EP2104702A1 - Expandable polystyrene of reduced blowing agent content - Google Patents

Expandable polystyrene of reduced blowing agent content

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Publication number
EP2104702A1
EP2104702A1 EP07854713A EP07854713A EP2104702A1 EP 2104702 A1 EP2104702 A1 EP 2104702A1 EP 07854713 A EP07854713 A EP 07854713A EP 07854713 A EP07854713 A EP 07854713A EP 2104702 A1 EP2104702 A1 EP 2104702A1
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
weight
parts
expandable polystyrene
beads
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Withdrawn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
EP07854713A
Other languages
German (de)
French (fr)
Inventor
Jürgen SCHELLENBERG
Petra Dehnert
Regina Pinkert
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 Global Technologies LLC
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Dow Global Technologies LLC
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Filing date
Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Publication of EP2104702A1 publication Critical patent/EP2104702A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene

Definitions

  • This invention relates to expandable polystyrene.
  • the invention relates to expandable polystyrene comprising a blowing agent while in another aspect, the invention relates to expandable polystyrene comprising an organic blowing agent.
  • the invention relates to construction insulation and packaging materials.
  • expandable polystyrene (i) with a reduced content of organic, volatile blowing agent, (ii) with sufficient pre-foaming and foaming behavior in standard processing equipment, and (iii) that produces low-density pre-foamed polystyrene beads that can be fabricated into high-quality foam, is desirable.
  • Japanese Unexamined Patent Application No. 2001-201140 teaches styrene-type expandable resin particles comprising:
  • At least one plasticizer selected from paraffins that are liquid at ambient temperature or esters with a boiling point of at least 200C, and
  • an expansion agent e.g., 1-20 wt% butane, pentane and the like.
  • These styrene-type expandable resin particles are described as having excellent expansion properties that can achieve excellent mechanical strength in expansion-molded articles with little release of aromatic solvents.
  • relatively high levels of expansion agent are needed to produce resins with lower bulk densities, and the foam beads of these resins exhibit an undesirable hard and tough structure.
  • expandable polystyrene (i) with a reduced content of organic, volatile blowing agent, (ii) that exhibits conventional or superior pre- foaming and foaming behavior in standard processing equipment, and (iii) that produces low-density pre- foamed polystyrene beads that can be fabricated into high-quality foam sheets, is described.
  • the polystyrenes of this embodiment are easily and conventionally fabricated into construction insulation and packaging materials.
  • the expandable polystyrene composition comprises:
  • A 100 parts by weight of at least one styrene polymer or copolymer or a mixture of the two;
  • the expandable polystyrene used in the practice of this invention comprises units derived from at least one alkenyl aromatic monomer having the general formula:
  • Ar represents an aromatic hydrocarbon radical or an aromatic halohydrocarbon radical of the benzene series
  • R is hydrogen, a methyl group, or an ethyl group.
  • alkenyl aromatic polymers are the solid homopolymers of styrene, alpha-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ethylstyrene, vinylxylene, chlorostyrene, bromostyrene, vinyl toluene, or the solid copolymers of one or more of such alkenyl aromatic compounds with other copolymerizable monomers such as acrylonitrile, anhydrides of maleic or itaconic acids, acrylic or methacrylic acid, or rubber- reinforced (either synthetic or natural) styrene polymers, and the like.
  • the ester used in the practice of this invention is the reaction product of a saturated monocarboxylic acid having about 14-20 carbons and an alkyl alcohol having 3-5 carbon atoms.
  • Representative saturated monocarboxylic acids include myristic, palmitic, stearic, oleic, linoleic, linolenic, and the like.
  • Representative alkyl alcohols include propanol, isopropanol, 1 -butanol, isobutanol, tert-butanol, pentanol and tert-pentanol.
  • the ester is the ester of an unbranched saturated monocarboxylic acid having about 14-20 carbons and an alkyl alcohol having 3-5 carbon atoms, and more preferably the alcohol is a branched or unbranched alcohol of 4 carbon atoms.
  • One preferred ester is isobutyl stearate. More than one ester, i.e., a mixture of esters, can be used in the practice of the invention.
  • the ester, or mixture of esters is used in an amount of between about 0.01-2.2, preferably between about 0.1-2.0 and more preferably between about 0.2-1.7, parts by weight.
  • the at least one unsaturated aliphatic hydrocarbon used in the practice of this invention comprises about 20-60, preferably about 25-50, carbon atoms.
  • the unsaturated hydrocarbon used in this invention is a mixture of unsaturated hydrocarbons, and more preferably the mixture is further characterized as having a mass loss based on evaporation of at least about 50, preferably at least about 70, wt% in a temperature range from about 300-400 0 C measured by thermo gravimetric analysis (TGA) using TG/DTA 220 of Seiko at a heating rate of 10° Kelvin/minute (K/min) and an inert gas flow, e.g., argon, at a rate of 300 milliliters/minute (ml/min).
  • TGA thermo gravimetric analysis
  • the sample size for this measurement is about 20 milligrams (mg), and the evaporation loss is measured as the sample temperature is raised at a rate of 10K/min from 300 to 400 0 C in the presence of an argon flow of 300 ml/min.
  • Representative saturated hydrocarbons that can be used in mixtures as the third or (C) component of the expandable polystyrene include triacontane, 2,6,10,15,19,23-hexamethyltetracosane, hexatricosane, tetracosane and cyclotetraconsane.
  • the amount of saturated hydrocarbon, in either neat or mixture format, used in the practice of this invention is typically between about 0.01 and about 2.0, preferably between about 0.05 and about 1.8 and more preferably between about 0.10 and about 1.6, parts by weight.
  • the mono-alkylbenzene with an alkyl group having 3-5 carbon atoms is used in an amount of between about 0.0001 and about 0.5, preferably between about 0.001 and about 0.4 and more preferably between about 0.002 and about 0.2 parts by weight.
  • Representative mono-alkylbenzenes with a C 3 _ 5 , preferably a C 4 , alkyl group include propylbenzene, isopropylbenzene, butylbenzene, isobutylbenzene, tert-butylbenzene, pentylbenzene, isopentylbenzene and tert-pentylbenzene.
  • Isopropylbenzene is a preferred mono-alkylbenzene.
  • the total amount of ester, saturated aliphatic hydrocarbon and mono-alkylbenzene in the expandable polystyrene typically does not exceed about 3.8, preferably 3.6 and more preferably 3.5 parts by weight.
  • the minimum amount of the combined ester, saturated aliphatic hydrocarbon and mono-alkylbenzene content of the expandable polystyrene is typically at least about 0.02, preferably at least about 0.1 and more preferably at least about 0.2 parts by weight.
  • the expandable polystyrene can comprise one or more other additives in a total amount from about 0.1 to about 15, preferably from about 2 to about 14 and more preferably from about 3 to about 12 parts by weight.
  • additives if used, can be used alone or in combination with one another, and include such materials as fillers, pigments, lubricants, fire retardants, blowing agents, wetting agents, antioxidants, ignition resistant compounds, stabilizers and co-stabilizers (also known as extenders), and the like.
  • Fillers include talc, calcium silicate, barium and zinc stearate and magnesium oxide.
  • Flame retardants include a variety of halogenated compounds of which brominated compounds are preferred, e.g., hexabromocyclododecane, 2,2-bis(4-hydroxyethoxy-3,5- dibromophenyl) propane, 2,2-bis (4-(2,3-dibromo)propyloxy-3,5-dibromophenyl propane, tribromophenol and the like.
  • Blowing agents include n-butane, isobutane, n-pentane, isopentane, halogenated alkanes, water, carbon dioxide, ethyl chloride, nitrogen and mixtures of two or more of these agents.
  • Stabilizers include the various phosphates or sulphates, and the co- stabilizers or extenders include a wide array of materials, e.g., unsaturated mono-, di- and tricarboxylic acids such as acrylic, methacrylic, crotonic, sorbic, maleic, fumaric, citraconic, mesaconic, itaconic and aconitic acid, sodium bisulfite, alkaline salts of alkylaryl sulphonic acids, alkylsulphonic acids and alkyl sulphates with an alkyl chain length of C 2-20 , such as sodium dodecylbenzenesulfonate, sodium tetradecylsulphate, potassium stearate, compounds containing a terminal vicinal hydroxy-keto structure such as fructose, sorbose, 1,3-dihydroxy-acetone, monohydroxy acetone and invert sugar, vinyl sulphonate, and di-isobutyl n
  • additives examples include methyl methacrylate type copolymers, polyethylene wax, ethylene bis-stearylamide, methylene bis-stearylamide, and ethylene- vinyl acetate copolymer resin.
  • any conventional process can be used to make the expandable polystyrene.
  • One typical process is the polymerization of styrene and/or other alkenyl aromatic monomer in an aqueous suspension to form resin particles or beads.
  • the process can include the simultaneous incorporation or impregnation of a blowing agent into the beads, or the beads can be impregnated with the blowing agent in a post-polymerization step.
  • the resulting expandable polymer beads can then be expanded into polystyrene foam by any conventional process.
  • One typical process comprises the steps of (i) expanding the beads by mixing them with steam in a stirred tank, (ii) stabilizing the beads, e.g., exposing them to air, and (iii) welding the beads together in heated molds.
  • the expanded polystyrene foams of this invention can be made into various shapes for various end use applications. Exemplary shapes and applications include sheets and boards for construction insulation and packaging, shock absorbing foam liners for protective helmets and other sport gear, containers for plant cultivation, rings for life preservers, balls and "peanuts" for loose packaging, components in appliances and vehicles, sculptures for stage and film use, heads for wigs and the like.
  • Expandable polystyrene beads without a reduced content of blowing agent were received by suspension polymerization of styrene.
  • the impregnated polystyrene beads were separated from the liquid phase by filtration and centrifugation, and then dried under air, yielding expandable polystyrene beads with water, volatile residuals and residual styrene monomer content, number average molecular weight (Mn), weight average molecular weight (Mw), and polydispersity (MWD) as reported in Table 1.
  • the residual styrene monomer content was determined by gas chromatography.
  • Expandable polystyrene beads with a reduced content of blowing agent were prepared using the suspension polymerization procedure of Comparative Example A with the following modifications: (a) also dissolved in the styrene monomer were (i) isopropylbenzene (0.775g) as a mono-alkylbenzene with a branched alkyl group having 3 to 5 carbon atoms, (ii) isobutyl stearate (11.6g) as an ester of a saturated monocarboxylic acid having 14 to 20 carbon atoms with an alkyl alcohol having 3 to 5 carbon atoms, and (iii) a mixture (11.6g) of saturated aliphatic hydrocarbons having 29 to 43 carbon atoms with a mass loss based on evaporation of 83.5 wt% in a temperature range from 300 to 400 0 C by thermogravimetric analysis (TGA) at a heating rate of 10 K/min and at an inert gas rate of 300 ml/min, all related to
  • the properties of the expandable polystyrene beads are also reported in Table 1 , and the foaming behavior properties of the polystyrene beads are described in Table 2. Comparing the properties of these two polystyrene foam beads shows that the same pre- foaming density of 15.6 grams/liter (g/1) can be achieved at a much lower initial pentane concentration (3.0 wt%) while maintaining the same desirable structure of the beads.
  • Example 1 was repeated with the following modifications: isopropylbenzene (20.15g) was used as a mono-alkylbenzene with a branched alkyl group having 3 to 5 carbon atoms but without any addition of (i) an ester of a saturated monocarboxylic acid having 14 to 20 carbon atoms with an alkyl alcohol having 3 to 5 carbon atoms, and (ii) a mixture of saturated aliphatic hydrocarbons having 20 to 60 carbon atoms with a mass loss based on evaporation of at least 50 wt% in a temperature range from 300 0 C to 400 0 C by TGA at a heating rate of 10° K/min and at an inert gas flow rate of 300 ml/min.
  • Styrene monomer was suspension polymerized to produce expandable polystyrene beads with a reduced content of blowing agent according to the procedure of Comparative Example B.
  • isopropylbenzene (20.15g) as a mono- alkylbenzene with a branched alkyl group having 3 to 5 carbon atoms
  • isobutyl stearate (20.15g) as an ester of a saturated monocarboxylic acid having 14 to 20 carbon atoms with an alkyl alcohol having 3 to 5 carbon atoms was fed to the polymerization reactor without any mixture of saturated aliphatic hydrocarbons having 20 to 60 carbon atoms with a mass loss based on evaporation of at least 50 wt% in a temperature range from 300 0 C to 400 0 C by TGA at a heating rate of 10° K/min and at an inert gas rate of 300 ml/min.
  • the properties of these foam beads are reported in Tables 1 and 2 and although their pre- foaming density
  • expandable polystyrene beads with a reduced content of blowing agent were manufactured by suspension polymerization without any ester of a saturated monocarboxylic acid having 14 to 20 carbon atoms with an alkyl alcohol having 3 to 5 carbon atoms, but in this instance with a mixture (20.15g) of saturated aliphatic hydrocarbons having 29 to 43 carbon atoms with a mass loss based on evaporation of 83.5 wt% in a temperature range from 300 0 C to 400 0 C by TGA at a heating rate of 10° K/min and at an inert gas rate of 300 ml/min.
  • the properties of the foam beads are reported in Tables 1 and 2 and as is readily evident from this data, a low pre-foaming density could not be achieved with this composition.
  • the structure of the foam beads was hard and tough.
  • Comparative Examples B, C and D show that expandable polystyrene beads and the subsequent polystyrene foam with a reduced content of blowing agent and other desirable properties, e.g., low density, cannot be made using only one or two of the three components of the inventive composition. Comparative Example E
  • expandable polystyrene beads with a reduced content of blowing agent were made except that isopropylbenzene (0.775g) as a mono- alkylbenzene with a branched alkyl group having 3 to 5 carbon atoms, isobutyl stearate (5.8Ig) as an ester of a saturated monocarboxylic acid having 14 to 20 carbon atoms with an alkyl alcohol having 3 to 5 carbon atoms, and a mixture (7.75g) of saturated aliphatic hydrocarbons having 29 to 43 carbon atoms with a mass loss based on evaporation of 83.5 wt% in a temperature range from 300 0 C to 400 0 C by TGA at a heating rate of 10° K/min and at an inert gas rate of 300 ml/min were dissolved in styrene and pentane (38.7g), were used.
  • the properties of the foam beads made in this example are reported in Tables 1
  • expandable polystyrene beads with a reduced content of blowing agent were made except that isopropylbenzene (0.775g) as a mono- alkylbenzene with a branched alkyl group having 3 to 5 carbon atoms, isobutyl stearate (7.75g) as an ester of a saturated monocarboxylic acid having 14 to 20 carbon atoms with an alkyl alcohol having 3 to 5 carbon atoms, and a mixture (11.6g) of saturated aliphatic hydrocarbons having 29 to 43 carbon atoms with a mass loss based on evaporation of 83.5 wt% in a temperature range from 300° to 400 0 C by TGA at a heating rate of 10° K/min and at an inert gas rate of 300 ml/min were dissolved in styrene and pentane (38.7g), were used.
  • the properties of the foam beads made in this example are reported in Tables 1 and 2, and these
  • expandable polystyrene beads with a reduced content of blowing agent were made except that isopropylbenzene (0.775g) as a mono- alkylbenzene with a branched alkyl group having 3 to 5 carbon atoms, isobutyl stearate (3.87g) as an ester of a saturated monocarboxylic acid having 14 to 20 carbon atoms with an alkyl alcohol having 3 to 5 carbon atoms, and a mixture (3.87g) of saturated aliphatic hydrocarbons having 29 to 43 carbon atoms with a mass loss based on evaporation of 83.5 wt% in a temperature range from 300 0 C to 400 0 C by TGA at a heating rate of 10° K/min and at an inert gas rate of 300 ml/min were dissolved in styrene and pentane (38.7g), were used.
  • the properties of the foam beads made in this example are reported in Tables 1 and
  • the flame retardant behavior of the expandable polystyrene beads made in this example was also investigated.
  • Test specimens were prepared according to the procedure of DIN 4102. The specimens were prepared by sieving, coating, pre- foaming and drying the pre-foamed beads for 24 hours at 7OC, then foaming the beads in a block mold, cutting the specimens to size and storing the specimens for 24 hours at 70 0 C.
  • the flame retardant behavior of the test specimens was measured using the B2 test method of DIN 4102, and the results are reported in Table 3. These results demonstrate the excellent flame retardant behavior of the polystyrene foam.
  • the foam block exhibited a smooth surface with good sealing of the foam beads and an absence of lumps or plugs in the mold.

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Abstract

An expandable polystyrene composition having a reduced content of blowing agent comprises: A. 100 parts by weight of at least one styrene polymer or copolymer or a mixture of the two; B. About 0.01 to about 2.2 parts by weight of at least one ester of at least one C14-20 saturated monocarboxylic acid with at least one C3-5 alkyl alcohol; C. About 0.01 to about 2.0 parts by weight of at least one C20-60 saturated aliphatic hydrocarbon; D. About 0.0001 to about 0.5 parts by weight of at least one mono- alkylbenzene with a C3-5 alkyl group; and E. About 0.1 to about 15 parts by weight of at least one expandable polystyrene additive; with the proviso that the amount of components B, C and D does not exceed about 3.8 parts by weight.

Description

EXPANDABLE POLYSTYRENE OF REDUCED BLOWINGAGENT CONTENT
FIELD OF THE INVENTION This invention relates to expandable polystyrene. In one aspect, the invention relates to expandable polystyrene comprising a blowing agent while in another aspect, the invention relates to expandable polystyrene comprising an organic blowing agent. In another aspect, the invention relates to construction insulation and packaging materials.
BACKGROUND OF THE INVENTION Lowering the amount of organic, volatile blowing agent in expandable polystyrene is a desirable goal for various environmental, health and safety reasons. However, too low an amount of such a blowing agent, or a complete substitution of such a blowing agent with one or more other blowing agents, can produce a significant deterioration in the foaming behavior of the polystyrene beads. Poor foaming behavior can produce pre- foamed polystyrene beads of greater density and/or reduced or complete loss of processability on standard process equipment. As such, expandable polystyrene (i) with a reduced content of organic, volatile blowing agent, (ii) with sufficient pre-foaming and foaming behavior in standard processing equipment, and (iii) that produces low-density pre-foamed polystyrene beads that can be fabricated into high-quality foam, is desirable.
Japanese Unexamined Patent Application No. 2001-201140 teaches styrene-type expandable resin particles comprising:
A. 0.1 percent by weight (wt%) or less of residual styrene monomer,
B. 0.2 wt% or less of the sum of aromatic solvents such as ethylbenzene, toluene, o-xylene, m-xylene, p-xylene, isopropylbenzene, n-propylbenzene and the like,
C. 0.1-5 wt% of at least one plasticizer selected from paraffins that are liquid at ambient temperature or esters with a boiling point of at least 200C, and
D. an expansion agent, e.g., 1-20 wt% butane, pentane and the like. These styrene-type expandable resin particles are described as having excellent expansion properties that can achieve excellent mechanical strength in expansion-molded articles with little release of aromatic solvents. However, relatively high levels of expansion agent are needed to produce resins with lower bulk densities, and the foam beads of these resins exhibit an undesirable hard and tough structure.
SUMMARY OF THE INVENTION
In one embodiment of this invention, expandable polystyrene (i) with a reduced content of organic, volatile blowing agent, (ii) that exhibits conventional or superior pre- foaming and foaming behavior in standard processing equipment, and (iii) that produces low-density pre- foamed polystyrene beads that can be fabricated into high-quality foam sheets, is described. The polystyrenes of this embodiment are easily and conventionally fabricated into construction insulation and packaging materials.
In another embodiment of the invention, the expandable polystyrene composition comprises:
A. 100 parts by weight of at least one styrene polymer or copolymer or a mixture of the two;
B. About 0.01 to about 2.2 parts by weight of an ester of at least one saturated monocarboxylic acid having 14 to 20 carbon atoms with at least one alkyl alcohol having 3 to 5 carbon atoms;
C. About 0.01 to about 2.0 parts by weight of at least one saturated aliphatic hydrocarbon having about 20. to about 60 carbon atoms;
D. About 0.0001 to about 0.5 parts by weight of at least one mono- alkylbenzene with an alkyl group having 3 to 5 carbon atoms; and
E. About 0.1 to about 15 parts by weight of at least one expandable polystyrene additive;
with the proviso that the amount of components B, C and D does not exceed about 3.8 parts per weight. DESCRIPTION OF THE PREFERRED EMBODIMENTS
The expandable polystyrene used in the practice of this invention comprises units derived from at least one alkenyl aromatic monomer having the general formula:
R I
Ar- C = CH2
in which Ar represents an aromatic hydrocarbon radical or an aromatic halohydrocarbon radical of the benzene series, and R is hydrogen, a methyl group, or an ethyl group. Examples of such alkenyl aromatic polymers are the solid homopolymers of styrene, alpha-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ethylstyrene, vinylxylene, chlorostyrene, bromostyrene, vinyl toluene, or the solid copolymers of one or more of such alkenyl aromatic compounds with other copolymerizable monomers such as acrylonitrile, anhydrides of maleic or itaconic acids, acrylic or methacrylic acid, or rubber- reinforced (either synthetic or natural) styrene polymers, and the like.
The ester used in the practice of this invention is the reaction product of a saturated monocarboxylic acid having about 14-20 carbons and an alkyl alcohol having 3-5 carbon atoms. Representative saturated monocarboxylic acids include myristic, palmitic, stearic, oleic, linoleic, linolenic, and the like. Representative alkyl alcohols include propanol, isopropanol, 1 -butanol, isobutanol, tert-butanol, pentanol and tert-pentanol. Preferably the ester is the ester of an unbranched saturated monocarboxylic acid having about 14-20 carbons and an alkyl alcohol having 3-5 carbon atoms, and more preferably the alcohol is a branched or unbranched alcohol of 4 carbon atoms. One preferred ester is isobutyl stearate. More than one ester, i.e., a mixture of esters, can be used in the practice of the invention. The ester, or mixture of esters, is used in an amount of between about 0.01-2.2, preferably between about 0.1-2.0 and more preferably between about 0.2-1.7, parts by weight.
The at least one unsaturated aliphatic hydrocarbon used in the practice of this invention comprises about 20-60, preferably about 25-50, carbon atoms. Preferably, the unsaturated hydrocarbon used in this invention is a mixture of unsaturated hydrocarbons, and more preferably the mixture is further characterized as having a mass loss based on evaporation of at least about 50, preferably at least about 70, wt% in a temperature range from about 300-4000C measured by thermo gravimetric analysis (TGA) using TG/DTA 220 of Seiko at a heating rate of 10° Kelvin/minute (K/min) and an inert gas flow, e.g., argon, at a rate of 300 milliliters/minute (ml/min). Typically the sample size for this measurement is about 20 milligrams (mg), and the evaporation loss is measured as the sample temperature is raised at a rate of 10K/min from 300 to 4000C in the presence of an argon flow of 300 ml/min. Representative saturated hydrocarbons that can be used in mixtures as the third or (C) component of the expandable polystyrene include triacontane, 2,6,10,15,19,23-hexamethyltetracosane, hexatricosane, tetracosane and cyclotetraconsane. The amount of saturated hydrocarbon, in either neat or mixture format, used in the practice of this invention is typically between about 0.01 and about 2.0, preferably between about 0.05 and about 1.8 and more preferably between about 0.10 and about 1.6, parts by weight.
The mono-alkylbenzene with an alkyl group having 3-5 carbon atoms is used in an amount of between about 0.0001 and about 0.5, preferably between about 0.001 and about 0.4 and more preferably between about 0.002 and about 0.2 parts by weight. Representative mono-alkylbenzenes with a C3_5, preferably a C4, alkyl group include propylbenzene, isopropylbenzene, butylbenzene, isobutylbenzene, tert-butylbenzene, pentylbenzene, isopentylbenzene and tert-pentylbenzene. Isopropylbenzene is a preferred mono-alkylbenzene.
The total amount of ester, saturated aliphatic hydrocarbon and mono-alkylbenzene in the expandable polystyrene typically does not exceed about 3.8, preferably 3.6 and more preferably 3.5 parts by weight. The minimum amount of the combined ester, saturated aliphatic hydrocarbon and mono-alkylbenzene content of the expandable polystyrene is typically at least about 0.02, preferably at least about 0.1 and more preferably at least about 0.2 parts by weight.
In addition to the composition of ester, saturated aliphatic hydrocarbon and mono- alkylbenzene, the expandable polystyrene can comprise one or more other additives in a total amount from about 0.1 to about 15, preferably from about 2 to about 14 and more preferably from about 3 to about 12 parts by weight. These additives, if used, can be used alone or in combination with one another, and include such materials as fillers, pigments, lubricants, fire retardants, blowing agents, wetting agents, antioxidants, ignition resistant compounds, stabilizers and co-stabilizers (also known as extenders), and the like. Fillers include talc, calcium silicate, barium and zinc stearate and magnesium oxide. Flame retardants include a variety of halogenated compounds of which brominated compounds are preferred, e.g., hexabromocyclododecane, 2,2-bis(4-hydroxyethoxy-3,5- dibromophenyl) propane, 2,2-bis (4-(2,3-dibromo)propyloxy-3,5-dibromophenyl propane, tribromophenol and the like.
Blowing agents include n-butane, isobutane, n-pentane, isopentane, halogenated alkanes, water, carbon dioxide, ethyl chloride, nitrogen and mixtures of two or more of these agents. Stabilizers include the various phosphates or sulphates, and the co- stabilizers or extenders include a wide array of materials, e.g., unsaturated mono-, di- and tricarboxylic acids such as acrylic, methacrylic, crotonic, sorbic, maleic, fumaric, citraconic, mesaconic, itaconic and aconitic acid, sodium bisulfite, alkaline salts of alkylaryl sulphonic acids, alkylsulphonic acids and alkyl sulphates with an alkyl chain length of C2-20, such as sodium dodecylbenzenesulfonate, sodium tetradecylsulphate, potassium stearate, compounds containing a terminal vicinal hydroxy-keto structure such as fructose, sorbose, 1,3-dihydroxy-acetone, monohydroxy acetone and invert sugar, vinyl sulphonate, and di-isobutyl naphthalene sulphonate. -
Examples of other additives include methyl methacrylate type copolymers, polyethylene wax, ethylene bis-stearylamide, methylene bis-stearylamide, and ethylene- vinyl acetate copolymer resin.
Any conventional process can be used to make the expandable polystyrene. One typical process is the polymerization of styrene and/or other alkenyl aromatic monomer in an aqueous suspension to form resin particles or beads. The process can include the simultaneous incorporation or impregnation of a blowing agent into the beads, or the beads can be impregnated with the blowing agent in a post-polymerization step.
The resulting expandable polymer beads can then be expanded into polystyrene foam by any conventional process. One typical process comprises the steps of (i) expanding the beads by mixing them with steam in a stirred tank, (ii) stabilizing the beads, e.g., exposing them to air, and (iii) welding the beads together in heated molds.
Both the process of making the expandable polystyrene beads and expanding the beads into foam are more fully described in USP 5,189,071 and 6,271,272. The expanded polystyrene foams of this invention can be made into various shapes for various end use applications. Exemplary shapes and applications include sheets and boards for construction insulation and packaging, shock absorbing foam liners for protective helmets and other sport gear, containers for plant cultivation, rings for life preservers, balls and "peanuts" for loose packaging, components in appliances and vehicles, sculptures for stage and film use, heads for wigs and the like.
SPECIFIC EMBODIMENTS
Comparative Example A
Expandable polystyrene beads without a reduced content of blowing agent were received by suspension polymerization of styrene. Water (721 g), tri calcium phosphate (2.64g) as a stabilizer, calcium carbonate (0.0775g), a co-stabilizer (0.0078g), and a solution of dibenzoyl peroxide (2.48g), tert-amylperoxy-2-ethylhexyl carbonate (1.162g), dicumyl peroxide (1.63g), divinyl benzene (0.217g), a polyethylene wax (0.852g) and hexabromocyclodocecane (5.8Ig) in styrene (775g) containing zso-propylbenzene (60.5 ppm) were added into a stirred polymerization reactor at ambient temperature. By increasing the temperature to 900C polymerization was initiated, and then the reaction was held at this temperature for 4.5 hours producing polystyrene beads. After this time a solution (22.4g) of 5% polyvinyl alcohol in water was added, the reactor was closed and after 5 minutes, pentane (55.Og) was fed to the reactor. The polystyrene beads were then impregnated with pentane for 3 hours at 115°C. After cooling to ambient temperature, the impregnated polystyrene beads were separated from the liquid phase by filtration and centrifugation, and then dried under air, yielding expandable polystyrene beads with water, volatile residuals and residual styrene monomer content, number average molecular weight (Mn), weight average molecular weight (Mw), and polydispersity (MWD) as reported in Table 1. The residual styrene monomer content was determined by gas chromatography.
The foaming behavior properties of the polystyrene beads are described in Table 2.
These properties are the pre-foaming density determined as the volume increase of the polystyrene beads by addition of steam at atmospheric pressure within 180 seconds under constant conditions, and the structure of the foam beads. Further description of the foaming process in relation to the initial pentane content and concentration of other additives is also provided.
Example 1
Expandable polystyrene beads with a reduced content of blowing agent were prepared using the suspension polymerization procedure of Comparative Example A with the following modifications: (a) also dissolved in the styrene monomer were (i) isopropylbenzene (0.775g) as a mono-alkylbenzene with a branched alkyl group having 3 to 5 carbon atoms, (ii) isobutyl stearate (11.6g) as an ester of a saturated monocarboxylic acid having 14 to 20 carbon atoms with an alkyl alcohol having 3 to 5 carbon atoms, and (iii) a mixture (11.6g) of saturated aliphatic hydrocarbons having 29 to 43 carbon atoms with a mass loss based on evaporation of 83.5 wt% in a temperature range from 300 to 4000C by thermogravimetric analysis (TGA) at a heating rate of 10 K/min and at an inert gas rate of 300 ml/min, all related to the monomer, and (b) instead of using 55.Og of pentane, only 23.25g of pentane were fed to the polymerization reactor.
The properties of the expandable polystyrene beads are also reported in Table 1 , and the foaming behavior properties of the polystyrene beads are described in Table 2. Comparing the properties of these two polystyrene foam beads shows that the same pre- foaming density of 15.6 grams/liter (g/1) can be achieved at a much lower initial pentane concentration (3.0 wt%) while maintaining the same desirable structure of the beads.
Comparative Example B
Example 1 was repeated with the following modifications: isopropylbenzene (20.15g) was used as a mono-alkylbenzene with a branched alkyl group having 3 to 5 carbon atoms but without any addition of (i) an ester of a saturated monocarboxylic acid having 14 to 20 carbon atoms with an alkyl alcohol having 3 to 5 carbon atoms, and (ii) a mixture of saturated aliphatic hydrocarbons having 20 to 60 carbon atoms with a mass loss based on evaporation of at least 50 wt% in a temperature range from 3000C to 4000C by TGA at a heating rate of 10° K/min and at an inert gas flow rate of 300 ml/min. As seen by comparing the properties reported in Tables 1 and 2 of the polystyrene beads of this comparative example with those of Example 1, a low pre-foaming density of 10.8 g/1 can be achieved, but the polystyrene foam beads have a highly undesirable odor and are thus not suitable for commercial purposes.
Comparative Example C
Styrene monomer was suspension polymerized to produce expandable polystyrene beads with a reduced content of blowing agent according to the procedure of Comparative Example B. However, instead of using isopropylbenzene (20.15g) as a mono- alkylbenzene with a branched alkyl group having 3 to 5 carbon atoms, isobutyl stearate (20.15g) as an ester of a saturated monocarboxylic acid having 14 to 20 carbon atoms with an alkyl alcohol having 3 to 5 carbon atoms was fed to the polymerization reactor without any mixture of saturated aliphatic hydrocarbons having 20 to 60 carbon atoms with a mass loss based on evaporation of at least 50 wt% in a temperature range from 3000C to 4000C by TGA at a heating rate of 10° K/min and at an inert gas rate of 300 ml/min. The properties of these foam beads are reported in Tables 1 and 2 and although their pre- foaming density is a low 16.1 g/1, their structure is hard and tough.
Comparative Example D
Using the procedure of Comparative Example B, expandable polystyrene beads with a reduced content of blowing agent were manufactured by suspension polymerization without any ester of a saturated monocarboxylic acid having 14 to 20 carbon atoms with an alkyl alcohol having 3 to 5 carbon atoms, but in this instance with a mixture (20.15g) of saturated aliphatic hydrocarbons having 29 to 43 carbon atoms with a mass loss based on evaporation of 83.5 wt% in a temperature range from 3000C to 4000C by TGA at a heating rate of 10° K/min and at an inert gas rate of 300 ml/min. The properties of the foam beads are reported in Tables 1 and 2 and as is readily evident from this data, a low pre-foaming density could not be achieved with this composition. Moreover, the structure of the foam beads was hard and tough.
Comparative Examples B, C and D show that expandable polystyrene beads and the subsequent polystyrene foam with a reduced content of blowing agent and other desirable properties, e.g., low density, cannot be made using only one or two of the three components of the inventive composition. Comparative Example E
Using the procedure of Comparative Example A, expandable polystyrene beads were made with a reduced content of blowing agent (38.7g). The properties of the foam beads made by this Comparative Example are reported in Tables 1 and 2.
Example 2
Using the procedure of Example 1 , expandable polystyrene beads with a reduced content of blowing agent were made except that isopropylbenzene (0.775g) as a mono- alkylbenzene with a branched alkyl group having 3 to 5 carbon atoms, isobutyl stearate (5.8Ig) as an ester of a saturated monocarboxylic acid having 14 to 20 carbon atoms with an alkyl alcohol having 3 to 5 carbon atoms, and a mixture (7.75g) of saturated aliphatic hydrocarbons having 29 to 43 carbon atoms with a mass loss based on evaporation of 83.5 wt% in a temperature range from 3000C to 4000C by TGA at a heating rate of 10° K/min and at an inert gas rate of 300 ml/min were dissolved in styrene and pentane (38.7g), were used. The properties of the foam beads made in this example are reported in Tables 1 and 2, and these properties are favorable to those of the comparative examples.
Example 3
Using the procedure of Example 1 , expandable polystyrene beads with a reduced content of blowing agent were made except that isopropylbenzene (0.775g) as a mono- alkylbenzene with a branched alkyl group having 3 to 5 carbon atoms, isobutyl stearate (7.75g) as an ester of a saturated monocarboxylic acid having 14 to 20 carbon atoms with an alkyl alcohol having 3 to 5 carbon atoms, and a mixture (11.6g) of saturated aliphatic hydrocarbons having 29 to 43 carbon atoms with a mass loss based on evaporation of 83.5 wt% in a temperature range from 300° to 4000C by TGA at a heating rate of 10° K/min and at an inert gas rate of 300 ml/min were dissolved in styrene and pentane (38.7g), were used. The properties of the foam beads made in this example are reported in Tables 1 and 2, and these properties are favorable to those of the comparative examples.
Example 4
Using the procedure of Example 1 , expandable polystyrene beads with a reduced content of blowing agent were made except that isopropylbenzene (0.775g) as a mono- alkylbenzene with a branched alkyl group having 3 to 5 carbon atoms, isobutyl stearate (3.87g) as an ester of a saturated monocarboxylic acid having 14 to 20 carbon atoms with an alkyl alcohol having 3 to 5 carbon atoms, and a mixture (3.87g) of saturated aliphatic hydrocarbons having 29 to 43 carbon atoms with a mass loss based on evaporation of 83.5 wt% in a temperature range from 3000C to 4000C by TGA at a heating rate of 10° K/min and at an inert gas rate of 300 ml/min were dissolved in styrene and pentane (38.7g), were used. The properties of the foam beads made in this example are reported in Tables 1 and 2, and these properties are favorable to those of the comparative examples.
The flame retardant behavior of the expandable polystyrene beads made in this example was also investigated. Test specimens were prepared according to the procedure of DIN 4102. The specimens were prepared by sieving, coating, pre- foaming and drying the pre-foamed beads for 24 hours at 7OC, then foaming the beads in a block mold, cutting the specimens to size and storing the specimens for 24 hours at 700C. The flame retardant behavior of the test specimens was measured using the B2 test method of DIN 4102, and the results are reported in Table 3. These results demonstrate the excellent flame retardant behavior of the polystyrene foam. Moreover, the foam block exhibited a smooth surface with good sealing of the foam beads and an absence of lumps or plugs in the mold.
Table 1
Properties of the Expandable Polystyrene Beads of the Examples
*A11 weight percents and parts per million based on the weight of the polystyrene beads.
Table 2 Properties Characterizing the Foaming Behavior of the Polystyrene Beads of the Examples
*A11 weight percents and parts per million based on the weight of the monomer. Table 3 Flame Retardant Behavior of the Particle Foam Manufactured in Example 4
Although the invention has been described in considerable detail through the preceding examples, this detail is for the purpose of illustration and is not to be construed as a limitation on the scope and spirit of the appended claims. All U.S. patents and allowed U.S. patent applications cited above are incorporated herein by reference.

Claims

What is claimed is:
1. An expandable polystyrene composition comprising:
A. 100 parts by weight of at least one styrene polymer or copolymer or a mixture of the two;
B. About 0.01 to about 2.2 parts by weight of an ester of a saturated monocarboxylic acid having 14 to 20 carbon atoms and an alkyl alcohol having 3 to 5 carbon atoms, or a mixture of the two;
C. About 0.01 to about 2.0 parts by weight of at least one saturated aliphatic hydrocarbon having about 20 to about 60 carbon atoms;
D. About 0.0001 to about 0.5 parts by weight of at least one mono- alkylbenzene with an alkyl group having 3 to 5 carbon atoms; and
E. About 0.1 to about 15' parts by weight of at least one expandable polystyrene additive;
with the proviso that the amount of components B, C and D does not exceed about 3.8 parts by weight.
2. The expandable polystyrene of Claim 1 in which the saturated monocarboxylic acid component of the ester is unbranched.
3. The expandable polystyrene of Claim 1 in which the alkyl alcohol component of the ester comprises 4 carbon atoms.
4. The expandable polystyrene of Claim 1 in which the ester is isobutyl stearate.
5. The expandable polystyrene of Claim 1 in which the saturated aliphatic hydrocarbon is a mixture of saturated aliphatic hydrocarbons having about 20 to about 60 carbon atoms.
6. The expandable polystyrene of Claim 1 in which the saturated aliphatic hydrocarbon comprises about 25 to about 50 carbon atoms and has a mass loss based on evaporation of at least about 50 wt% in a temperature range from about 300-4000C measured by thermogravimetric analysis at a heating rate of 10° K/min and an inert gas rate of 300 ml/min.
7. The expandable polystyrene of Claim 1 in which the saturated aliphatic hydrocarbon comprises about 25 to about 50 carbon atoms and has a mass loss based on evaporation of at least about 70 wt% in a temperature range from about 300-4000C measured by thermogravimetric analysis at a heating rate of 10° K/min and an inert gas rate of 300 ml/min.
8. The expandable polystyrene of Claim 1 in which the alkyl group of the mono-alkylbenzene has 4 carbon atoms.
9. The expandable polystyrene of Claim 1 in which the mono-alkylbenzene is isopropylbenzene.
10. Expanded polystyrene foam made from the expandable polystyrene of any of Claims 1-9.
11. Construction insulation or packaging material comprising the expanded polystyrene foam of Claim 10.
12. A process for making expandable polystyrene beads, the process comprising (i) polymerizing 100 parts by weight of styrene and/or another alkenyl aromatic monomer to form resin beads, and (ii) simultaneously or subsequent to the formation of the beads and addition of an organic volatile blowing agent, incorporating into the beads a mixture comprising:
A. About 0.01 to about 2.2 parts by weight of at least one ester of at least one saturated monocarboxylic acid having 14 to 20 carbon atoms and at least one alkyl alcohol having 3 to 5 carbon atoms;
B. About 0.01 to about 2.0 parts by weight of at least one saturated aliphatic hydrocarbon having about 20 to about 60 carbon atoms; and
C. About 0.0001 to about 0.5 parts by weight of at least one mono- alkylbenzene with an alkyl group having 3 to 5 carbon atoms; with the proviso that the amount of components A, B and C does not exceed about 3.8 parts by weight.
EP07854713A 2007-01-17 2007-11-20 Expandable polystyrene of reduced blowing agent content Withdrawn EP2104702A1 (en)

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