EP1208120A1 - Produits reticules ne presentant pas de dispersion et a nebulisation reduite - Google Patents

Produits reticules ne presentant pas de dispersion et a nebulisation reduite

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Publication number
EP1208120A1
EP1208120A1 EP00965960A EP00965960A EP1208120A1 EP 1208120 A1 EP1208120 A1 EP 1208120A1 EP 00965960 A EP00965960 A EP 00965960A EP 00965960 A EP00965960 A EP 00965960A EP 1208120 A1 EP1208120 A1 EP 1208120A1
Authority
EP
European Patent Office
Prior art keywords
anhydride
weight
copolymer
acid
peroxide
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP00965960A
Other languages
German (de)
English (en)
Inventor
Jernej Jelenic
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Akzo Nobel NV
Original Assignee
Akzo Nobel NV
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 Akzo Nobel NV filed Critical Akzo Nobel NV
Priority to EP00965960A priority Critical patent/EP1208120A1/fr
Publication of EP1208120A1 publication Critical patent/EP1208120A1/fr
Withdrawn legal-status Critical Current

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
    • C08C19/08—Depolymerisation

Definitions

  • the present invention relates to compositions comprising peroxide and a specific copolymer, compositions comprising said copolymer and carrier materials, a cross-linking process of polymers/elastomers involving the use of peroxides and said copolymer, and the products obtained by this process.
  • the resulting (cross-linked) products show essentially no blooming, reduced emission of volatile compounds, and less fogging.
  • the cross-linking is predominantly of a polyolefin or elastomer through reactions initiated by radicals obtained by decomposition of the peroxide.
  • the resulting cross-linked products can be in the form of finished articles or intermediates.
  • the phthalic anhydride reacts with an OH group-bearing decomposition product of the peroxide. While the OH group-bearing decomposition product would lead to blooming, the reaction product with the phthalic anhydride does not.
  • the phthalic anhydride was used in a quantity of at least 2 moles per mole of (difunctional) peroxide used.
  • the use of phthalic anhydride has its drawbacks. More particularly, the quantity of OH group-bearing peroxide decomposition products formed will depend on the reaction conditions when the peroxide decomposes.
  • reaction conditions are such that the radicals undergo ⁇ -scission, for example, a significantly reduced quantity of OH group- bearing products is formed (i.e. because ketones are formed).
  • the radicals may react with the unsaturated moiety, resulting in fewer OH group-bearing decomposition products.
  • "in-cage" termination reactions might occur, wherein two radical fragments of the peroxide, after one or more rearrangements, terminate with one another.
  • the quantity of phthalic anhydride needed to react with the OH group-bearing peroxide decomposition products that are formed is dependent on many factors that, more often than not, cannot be controlled beforehand. Consequently, there will hardly ever be stoichiometric quantities of phthalic anhydride and OH group-bearing peroxide decomposition products.
  • the solution to the blooming problem should not interfere with the cross-linking process so that recipes do not have to be changed other than in adding a certain ingredient.
  • the invention is characterized in that peroxide is used in combination with one or more copolymers comprising olefin-derived moieties and one or more anhydride and/or acid groups, the copolymer being used in a quantity of from 0.1 to 500 per cent by weight of the weight of the peroxide.
  • Japanese patent application No. 08157646 discloses the use of such copolymers in elastomer compositions that contain brass and/or brass-plated iron in order to improve the adhesion of the elastomer, after peroxide-initiated vulcanization, to said brass. Such compositions are not the subject of the present invention. Furthermore, this Japanese patent application is silent with respect to blooming, the emission of volatile products and/or fogging.
  • copolymers containing olefin-derived moieties and anhydride and/or acid groups can be suitably obtained through (random) copolymerization or grafting processes.
  • EP-A-0 429 123 discloses a suitable process wherein olefins (1), or mixtures of olefins, are reacted with ⁇ , ⁇ - unsaturated dicarboxylic compounds (2), in the presence of a polymerization inhibitor, and preferably in the substantial absence of the well-known polymerization initiators, at temperatures from about 180°C to about 350°C and at subatmospheric, atmospheric or superatmospheric pressures, but preferably at atmospheric pressure.
  • the reaction is preferably carried out in the absence of oxygen, i.e. under an inert (nitrogen) atmosphere. Reaction times can range from about 0.5 to about 15 hours.
  • the inhibitor utilized is said to be used preferably in a quantity of from about 0.01% to about 3% by weight, based on the combined weight of components (1) and (2).
  • Components (1) and (2) may be reacted in a single dose or may be dosed continuously or periodically throughout the reaction cycle.
  • the copolymers so obtained may additionally be hydrogenated, for example by heating at 130 - 200°C in the presence of a catalyst, e.g., nickel or palladium. Such hydrogenated compositions typically have improved thermo-oxidative stability.
  • Typical examples of preferred copolymers as used according to the present invention are Dapral® PX 200 and Ricobond® as supplied by Akzo Nobel and Ricon Resins Inc., respectively.
  • Olefins suitable for use in the copolymer of the invention include propylene, butadiene, isobutylene, and C 6 to C 24 ⁇ -olefins.
  • Preferred olefins for use in these copolymers have 12 to 18 carbon atoms. More preferably, at least one C 12 to C 18 ⁇ -olefin, such as dodecene-1 , tridecene-1 , tetradecene-1 , pentadecene-1 , hexadecene-1 , heptadecene-1 , and octadecene-1 , is used.
  • Preferred unsaturated anhydride and/or acid moiety-containing compounds used to introduce anhydride and/or acid groups into the copolymer include maleic anhydride; (di)alkyl/aryl-maleic anhydride, such as n-dodecyl maleic anhydride, citraconic anhydride, and maleic phenyl anhydride; (substituted) norbornene-2,3-dicarboxylic anhydride; (meth)acrylic acid; maleic acid; fumaric acid; itaconic acid; citraconic acid; and other anhydrides and/or acids with an unsaturated group that can be linked with an olefin.
  • the copolymer contains anhydride and/or acid groups derivable from maleic anhydride or methacrylic acid.
  • the copolymers might also be adducts of alkadiene polymers and cyclic or acyclic anhydrides of mono- or dicarboxylic acids containing 4 to 18 carbon atoms as disclosed in US patent No. 4,423,177.
  • the copolymers preferably have a composition as obtainable by reacting one or more olefins and one or more anhydride/acid group-containing monomers, with the anhydride/acid group-containing monomers being present in a quantity of 5-75 per cent by weight (%w/w). More preferably, the anhydride/acid group-containing monomers are present in a quantity of 10-50 %w/w.
  • the copolymers were found not to bloom from products comprising them, possibly due to their molecular weight. To avoid blooming, the molecular weight of the copolymer, most likely, will have to be over 500, preferably over 800, and more preferably over 1100 Dalton. However, in order to facilitate processing of compositions comprising the copolymer, and to allow for sufficient mobility of the copolymer in the final matrix, the molecular weight of the copolymer must be below 50,000, preferably below 25,000, and more preferably below 15,000 Typically, an alternating copolymer with 5 to 50 repeating units can suitably be used
  • the quantity of said copolymer that is to be used in the peroxide-containing elastomer/polyolefin compositions can vary over a wide range and can be optimized on the particular composition and the conditions during peroxide decomposition However, since the copolymer does not bloom at all, it can be used in a more than stoichiomet ⁇ c quantity, based on the quantity of OH group-bearing decomposition products that can be formed by the peroxide (by radical abstraction) Because it is estimated that as little as 50% of the radicals from the decomposing peroxide might actually lead to the formation of OH group-bearing decomposition products, the minimum quantity of copolymer to be used in the peroxide-containing elastomer/polyolefin compositions of the invention is such that the total number of anhydride/acid groups of the copolymer equals 50% of the maximum quantity of OH groups that can be formed from the decomposing peroxide Typically this means that at least 0 1 %w/
  • the polymer/elastomer can be cross-linked in a conventional way using a peroxide in combination with the copolymer.
  • the copolymer and the peroxide may be blended/mixed together or separately with the polymer/elastomer at any time using conventional equipment, such as a (twin-screw) extruder.
  • they are blended/mixed into the polymer/elastomer together and jointly with optional further ingredients, so that just one mixing step is required.
  • differences in viscosity of the compounds to be blended/mixed may dictate otherwise. Large viscosity differences, for example, may require that one of the components be introduced in a stepwise fashion to ensure efficient mixing/blending.
  • polymer/elastomer as used throughout this document is meant to denominate all thermoplastic and/or rubbery polymers.
  • the polymer/elastomer is a (co)polymer of ethylene, propylene and/or a synthetic or natural rubber.
  • Examples include, but are not limited to, polypropylene (PP) and/or one of the more preferred polymers/elastomers selected from the group consisting of polyethylene (LDPE, LLDPE, HDPE); chlorinated polyethylene; ethylene- ⁇ -olefin copolymers, such as ethylene/propylene copolymers (EPM and EPDM), ethylene octene copolymer (EOP); ethylene-vinyl acetate copolymer (EVA) polyacrylic acid ester; natural rubber (NR); polybutadiene rubber (BR) polybutylene; polyisobutylene; styrene butadiene rubber (SBR) acrylonitrile-butadiene-styrene terpolymer (ABS); (acrylo)nitrile butadiene rubber (NBR); hydrogenated (acrylo)nitrile butadiene rubber (HNBR); polyisoprene; polychloroprene rubber (CR); silicone rubber (VMQ,
  • polymer/elastomer More preferred types include polyethylene, ethylene-vinyl acetate copolymer, butadiene-acrylonitrile copolymer, EPM; EPDM, such as Vistalon®606 and Vistalon®7500 ex Exxon and Buna ⁇ EP 6550 and Buna®EP G8450 ex Bayer; EOP, such as Engage®8150 and Engage®8180 ex DuPont-Dow- Elastomers; VMQ, such as Silopren®HV ex Bayer; and FKM, such as Viton® products ex DuPont-Dow-Elastomers, all of which are low-priced, widely available, and have excellent physical properties that allow wide- ranging use. Most preferred are compositions based on synthetic rubbers, since here the blooming phenomenon is most pronounced, such as EPM, EPDM, and EOP.
  • cross-linking is used in the usual way, meaning that a three- dimensional network of polymer chains is formed as is detailed in, for instance, chapter 1.3 of W. Hofmann's Rubber technology handbook (Carl Hanser Verlag, 1989).
  • the term does not comprise the very different grafting process such as described in FR-A-2 559 774, wherein a monomer unit is grafted onto a polymer to increase its adhesion to polar polymers and/or metals.
  • Blooming typically is the result of products migrating to the surface of a polymeric/elastomeric article. Whether a product is subject to blooming or not depends on the solubility of the compound and the rate of diffusion. As is conventional, products are considered not to bloom when no changes on the surface are observed (visual inspection) upon storage for a prolonged time at temperatures above the temperatures that may be encountered during projected use of the products. To determine whether the cross-linked polymeric/elastomeric article emits volatile compounds over time, conveniently use is made of a fogging test.
  • the peroxide as used in the compositions according to the invention can be any conventional peroxide.
  • the peroxides are chosen from products conventionally used in cross-linking and degradation reactions, such as dialkyl peroxides, perketals, peroxycarbonates, and the like.
  • the peroxide or mixture of peroxides that is used comprises a peroxide selected from the group consisting of bis(tert- butylperoxyisopropyl)benzene, "liquified" versions of this peroxide, meaning that one or more tert-butyl groups are replaced by other (more) bulky groups or that may contain substituents on the benzene ring, dicumyl peroxide, 2,5-bis(tert-butylperoxy)-2,5,dimethylhexane, 2,5-bis(tert-butyl- peroxy)-2,5-dimethyl-3-hexyne, 1 ,3,5-tris(tert-butylperoxy- isopropyl)benzene, tert-butyl cumyl peroxide, di-t-butyl peroxide, 1 ,1- bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1 , 1 -
  • the most preferred peroxides for use in the process according to the invention are the conventional ones, bis(tert-butylperoxyisopropyl)benzene in particular.
  • the amount of peroxide used preferably ranges from 1 to 5 per cent by weight, based on the weight of the polymer/elastomer to be degraded or cross-linked. More preferably, the peroxide is used in an amount of 1.5 - 4.0 per cent by weight, based on the weight of the polymer/elastomer.
  • the invention relates to compositions comprising peroxide and a copolymer with olefin-derived moieties and anhydride and/or acid groups, which compositions are pre-eminently suited for use in the cross-linking process.
  • These compositions may contain further conventional additives, such as plasticizers (e.g. paraffinic oils and/or esters), antioxidants, scorch retarders, and the like, and conventional carrier materials, such as silica and/or chalk.
  • plasticizers e.g. paraffinic oils and/or esters
  • antioxidants e.g. paraffinic oils and/or esters
  • scorch retarders e.g., scorch retarders, and the like
  • carrier materials such as silica and/or chalk.
  • compositions will contain 5-60% by weight, based on the total weight of the composition, of peroxide, 0.1-500% by weight, based on the weight of the peroxide(s), of the copolymer, optional further additives, and 0-50% by weight of carrier material, up to a total of 100%.
  • Preferred compositions comprise one or more peroxides, copolymer with olefin-derived moieties and anhydride and/or acid groups, one or more fillers selected from the group consisting of silica, clay, chalk, kaolin, and carbon black, and optional further conventional additives.
  • the invention relates to compositions comprising one or more of the conventional additives and/or conventional carrier materials, as mentioned below, and copolymer with olefin-derived moieties and anhydride and/or acid groups.
  • such compositions will contain 1-99.9% by weight, based on the total weight of the composition, of additives and/or carrier material and 99-0.1 % by weight, based on the weight of the composition, of the copolymer, up to a total of 100%. More preferably, the compositions will contain 10-99% of additives and/or carrier material and 90-1% of the copolymer. Even more preferred are compositions containing 25-90% of additives and/or carrier material and 75-10% of the copolymer.
  • compositions comprise copolymer with olefin-derived moieties and anhydride and/or acid groups, one or more fillers selected from the group consisting of silica, clay, chalk, kaolin, and carbon black, and optional further conventional additives mentioned above.
  • the products obtainable by this process which show essentially no blooming and reduced emission of volatiles, are typically but not limited to: building profiles; automotive profiles, such as sponge door seals and weatherstrips; mechanical goods, such as hose, conveyor belt cover materials, and seals; and the like.
  • the products may be in the final form and shape, or be present as an intermediate that needs further processing.
  • Such an intermediate may be a granulate of (partially) cross- linked polymer/elastomer.
  • additives include co-agents; monomers; chain transfer agents; initers, such as NO compounds; fillers; stabilizers, such as inhibitors of oxidative, thermal, or ultraviolet degradation, also known as antioxidants, antidegradants and/or scorch retarders; lubricants; extender oils; pH controlling substances, such as magnesium oxide and calcium carbonate; release agents; vulcanizing agents, such as sulfur; colourants; plasticizers; diluents; accelerators; and the like.
  • reinforcing or non-reinforcing fillers are: silica, clay, chalk, carbon black, and fibrous materials, such as glass fibres, and the like.
  • Perkadox® 14 R Di(tert-butylperoxyisopropyl)benzene (ex Akzo Nobel) Perkadox® 14 40 B pd ex Akzo Nobel) Keltan® 520 - EPDM (ex DSM) Carbon black SRF N-772 (ex Cabot)
  • Dapral® PX 200 - ⁇ -olefin maleic anhydride copolymer (ex Akzo Nobel) of
  • Cis-hexahydrophthalic anhydride (ex Acros Organics) Succinic anhydride (ex Fluka Chemie )
  • Methylnorbomene-2,3 dicarboxylic anhydride (ex Acros Organics) 1 ,2,4,5 benzene tetracarbacid (ex Acros Organics) 1 ,3,5-tris-(t-butyl-peroxyisopropyl)benzene (ex Akzo Nobel)
  • Px-14R Perkadox® 14 R, 50% by weight of peroxide.
  • the extractable matter in the rubber, after cross-linking, was determined by extraction with dichloromethane and subsequent GC-analysis.
  • the quantity of extractable matter is an indication of the likelihood that the cross-linked product will show blooming or emit volatile matter.
  • Some products were evaluated using dynamic head space GC analysis to determine the quantity of volatile matter in the product. To this end, a sample of 30-50 mg of the product was heated in a glass tube under a stream of inert gas. The desorbed volatile compounds were trapped in a liquid nitrogen cooled trap placed downstream of the sample. After the heat cycle "desorption time" the cold trap was heated rapidly and the condensed volatile compounds evaporated. The compounds were transferred directly to a capillary GC column and separated by means of normal GC analysis. The heating temperature/desorption time was either 90°C/30 minutes (cycle A) or 120°C/60 minutes (cycle B).
  • the total GC peaks surface area was tallied up and given as toluene equivalents (ppm toluene), being the quantity of toluene that would give the same peak area when analysed under the same conditions.
  • the effect of volatile matter in cross-linked materials was analyzed by determining fogging in accordance with method DIN 75201 (gravimetrically).
  • the blooming of peroxide decomposition products and other ingredients on the surface of rubber sheets was determined visually.
  • the sheets were stored in sealed glass bottles at room temperature. After a defined time period (1 week / 1 month) the rubber sheets were inspected visually. If the surface of the rubber sheets remained glossy, they were said not to show blooming. When the surface was not glossy or was covered with crystals, the sheets were said to show blooming.
  • Example 6 When analysed for extractable/volatile matter, the product of Example 6 showed that a total of 2,180 ppm of C 6 H 3 -(C(CH 3 ) 2 -OH) 3 and CH 3 C(O)- C 6 H 3 -(C(CH 3 ) 2 -OH) 2 could be extracted, while the product of Comparative Example I contained 4,500 ppm of such extractable compounds.
  • Head space GC analysis using cycles A and B showed the product of Example 6 to contain 150 and 850 ppm toluene, respectively, while the product of Comparative Example I contained 165 and 1 ,700 ppm toluene, respectively. Each number is the average result of two samples.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne l'utilisation de copolymères contenant des fractions de dérivés oléfiniques ainsi que des fractions d'anhydride et/ou des fractions d'acides lors de la réticulation de polymères/élastomère utilisant des radicaux libres obtenus par décomposition d'un peroxyde. Les produits réticulés ne présentent généralement pas de dispersion et des niveaux très bas de composés volatiles lorsqu'on les compare à des produits réticulés en absence dudit copolymère.
EP00965960A 1999-09-03 2000-09-01 Produits reticules ne presentant pas de dispersion et a nebulisation reduite Withdrawn EP1208120A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP00965960A EP1208120A1 (fr) 1999-09-03 2000-09-01 Produits reticules ne presentant pas de dispersion et a nebulisation reduite

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
EP99202867 1999-09-03
EP99202867 1999-09-03
US16384199P 1999-11-05 1999-11-05
US163841P 1999-11-05
PCT/EP2000/008843 WO2001018074A1 (fr) 1999-09-03 2000-09-01 Produits reticules ne presentant pas de dispersion et a nebulisation reduite
EP00965960A EP1208120A1 (fr) 1999-09-03 2000-09-01 Produits reticules ne presentant pas de dispersion et a nebulisation reduite

Publications (1)

Publication Number Publication Date
EP1208120A1 true EP1208120A1 (fr) 2002-05-29

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP00965960A Withdrawn EP1208120A1 (fr) 1999-09-03 2000-09-01 Produits reticules ne presentant pas de dispersion et a nebulisation reduite

Country Status (4)

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EP (1) EP1208120A1 (fr)
JP (1) JP2003508603A (fr)
AU (1) AU7652700A (fr)
WO (1) WO2001018074A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2360021T3 (es) * 2007-10-09 2011-05-31 Basf Se Aglutinante acuoso para sustratos fibrosos o granulares.
EP2851394B1 (fr) 2013-09-19 2016-09-14 Arlanxeo Netherlands B.V. Composition de caoutchouc vulcanisable pour articles à faible nébulisation
JP6324545B2 (ja) 2014-06-12 2018-05-16 アクゾ ノーベル ケミカルズ インターナショナル ベスローテン フエンノートシャップＡｋｚｏ Ｎｏｂｅｌ Ｃｈｅｍｉｃａｌｓ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｂ．Ｖ． ポリプロピレンの溶融強度を増強する方法
EP3387055B1 (fr) 2015-12-08 2019-08-28 Nouryon Chemicals International B.V. Procédé de réduction de la formation de buée à partir de polypropylène à résistance élevée à la fusion

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US3257346A (en) * 1961-08-07 1966-06-21 Phillips Petroleum Co Rubbery polymer-acidic carbon black-carboxylic acid mixtures cured with organic peroxides
FR1336414A (fr) * 1961-08-21 1963-08-30 Phillips Petroleum Co Réduction de l'écoulement à froid du polybutadiène-cis
NL302786A (fr) * 1963-02-21 1900-01-01
US3420891A (en) * 1966-12-08 1969-01-07 Wallace & Tiernan Inc Tris-peroxides from 1,3,5-triisopropylbenzene
US3562304A (en) * 1968-02-13 1971-02-09 North American Rockwell Ablative composition of matter
US4268637A (en) * 1979-06-07 1981-05-19 Hercules Incorporated Elimination of bloom in [vul-cup] peroxide crosslinked elastomer compounds
FR2559774A1 (fr) * 1984-02-17 1985-08-23 Neste Oy Procede pour ameliorer les proprietes adhesives des polyolefines
US4774293A (en) * 1985-06-26 1988-09-27 Akzo N.V. Process for cross-linking or degrading polymers and shaped articles obtained by this process
CA1335911C (fr) * 1986-10-29 1995-06-13 Shizuo Shimizu Composition thermoplastique d'elastomere
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KR920005384B1 (ko) * 1988-11-21 1992-07-02 미쓰이세끼유 가가꾸고오교오 가부시끼 가이샤 변성 폴리올레핀입자 및 그의 제조방법
JP2794867B2 (ja) * 1990-01-08 1998-09-10 住友電気工業株式会社 反応性酸化防止剤およびこれを含有する高分子組成物
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Publication number Publication date
AU7652700A (en) 2001-04-10
WO2001018074A1 (fr) 2001-03-15
JP2003508603A (ja) 2003-03-04

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