EP1123347A1 - Resines aromatiques de monovinylidene - Google Patents

Resines aromatiques de monovinylidene

Info

Publication number
EP1123347A1
EP1123347A1 EP99942100A EP99942100A EP1123347A1 EP 1123347 A1 EP1123347 A1 EP 1123347A1 EP 99942100 A EP99942100 A EP 99942100A EP 99942100 A EP99942100 A EP 99942100A EP 1123347 A1 EP1123347 A1 EP 1123347A1
Authority
EP
European Patent Office
Prior art keywords
resin
monovinylidene aromatic
percent
weight
aromatic resin
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Withdrawn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
EP99942100A
Other languages
German (de)
English (en)
Inventor
William C. Pike
Jerry L. Hahnfeld
Kurt A. Koppi
Mehemet Demirors
John L. Sugden
Gary C. Welsh
Brent A. Salamon
Luc Bosiers
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.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
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 Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP1123347A1 publication Critical patent/EP1123347A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or 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; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • MONOVINYLIDENE AROMATIC RESINS The process of the present invention relates to monovinylidene aromatic resins.
  • Monovinylidene aromatic resins have been used in applications such as foam sheet, extrusion and oriented articles.
  • Plasticizers have typically been used in such resins to increase the flow and increase the rate of production of molded or extruded articles.
  • plasticizers such as mineral oil, significantly lower the glass transition temperature (Tg) of the resin. This can slow the production time, since the products produced must be cooled to a lower temperature for adequate setting to occur prior to mold removal.
  • Tg glass transition temperature
  • the use of plasticizers such as limonene add significant cost to the resins, making their use undesirable.
  • JP-08-172959 discloses a method of modifying aromatic plastics by compounding styrene oligomers having a molecular weight of 2200-3800 and a polydispersity of 1.6 to 2.1 with aromatic plastics such as polystyrene.
  • the polystyrene compositions disclosed still have significantly reduced Tg due to the presence of mineral oil plasticizer in Styron 666 and the flexural strength is significantly reduced.
  • the present invention is a monovinylidene aromatic resin having a bimodal weight average molecular weight (Mw) distribution such that 85 to 95 percent by weight of the resin is a fraction having an average Mw of from 250,000 to 400,000 and from 2 to 15 percent by weight of the resin is a fraction having a Mw of 1 ,000 to 20,000, wherein each fraction has a polydispersity (Mw/Mn) of from 1.5 to 3.0.
  • Mw weight average molecular weight
  • This resin has good flow and Tg properties and can be used in various applications, such as injection molding, foam sheet and oriented polystyrene extruded sheet, resulting in increased production rates.
  • the present invention is a monovinylidene aromatic resin having a specific Mw profile having an improved balance of melt flow and strength without the addition of a traditional plasticizer.
  • the monovinylidene aromatic resin has a bimodal Mw distribution such that 85 to 95 percent by weight of the resin has an average Mw of from 250,000 to 400,000 and from 2 to 15 percent by weight of the resin has a Mw of 1 ,000 to 20,000, wherein each fraction has a polydispersity (Mw/Mn) of from 1.5 to 3.0.
  • Monovinylidene aromatic polymers suitable for the process of the present invention are those produced by polymerizing a vinyl aromatic monomer.
  • Vinyl aromatic monomers include, but are not limited to those described in US-A-4,666,987, US-A-4,572,819 and US-A-4,585,825.
  • the monomer is of the formula:
  • Ar is an aromatic ring structure having from 1 to 3 aromatic rings with or without alkyl, halo, or haloalkyl substitution, wherein any alkyl group contains 1 to 6 carbon atoms and haloalkyl refers to a halo substituted alkyl group.
  • Ar is phenyl or alkylphenyl, wherein alkylphenyl refers to an alkyl substituted phenyl group, with phenyl being most preferred.
  • Typical vinyl aromatic monomers which can be used include: styrene, alpha-methylstyrene, all isomers of vinyl toluene, especially paravinyltoluene, all isomers of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, and mixtures thereof.
  • the vinyl aromatic monomers may also be combined with other copolymerizable monomers.
  • Examples of such monomers include, but are not limited to acrylic monomers such as acrylonitrile, methacrylonitrile, methacrylic acid, methyl methacrylate, acrylic acid, and methyl acrylate; maleimide, phenylmaleimide, and maleic anhydride.
  • the polymerization of the vinyl aromatic monomer may be conducted in the presence of predissolved elastomer to prepare impact modified, or grafted rubber containing products, examples of which are described in US-A-3,123,655, US-A-3,346,520, US-A-3,639,522, and US-A-4,409,369.
  • Polymerization processes and process conditions for the polymerization of vinyl aromatic monomers are well known in the art. Although any polymerization process can be used, typical processes are continuous bulk or solution polymerizations as described in US-A-2,727,884 and US-A-3,639,372. Cationic polymerization processes can also be used, especially in preparing the low molecular weight component. Such processes are well known in the art such as in US-A-4,087,599, US-A-4,161 ,573 and US-A-4,112,209.
  • the major proportion of the monovinylidene aromatic resin is a high molecular weight fraction.
  • at least 85 percent, preferably at least 90 percent and most preferably at least 95 percent of the resin has a molecular weight from 250,000, preferably from 260,000, more preferably from 270,000 and most preferably from 280,000 to 400,000, preferably to 375,000, more preferably to 350,000 and most preferably to 325,000.
  • the resin also contains a lower molecular weight fraction which is typically from 2 percent, preferably from 2.5 percent, more preferably from 3 percent and most preferably from 3.5 percent, and even more preferably from 5 percent to 15 percent, preferably to 12 percent and most preferably to 10 percent, and even more preferably to 8 percent by weight.
  • This lower molecular weight fraction has a Mw which is typically from 1 ,000, preferably from 1 ,500, more preferably from 2,000 and most preferably from 2,500 to 20,000, preferably to 18,000, more preferably to 16,000 and most preferably to 14,000.
  • Mw which is typically from 1 ,000, preferably from 1 ,500, more preferably from 2,000 and most preferably from 2,500 to 20,000, preferably to 18,000, more preferably to 16,000 and most preferably to 14,000.
  • Molecular weight values are measured using gel permeation chromatography techniques (GPC) which are well known in the art.
  • the polydispersity (weight average molecular weight(Mw))/(number average molecular weight (Mn)) for each fraction described above is typically from 1.5, preferably from 1.6, more preferably from 1.7 and most preferably from 1.8 to 3.0, preferably to 2.8, more preferably to 2.7 and most preferably to 2.6. It has been discovered that resins falling within this bimodal Mw profile have excellent flow and Tg properties without using plasticizers such as mineral oil.
  • Typical polymer additives can also be included in the resin of the present invention, including antioxidants, stabilizers, mold release agents, and chain transfer agents
  • the high Mw fraction and the low Mw fraction are made in separate reactors and combined in the appropriate proportions to produce the resin of the present invention.
  • the individual resins can be made simultaneously and combined within the same process or the two resins can be blended using any blending method including solution or dry blending.
  • the resin of the present invention can also be produced within one continuous process wherein the low molecular weight fraction is produced in situ while producing the high molecular weight fraction within the same process. This can be accomplished using methods described in EP-797,600.
  • the monovinylidene aromatic polymer is a polystyrene resin having a high molecular weight fraction of at least 320,000 and a low molecular weight fraction of from 1 ,000 to 20,000, which is used to produce foam sheet.
  • Methods of producing foam sheet are well known in the art, any of which can be used to produce foam sheet from the resin of the present invention.
  • Typical blowing agents include carbon dioxide, hydrochlorofluorocarbons, and alcohols, mixtures thereof.
  • the lower molecular weight fraction increases the flow of the polystyrene resin without substantially lowering the Tg, thus production can occur at higher rates compared to resins containing plasticizers which lower the Tg.
  • the monovinylidene aromatic resin of the present invention can also be used in blends with other polymers, such as high impact monovinylidene aromatic polymers. These blends can be used in applications such as form-fill-seal products, especially yogurt type containers.
  • the monovinylidene aromatic resin of the present invention can also be used in various applications including foam sheet, meat trays, egg cartons, cups, biaxially oriented sheet, injection molded articles and oriented products.
  • foam sheet, meat trays, egg cartons, cups, biaxially oriented sheet, injection molded articles and oriented products are provided to illustrate the present invention. The examples are not intended to limit the scope of the present invention and they should not be so interpreted. Amounts are in weight parts or weight percentages unless otherwise indicated. EXAMPLE 1
  • a solution of 3.5 weight percent low molecular weight polystyrene (Mw 1 ,400, Mn 660), 3.0 percent ethylbenzene, 93.5 percent styrene, 75 ppm of 1 ,1-bis(tert- butylperoxy)cyclohexane initiator and 25 ppm sulfoethyl methacrylate is passed through a series of stirred tube reactors with a temperature gradient from 128 to 150°C.
  • a slurry of zinc stearate in ethylbenzene is added halfway through the reactors such that the final concentration of zinc stearate in the product is approximately 1200 ppm.
  • the partial polymer is devolatilized at 230°C and 10 mm, followed by pelletization, to give a bimodal polystyrene resin with 94.5 percent of the resin having a Mw of 328,000 (Mn of 134,000) and 5.5 percent having a Mw of 1 ,400.
  • This resin exhibits an enhanced flow rate (MFR of 2.5 vs. 1) over monomodal high MW prepared from styrene under identical polymerization conditions while decreasing the Tg of the resin only slightly (106°C vs. 108°C).
  • the following molding conditions are used for ASTM specimen molding:
  • Control 1 and 2 are StyronTM 685 D available from The Dow Chemical Company.
  • Un-notched Izod (kg-cm/cm) 20 20 37 Fill time (seconds) 0.7 unavailable 0.49 Hold time (seconds) 0.6 unavailable 0.7 Cooling time (seconds) 2.6 2.2 2 Plastication time (seconds) 3.87 4.05 3.41 Cycle time (seconds) 7.2 7.4 6.75
  • the bimodal resin is also used to produce foam sheet and meat trays therefrom.
  • Meat trays are manufactured using a continuos roll fed thermoformer where a roll of the bimodal resin foam sheet (produced using a tandem extrusion process) is passed through a heated oven and is heated to a temperature sufficient to soften and expand the sheet. The expanded foam sheet is vacuum formed into meat trays and cooled. The formed sheet containing the meat trays is mechanically cut to form the trays. The remaining portion of the sheet or web is fed into a grinder, re-ground and later extruded into additional foam sheet.
  • the typical gauge and density of foam sheet used to make meat trays is 110 to 125 mils and 48 to 56 g/l, respectively.
  • a resin blend of 80 percent high heat general purpose polystyrene (STYRONTM 685D) and 20 percent STYRONTM 685D regrind and a resin blend of 80 percent bimodal polystyrene resin as prepared above and 20 percent bimodal polystyrene resin regrind are extruded and compared using a commercial tandem extrusion process (two extruders in series).
  • foam sheet samples are made with the same gauge, density, basis wt. and cell size. These parameters are controlled by adjusting the percent blowing agent, percent talc, and the rate at which the sheet is pulled.
  • the blowing agent is a blend of hydrocarbon and carbon dioxide. The carbon dioxide was the lesser of the two blowing agent components.
  • Post expansion is the amount the foam sheet expands versus its initial gauge within a thermoformer.
  • Post expansion of the meat trays is measured by measuring stacks of 125 number 2 type meat trays for their overall average heights. The results are listed in Table IV. The bimodal resin shows a 7 percent increase in stack height. TABLE IV Stack Height of 125 Number 2 Type Meat Trays

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une résine aromatique de monovinylidène présentant une distribution bimodale ayant une distribution bimodale du poids moléculaire moyen (Mw) en poids telle que 85 à 95 % en poids de la résine à un Mw compris entre 250000 et 400000 et de 2 à 15 % en poids de la résine a un Mw de 1000 à 20000, chacune des fractions ayant une polydispersité (Mw/Mn) de 1,5 à 3,0.
EP99942100A 1998-09-09 1999-08-11 Resines aromatiques de monovinylidene Withdrawn EP1123347A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US9957298P 1998-09-09 1998-09-09
US99572P 1998-09-09
PCT/US1999/018221 WO2000014157A1 (fr) 1998-09-09 1999-08-11 Resines aromatiques de monovinylidene

Publications (1)

Publication Number Publication Date
EP1123347A1 true EP1123347A1 (fr) 2001-08-16

Family

ID=22275652

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99942100A Withdrawn EP1123347A1 (fr) 1998-09-09 1999-08-11 Resines aromatiques de monovinylidene

Country Status (5)

Country Link
EP (1) EP1123347A1 (fr)
CN (1) CN1317036A (fr)
AU (1) AU5554899A (fr)
CO (1) CO5050401A1 (fr)
WO (1) WO2000014157A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004044087A1 (de) * 2004-09-09 2006-03-16 Tesa Ag Funktionalisierte Polymere
DE112005001945A5 (de) 2004-09-09 2007-08-02 Tesa Ag Verfahren zur Herstellung von acrylhaltigen Haftklebemassen
TW200837129A (en) * 2007-01-10 2008-09-16 Albemarle Corp Brominated styrenic polymer compositions and processes for producing same
TW200838919A (en) * 2007-01-10 2008-10-01 Albemarle Corp Brominated styrenic polymer compositions and processes for producing same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2864802A (en) * 1955-11-28 1958-12-16 Dow Chemical Co Molding compositions of high molecular weight and low molecular weight polymers
DE2239356A1 (de) * 1972-08-10 1974-02-21 Basf Ag Styrolpolymerisate mit verbesserter fliessfaehigkeit
HU220442B1 (hu) * 1993-06-04 2002-02-28 The Dow Chemical Company Eljárás polimer hab előállítására és habosításra alkalmas, javított tulajdonságú képlékeny elegy és hab
JPH09328589A (ja) * 1996-06-12 1997-12-22 Yasuhara Chem Kk 芳香族系プラスチックの改質方法

Non-Patent Citations (1)

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Title
See references of WO0014157A1 *

Also Published As

Publication number Publication date
CN1317036A (zh) 2001-10-10
CO5050401A1 (es) 2001-06-27
WO2000014157A1 (fr) 2000-03-16
AU5554899A (en) 2000-03-27

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