13 Kometra Kunststoff-Modifikatoren Und -Additiv Gmbh Polypropylen-Verbunde
CN100523029C (zh) * 2005-10-11 2009-08-05 中国科学技术大学 一种聚丙烯悬浮固相接枝制备马来酸酐共聚物的方法
EP2976367B1 (fr) * 2013-03-20 2021-04-28 BYK-Chemie GmbH Procédé de fabrication d´un élastomère thermoplastique fonctionnalisé

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1376777A (en) * 1972-07-05 1974-12-11 Dart Ind Inc Blends of olefin polymers
DE19607430C1 (de) * 1996-02-28 1997-04-24 Danubia Petrochem Polymere Kontinuierliches Verfahren zur Modifizierung von Polyolefinen in der festen Phase
EP0792894A2 (fr) * 1996-02-28 1997-09-03 PCD-Polymere Gesellschaft m.b.H. Modification de polyoléfines en continu en phase solide

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD266358A1 (de) * 1987-12-14 1989-03-29 Buna Chem Werke Veb Verfahren zur herstellung von polarmodifiziertem polypropylen
RU2068421C1 (ru) * 1992-10-02 1996-10-27 Институт синтетических полимерных материалов РАН Способ получения модифицированных полиолефинов
FR2738841B1 (fr) * 1995-09-15 1997-11-21 Centre Nat Rech Scient Procede de polymerisation de sequences d'acides nucleiques et ses applications

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1376777A (en) * 1972-07-05 1974-12-11 Dart Ind Inc Blends of olefin polymers
DE19607430C1 (de) * 1996-02-28 1997-04-24 Danubia Petrochem Polymere Kontinuierliches Verfahren zur Modifizierung von Polyolefinen in der festen Phase
EP0792894A2 (fr) * 1996-02-28 1997-09-03 PCD-Polymere Gesellschaft m.b.H. Modification de polyoléfines en continu en phase solide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10123825A1 (de) * 2001-05-16 2002-11-28 Kometra Kunststoff Modifikatoren & Additiv Durch Maleinsäureanhydrid modifizierte Polypropylene und Verfahren zu ihrer Herstellung

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JP2002540267A (ja) 2002-11-26
EP1181322A1 (fr) 2002-02-27
DE19914146A1 (de) 2000-10-05

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