US20110204536A1 - Injection-foamable styrenic monomer-diolefin copolymer, a method for the preparation thereof and use thereof - Google Patents

Injection-foamable styrenic monomer-diolefin copolymer, a method for the preparation thereof and use thereof Download PDF

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US20110204536A1
US20110204536A1 US13/054,302 US200913054302A US2011204536A1 US 20110204536 A1 US20110204536 A1 US 20110204536A1 US 200913054302 A US200913054302 A US 200913054302A US 2011204536 A1 US2011204536 A1 US 2011204536A1
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monomer
diolefin
copolymer
styrenic monomer
reaction
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Hongwen Liang
Aimin Zhang
Lixin Zhou
Jinkui Xia
Zhibin Zhang
Weiping Zhou
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China Petrochemical Corp
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China Petrochemical Corp
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/022—Foaming unrestricted by cavity walls, e.g. without using moulds or using only internal cores
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
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    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
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    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
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    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/46—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals
    • C08F4/48—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals selected from lithium, rubidium, caesium or francium
    • C08F4/482—Metallic lithium, rubidium, caesium or francium
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C—CHEMISTRY; METALLURGY
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/08—Copolymers of ethylene
    • B29K2023/083—EVA, i.e. ethylene vinyl acetate copolymer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/772—Articles characterised by their shape and not otherwise provided for
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08J2325/08—Copolymers of styrene
    • C08J2325/10—Copolymers of styrene with conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2331/00—Characterised by the use of 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 acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
    • C08J2331/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
    • C08J2331/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
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    • C08J2347/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
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    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers

Definitions

  • the invention relates to an injection-foamable styrenic monomer-diolefin copolymer, a method for the preparation thereof, and use thereof. More specifically, the invention relates to a styrenic monomer-diolefin copolymer comprising micro-blocks of polystyrenic monomer and micro-blocks of polydiolefin monomer, a method for the preparation thereof, and use thereof.
  • SBS's styrene/butadiene block copolymers
  • SBS's can be used, for example, in the preparation of soles, adhesives and elastomeric commodities, and for modifying bitumen and plastics.
  • the largest application field of SBS's is the production of soles, and SBS's used for soles comprise more than 50% of the world SBS's consumption.
  • SBS's are phase-separated block copolymers, and shearing viscosities of their melts are quite insensitive to temperature and shearing rate.
  • the physical entanglement of styrene will result in the inhomogeneity of viscosity of their melts (PB segments have a lower viscosity, and the interfaces of the PB and PS phases have a higher viscosity), so that AC as a flowing agent is dispersed unevenly, leading to uneven cellules.
  • articles obtained by foaming SBS's do not meet the requirements to soles in tearing strength, stretching strength, wearing resistance, etc.
  • Random styrenic monomer-diolefin copolymer and preparation thereof are also disclosed in numerous scientific literatures and patents.
  • Chinese Patent Application CN 101113188A discloses a continuous method for preparing a conjugated diene/vinylarene random copolymer.
  • the vinylarene may be styrene
  • the conjugated diene may be 1,3-butadiene
  • This copolymer is designed for automobile tire tread.
  • the large molecular weight of this copolymer renders its melt viscosity too large to be foamed, let alone injection processed.
  • U.S. Pat. No. 4,367,325 discloses a styrene/butadiene random copolymer and a process for the production thereof.
  • This styrene/butadiene random copolymer has a styrene monomer content of 3 to 30%, and a content of 1,2-structure in the butadiene monomer units ranging from 70 to 90%.
  • This copolymer can be used to produce automobile tire, and has a low rolling resistance and a high wet skid resistance.
  • This copolymer has a high melt viscosity and thus cannot be injection processed.
  • EVA foamed articles exhibit predominantly plastic character in stretching strength, tearing strength, compression set, wearing resistance, skid resistance, etc., and thus cannot fully meet the requirements applied by shoe production.
  • polyurethanes When used as sole raw materials, polyurethanes also have drawbacks, such as a high production cost, a large toxicity of the monomers for the polyurethanes, a complexity of the foaming process, an inferior wet skid resistance, easiness of cracking, fracture of shoe heel, etc., and cannot also be injection foamed.
  • styrenic monomer-diolefin copolymers having a suitable molecular weight and a suitable content of styrenic monomer(s) and comprising micro-blocks of polystyrenic monomer and micro-blocks of polydiolefin monomer have a good injection-foamable property.
  • these copolymers have a low melt viscosity in thermally processing so that they can be conveniently injection processed and that a chemical flowing agent can easily generate tiny and uniform cellules.
  • the uniformly distributed polydiolefin micro-blocks provide a suitable number of chemically crosslinking sites.
  • the copolymer molecular network formed through these crosslinking sites by means of a crosslinking agent and physical crosslinkage formed through the polystyrenic monomer micro-blocks function together to stabilize the tiny cellules generated by the chemical flowing agent.
  • the inventors have further found that, since the polydiolefin micro-blocks are uniformly distributed among the polystyrenic monomer micro-blocks, the styrenic monomer-diolefin copolymers of the invention avoid essentially the rapid, exothermal chain crosslinking reaction resulted from the aggregation of polybutadiene, and thus during the crosslinking, no “scorching” phenomenon suffered by SBS's occurs.
  • This copolymer structure design ensures that the foamed materials produced from these copolymers have a sufficient elasticity similar to that of a rubber material, and the physical crosslinkage formed through the polystyrenic monomer micro-blocks results in that these materials remain reprocessibility possessed by conventional SBS's.
  • the styrenic monomer-diolefin copolymers of the invention are environment-friendly.
  • the styrenic monomer-diolefin copolymers of the invention can be used to produce soles, and the copolymers can be processed at a low cost through the existing injection foaming equipment. On this basis, the invention is made.
  • An object of the present invention is to provide a styrenic monomer-diolefin copolymer comprising micro-blocks of polystyrenic monomer and micro-blocks of polydiolefin monomer.
  • Another object of the present invention is to provide a method for the preparation of the styrenic monomer-diolefin copolymer comprising micro-blocks of polystyrenic monomer and micro-blocks of polydiolefin monomer according to the invention.
  • Still another object of the present invention is to provide use of the styrenic monomer-diolefin copolymer comprising micro-blocks of polystyrenic monomer and micro-blocks of polydiolefin monomer according to the invention.
  • Still another object of the present invention is to provide a foamed article produced from the styrenic monomer-diolefin copolymer according to the invention.
  • FIG. 1 shows a 1 H NMR spectrum of the styrene-butadiene copolymer of Example 1.
  • FIG. 2 shows a two-dimensional infrared correlation spectrum of the styrene-butadiene copolymer of Example 2.
  • FIG. 3 shows a two-dimensional infrared correlation spectrum of a conventional triblock SBS.
  • FIG. 4 shows a two-dimensional infrared correlation spectrum of a fully random styrene-butadiene copolymer.
  • FIG. 5 shows a two-dimensional infrared correlation spectrum of a SIS.
  • FIG. 6 shows a two-dimensional infrared correlation spectrum of a styrene-isoprene micro-block copolymer.
  • FIG. 7 shows a two-dimensional infrared correlation spectrum of a SIBS.
  • FIG. 8 shows a two-dimensional infrared correlation spectrum of a styrene-isoprene-butadiene micro-block copolymer.
  • FIG. 9 shows a scanning electron microscope micrograph of the foamed material obtained in Example 8.
  • the invention provides a styrenic monomer-diolefin copolymer comprising micro-blocks of polystyrenic monomer and micro-blocks of polydiolefin monomer.
  • micro-block of polystyrenic monomer is intended to mean a segment of polystyrenic monomer having a polymerization degree of from 2 to 100, and preferably from 3 to 70.
  • micro-block of polydiolefin monomer is intended to mean a segment of polydiolefin having a polymerization degree of from 2 to 400, and preferably from 3 to 330.
  • the styrenic monomer-diolefin copolymer comprising micro-blocks of polystyrenic monomer and micro-blocks of polydiolefin monomer according to the invention has a content of styrenic monomer units ranging from 10 to 80 wt %, a ratio of 1,2-polymerized diolefin units to total diolefin units of less than 30%, and a number average molecular weight (Mn) ranging from 25,000 to 500,000.
  • the styrenic monomer-diolefin copolymer comprising micro-blocks of polystyrenic monomer and micro-blocks of polydiolefin monomer according to the invention has a linear structure, and may be represented by the formula (I):
  • PS represents a polymeric segment of styrenic monomer
  • PB represents a polymeric segment of diolefin monomer
  • X1, X2, X3 and Y each represents the polymerization degree of the respective polymeric segment
  • X1 is an integer ranging from 0 to 150
  • X2 in each appearance, is independently an integer ranging from 1 to 150, preferably from 1 to 100, and more preferably from 1 to 70,
  • Y in each appearance, is independently an integer ranging from 1 to 500, preferably from 1 to 400, and more preferably from 1 to 330,
  • X3 is an integer ranging from 0 to 150
  • n is an integer ranging from 5 to 3000, and preferably from 10 to 3000,
  • the styrenic monomer-diolefin copolymer comprising micro-blocks of polystyrenic monomer and micro-blocks of polydiolefin monomer according to the invention has a multi-arm star-like structure, and may be represented by the formula (II):
  • PS, PB, X1, X2, X3, Y and n are as defined for the formula (I) above,
  • R is a star-shaped coupling agent “nucleus”,
  • n is an integer of from 3 to 10
  • the styrenic monomer-diolefin copolymer comprising micro-blocks of polystyrenic monomer and micro-blocks of polydiolefin monomer according to the invention is a combination of linear molecules and star-shaped molecules having from 3 to 10 arms.
  • a plurality of PS X2 PB Y segments constitute a styrenic monomer-diolefin tapered block, of which composition varies gradually, and the (PS X2 PB Y ) n segment consists of a plurality of such tapered blocks.
  • the styrenic monomer-diolefin copolymer of the invention has a content of styrenic monomer-derived units ranging from 10 to 80 wt %, or from 20 to 80 wt %, or from 30 to 75 wt %, or from 30 to 60 wt %, or from 35 to 60 wt %, or from 35 to 50 wt %, or from 40 to 48 wt %, or from 50 to 70 wt %.
  • styrenic monomer examples include, but are not limited to, styrene, methyl styrene, ethyl styrene, butyl styrene, tert-butyl styrene, dimethyl styrene, chlorostyrene, bromostyrene, methoxy styrene, acetoxystyrene, ⁇ -methyl styrene and combinations thereof, preferably styrene, p-methyl styrene and p-tert-butyl styrene.
  • the copolymer of the invention further comprises diolefin monomer-derived units.
  • diolefin monomer examples include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene and combinations thereof, and preferably 1,3-butadiene and 2-methyl-1,3-butadiene.
  • a ratio of 1,2-polymerized diolefin units to the total diolefin units may be less that 30 mol %, preferably less than 25 mol %, more preferably less than 20 mol %, still preferably from 5 to 20 mol %, and more preferably from 10 to 20 mol %.
  • the styrenic monomer-diolefin copolymer of the invention has a number average molecular weight (M n ) ranging from 25,000 to 500,000, preferably from 25,000 to 300,000, more preferably from 25,000 to 250,000, and more preferably from 30,000 to 180,000.
  • M n number average molecular weight
  • the styrenic monomer-diolefin copolymer of the invention may have a molecular weight distribution, M w /M n , ranging from 1.01 to 1.40, preferably from 1.01 to 1.30, preferably from 1.01 to 1.20, more preferably from 1.01 to 1.15, and still more preferably from 1.01 to 1.10.
  • the polymerized styrenic monomers and the polymerized diolefin monomers are present mainly in the polymer molecule chains as micro-blocks, so that the phase separation extent between the polystyrenic monomer phase regions and the polydiolefin phase regions is very low and, at the same time, a single polystyrenic monomer phase region has a low molecular weight.
  • the polymer has a low shearing viscosity and a low plasticizing temperature, and can be blended with a processing aid and injection molded at a temperature below the decomposition temperature of a crosslinking agent such as DCP (140° C.).
  • a crosslinking agent such as DCP (140° C.
  • the copolymer of the invention consists essentially of micro-blocks of polystyrenic monomer and micro-blocks of polydiolefin monomer.
  • the expression “consists essentially of micro-blocks of polystyrenic monomer and micro-blocks of polydiolefin monomer” it is meant that the micro-blocks of polystyrenic monomer and the micro-blocks of polydiolefin monomer together comprise at least 90 wt %, preferably at least 95 wt %, more preferably at least 98 wt %, and more preferably at least 99 wt % of the total copolymer.
  • the styrenic monomer-diolefin copolymer comprising micro-blocks of polystyrenic monomer and micro-blocks of polydiolefin monomer according to the invention has a moving-window two-dimensional infrared correlation spectrum different from those of the known styrenic monomer-diolefin block copolymers and styrenic monomer-diolefin random copolymers.
  • the copolymers of the invention have moving-window two-dimensional correlation infrared spectra having two or three continuous thermal transition peaks in a temperature range of from about 70 to 150° C.
  • both the styrenic monomer-diolefin block copolymer and the styrenic monomer-diolefin copolymer have a single or multiple discrete thermal transition peaks in the above ranges.
  • the invention provides a method for preparing a linear styrenic monomer-diolefin copolymer comprising micro-blocks of polystyrenic monomer and micro-blocks of polydiolefin monomer, comprising:
  • the solvent useful in the present method may be any of those commonly used in the production of solution polybutadiene-styrene rubbers. Examples include, but are not limited to, cyclohexane, n-hexane, benzene, toluene, xylenes and hexanes, and combinations thereof.
  • the amount of the solvent used may be such that the concentration of the monomers ranges from 5 to 30 wt %, based on the total weight of the reaction mixture.
  • the initiator useful in the present method includes a variety of alkyllithiums commonly used in anionic polymerization, such as n-butyllithium and sec-butyllithium.
  • the amount of the initiator used may be selected depending on the desired molecular weight of the product, and this is within the knowledge of a person skilled in the art.
  • an example of the activator useful in the present method is tetrahydrofuran (THF), and it can be used in an amount ranging from 50 to 1200, preferably from 80 to 500, more preferably from 100 to 300, still more preferably from 120 to 220, and most preferably from about 150 to 200 mg THF/kg polymerization solvent.
  • THF tetrahydrofuran
  • the present method further employees a microstructure modifier.
  • a microstructure modifier examples include Lewis base compounds, such as tetramethyl ethylenediamine, diethyl ether of ethylene glycol, and the like, and they can be used in an amount ranging from 1 to 50 mg/kg polymerization solvent.
  • the styrenic monomer comprises from 10 to 80 wt %, or from 20 to 80 wt %, or from 30 to 75 wt %, or from 30 to 60 wt %, or from 35 to 60 wt %, or from 35 to 50 wt %, or from 40 to 48 wt %, or from 50 to 70 wt %, of the total monomers, with the balance being diolefin monomer.
  • the monomer mixture may be added to the polymerization reactor over a period of time ranging from 5 to 180 minutes, preferably from 10 to 120 minutes, more preferably from 15 to 90 minutes, and most preferably from 20 to 60 minutes.
  • the reaction is optionally allowed to continue for further 5 to 120 minutes, and preferably 10 to 60 minutes.
  • the reaction temperature is controlled in a range of from 50 to 110° C., preferably from 60 to 100° C., and more preferably from 70 to 90° C.
  • a termination agent is added to terminate the reaction.
  • the termination agent useful in the invention may be any of those commonly used in the art, such as water, alcohols and other compounds containing an active hydrogen.
  • the resultant copolymer can be recovered through techniques well known by those skilled in the art. For example, it is possible to add an amount of a conventional antioxidant to the reaction mixture, and then to subject the product to coagulation and drying, to give a finished copolymer.
  • the star-shaped copolymer of the invention may be prepared by a method comprising the steps of:
  • step 6 for the coupling reaction, the above method employees the same materials and process conditions as described above for the method for preparing the linear copolymer according to the invention.
  • synthesis conditions should be controlled so that the living chain ends used for a coupling reaction are polydiolefin segments or polystyrenic monomer-diolefin copolymer segment with a high diolefin unit content, to enhance coupling degree and coupling efficiency.
  • the coupling agent may be silicon tetrachloride, divinylbenzene, dichlorodimethylsilicane, tetraethoxysilicane, or diphenyldimethoxysilicane, the equivalent ratio of the coupling agent to the living chain end may vary widely, and the coupling reaction may be conducted at a temperature ranging from 50 to 110° C. for, for example, 5 to 60 minutes.
  • the equivalent ratio of the coupling agent to the living chain end is about 1:1 or more
  • the equivalent ratio of the coupling agent to the living chain end is less than 1:1, for example less than 0.95:1
  • the mechanism described below may help to understand how the styrenic monomer-diolefin copolymer comprising micro-blocks of polystyrenic monomer and micro-blocks of polydiolefin monomer according to the invention forms.
  • Bu represents butadiene monomer or its polymerized form
  • St represents styrene monomer or its polymerized form
  • LiR represents an alkyllithium as an initiator
  • the styrene monomer and butadiene monomer in the monomer mixture will react with an alkyllithium initiator such as butyllithium to form living initiating species, BuLi and StLi. Since the butadiene has a low boiling point, at the moment of feeding, most butadiene molecules are vaporized so that the species participating in the initiating reaction are predominately styrene, and thus the initial reaction forms mainly StLi. StLi will react preferentially with styrene in the mixed monomers, and thus what are predominately formed are polystyrene blocks.
  • an alkyllithium initiator such as butyllithium to form living initiating species, BuLi and StLi. Since the butadiene has a low boiling point, at the moment of feeding, most butadiene molecules are vaporized so that the species participating in the initiating reaction are predominately styrene, and thus the initial reaction forms mainly StLi. StLi
  • the addition duration of the monomer mixture should be controlled so that the rate at which the monomers are consumed in the polymerization is comparable to or larger than the rate at which the monomers are added; if a continuous addition of the feedstocks is employed, the addition duration of the monomer mixture should be controlled so that the rate at which the monomers are consumed in the polymerization is comparable to or slightly larger than the rate at which the monomers are added.
  • a polymer (PS X2 PB Y ) n which comprises a lot of polystyrene micro-blocks and polybutadiene micro-blocks, can be formed.
  • a plurality of PS X2 PB Y segments will constitute a styrenic monomer-diolefin tapered block, of which composition varies gradually, and the (PS X2 PB Y ) n segment consists of a plurality of such tapered blocks.
  • the invention provides use of the styrenic monomer-diolefin copolymer of the invention.
  • the styrenic monomer-diolefin copolymer of the invention may be blended with various additives at a temperature below 110° C., and then subjected to injection foaming in a mould at 170 to 195° C.
  • the foaming process is similar to those used for EVA, and the foaming equipment may be identical to those used for EVA.
  • a foamed article may be prepared from the copolymer of the invention by a method comprising: kneading the copolymer of the invention with an additive such as stearic acid, zinc stearate, and talc powder, a crosslinking agent such as dicumyl peroxide (DCP), a flowing agent such as azodicarbonamide (flowing agent AC or AC) in an internal mixer at 80° C. for 5 to 10 minutes; pressing the resulting mixture in an open mixer into a sheet and then pelletizing it in a single screw extruder at 90° C.; feeding the resulting pellets into a single screw injector and then injecting it at 90° C. into a mould at a temperature ranging from 170 to 195° C.; maintaining at that temperature for 200 to 500 seconds; and then depressurizing and opening the mould, to remove the foamed article.
  • DCP dicumyl peroxide
  • AC or AC flowing agent
  • the invention provides a foamed article prepared by foaming the copolymer of the invention.
  • the foamed article of the invention there exist both physically crosslinked points resulted from styrene entanglement and chemically crosslinked points, so that the foamed article possesses good stretching strength, tearing strength and wearing resistance, and can be reprocessed. At the same time, the foamed article of the invention possesses excellent skid resistance.
  • the foamed article of the invention may be used for manufacturing sand bench shoes and slippers, for manufacturing midsoles of tourist shoes and sports shoes, for manufacturing outsoles of leather shoes, as vehicle interior decorative materials, or as heat insulators used in various situations.
  • the styrenic monomer-diolefin copolymers may be produced by using the current plants for producing styrenic monomer-based thermoplastic elastomers, without reconstructing the production plants.
  • the physical entanglement points of the styrenic polymer may replace for the chemically crosslinked points, so that the amount of a chemical crosslinking agent used can be significantly reduced.
  • a chemical crosslinking agent used for application fields where high wearing resistance and temperature resistance are not required, it is even allowable to highly expand in the absence of a chemical crosslinking agent, thereby providing a possibility that a foamed material can be fully reused and that a low-taste or taste-free, environment-friendly foamed material can be produced.
  • the foamed materials of the styrenic monomer-diolefin copolymers remain their rubber characteristics, have a low-temperature performance better than that of EVA foamed material, and are comfortable for body.
  • the foamed materials of the styrenic monomer-diolefin copolymers have excellent wet-skid resistance.
  • the foamed materials of the styrenic monomer-diolefin copolymers have a low compression set and a good resilience, and their wearing resistance, stretching strength at break and tearing strength are superior to those of EVA foamed materials.
  • the foamed materials of said polymers have hardnesses varying widely.
  • the styrenic monomer-diolefin copolymers may be injection foamed in a mould, and the pores are uniform.
  • the foamed products of the styrenic monomer-diolefin copolymers may be used for manufacturing sand bench shoes and slippers, for manufacturing midsoles of tourist shoes and sports shoes, for manufacturing outsoles of leather shoes, as vehicle interior decorative materials, or as heat insulators used in various situations.
  • the foamed products of the styrenic monomer-diolefin copolymers can be produced at a cost comparable to that of EVA, but have better properties, so that they will be more commercially interested.
  • This copolymer was found to have a molecular weight of 31,000 (M n ), a molecular weight distribution of 1.02, a content of 1,2-structure in diolefin units of 17.5%, and a Shore C hardness of 65.
  • M n molecular weight
  • This polymer was a random copolymer of styrene and butadiene, and its NMR spectrum is shown in FIG. 1 . This product can be used for a highly damping material.
  • the reaction was allowed to continue for further 25 minutes, and 5 ml of water was then added to terminate the reaction.
  • the product was added to a mixture of steam and water, whereby the solvent was evaporated, and the polymer isolated out as solids and suspended in the water. The solids were separated, dewatered with an extruding-desiccation machine, and devolatilized in a dry box, to give styrene/butadiene copolymer 2.
  • This copolymer was found to have a molecular weight of 140,000 (M n ), a molecular weight distribution of 1.01, a content of 1,2-structure in diolefin units of 15.6%, and a Shore C hardness of 80.
  • M n molecular weight
  • the moving-window two-dimensional correlation infrared spectrum of this copolymer is shown in FIG. 2 .
  • FIG. 3 It can be seen from FIG. 3 that the two-dimensional correlation infrared spectrum of the triblock SBS is relatively simple. 70° C. represents the melting of the micro-crystal of polybutadiene block; 126° C. represents the glass transition of the polystyrene block; 144° C. represents the viscous flow temperature of the polystyrene block.
  • FIGS. 4 to 8 show different thermal transitions due to the different molecular structures of the copolymers.
  • the two-dimensional correlation infrared spectrum of the inventive polymer has distinct thermal transition peaks at 80° C., 101° C. and 126° C. 80° C. is the glass transition temperature of the styrene-butadiene random copolymer segment. 101° C. is the glass transition temperature of short polystyrene blocks; and 126° C. is the viscous flow temperature of the short polystyrene blocks.
  • the polymer obtained in this Example has a typical micro-block structure with styrene-diolefin random copolymer segments mingled in the micro-blocks.
  • This comparative copolymer 1 was found to has a molecular weight of 146,000 (M n ), a molecular weight distribution of 1.01, a content of 1,2-structure in the total diolefin units of 13.0%, a Shore C hardness of 89, and a stretching strength at break of 17.8 MPa.
  • This polymer had a plasticizing temperature of 135° C. When processing aids such as DCP and AC were added at a temperature above the plasticizing temperature of the polymer, 135° C., crosslinking took place in the internal mixer and bubbles were generated.
  • the reaction was allowed to continue for further 20 minutes, and additional 9.6 g of 2-methyl-1,3-butadiene was then added to the reactor. After polymerizing for 20 minutes, 0.875 mmol of silicon tetrachloride as a coupling agent was added. After allowing the coupling reaction to conduct for 30 minutes, 5 ml of water was added to terminate the reaction. 0.2 wt % of Antioxidant 1076 and 0.4 wt % of Antioxidant 168, based on the weight of the polymer, were added to the reaction mixture and stirred for 5 minutes.
  • the product was added to a mixture of steam and water, whereby the solvent was evaporated, and the polymer isolated out as solids and suspended in the water.
  • the solids were separated, dewatered with an extruding-desiccation machine, and devolatilized in a dry box, to give a star-shaped styrene/2-methyl-1,3-butadiene copolymer, which was found to have a molecular weight per arm of 48,600 (M n ), an average number of arms of 3.70, a polymer molecular weight of 180,000 (M n ), a molecular weight distribution of 1.02, and a Shore C hardness of 52.
  • the reaction was allowed to continue for further 20 minutes, and additional 8.7 g of butadiene was added to the reactor. After polymerizing for 20 minutes, 11.6 mmol of divinyl benzene as a coupling agent was added. After allowing the coupling reaction to conduct for 30 minutes, 5 ml of water was added to terminate the reaction. 0.2 wt % of Antioxidant 1076 and 0.4 wt % of Antioxidant 168, based on the weight of the polymer, were added to the reaction mixture and stirred for 5 minutes. Finally, the product was added to a mixture of steam and water, whereby the solvent was evaporated, and the polymer isolated out as solids and suspended in the water.
  • the solids were separated, dewatered with an extruding-desiccation machine, and devolatilized in a dry box, to give a star-shaped styrene/butadiene copolymer.
  • This copolymer was found to be a 6-armed star-shaped styrene-butadiene copolymer, have a number average molecular weight of 150,000, a molecular weight distribution of 1.07, a content of 1,2-structure in the diolefin units of 13.2%, and a Shore C hardness of 55.
  • the reaction was allowed to continue for further 20 minutes, and 5 ml of water was then added to terminate the reaction.
  • the product was added to a mixture of steam and water, whereby the solvent was evaporated, and the polymer isolated out as solids and suspended in the water. The solids were separated, dewatered with an extruding-desiccation machine, and devolatilized in a dry box, to give a styrene/butadiene copolymer.
  • This copolymer was a styrene/butadiene copolymer wherein styrene units were present in micro-blocks.
  • This polymer was found to have a molecular weight of 111,000 (M n ), a molecular weight distribution of 1.05, a content of 1,2-structure in diolefin units of 16.0%, and a Shore C hardness of 75.
  • This polymer was combined with DCP, a flowing agent, talc powder, zinc stearate, zinc oxide. Then the mixture was added into an internal mixer, mixed therein below 75° C. for 10 minutes, and then pelletized through a single screw extruder below 110° C. The resulting pellets were injected below 110° C. into a mould at 180° C. to be foamed.
  • the foamed product could be used as an external thermal-insulation material of piping.
  • the reaction was allowed to continue for further 20 minutes, and additional 8.75 g of 2-methyl-1,3-butadiene was added to the reactor. After allowing the polymerization to continue for 20 minutes, 0.825 mmol of silicon tetrachloride as a coupling agent was added thereto. The coupling reaction was conducted for 30 minutes, and 5 ml of water was then added to terminate the reaction. 0.2 wt % of Antioxidant 1076 and 0.4 wt % of Antioxidant 168, based on the weight of the polymer, were added to the reaction mixture and stirred for 5 minutes.
  • the product was added to a mixture of steam and water, whereby the solvent was evaporated, and the polymer isolated out as solids and suspended in the water.
  • the solids were separated, dewatered with an extruding-desiccation machine, and devolatilized in a dry box, to give a star-shaped styrene/2-methyl-1,3-butadiene copolymer.
  • This star-shaped polymer was found to have a molecular weight per arm of 47,000 (M n ), an average number of arms of 3.72, a polymer molecular weight of 175,000 (M a ), a molecular weight distribution of 1.02, and a Shore C hardness of 65.
  • This polymer could be injection foamed in a mould at 185° C., and the foamed product could be used as a vehicle interior decorative material.
  • the reaction was allowed to continue for further 20 minutes, and 5 ml of water was then added to terminate the reaction.
  • the product was added to a mixture of steam and water, whereby the solvent was evaporated, and the polymer isolated out as solids and suspended in the water.
  • the solids were separated, dewatered with an extruding-desiccation machine, and devolatilized in a dry box, to give a tert-butyl styrene/butadiene copolymer, wherein the tert-butyl styrene units were present in micro-blocks.
  • the polymer was found to have a molecular weight of 234,000 (M n ), a molecular weight distribution of 1.08, a content of 1,2-structure in diolefin units of 15.5%, and a Shore C hardness of 68.
  • This polymer could be injection foamed in a mould at 185° C., and the foamed product could be used to manufacture a highly resilient material.
  • the styrene/butadiene copolymer 2 obtained from Example 2 was formulated according to the formulation shown in Table 1 below, and the combined materials were mixed in an internal mixer at 90° C. and then pelletized through a single screw extruder. The pellets were injected below 110° C. into a mould at 180° C. to be foamed, to give a foamed material. This foaming process is similar to that used for ordinary EVA's. The properties of the resultant foamed material are shown in Table 2 below. The scanning electron microscope micrograph of a cross-section of the foamed material is shown in FIG. 9 . It can be seen that a foamed material having uniform pores can be obtained from this styrene/butadiene copolymer. The foamed product obtained in this Example could be used to manufacture sand bench shoes and slippers.
  • the reaction was allowed to continue for further 25 minutes, and 5 ml of water was then added to terminate the reaction.
  • the product was added to a mixture of steam and water, whereby the solvent was evaporated, and the polymer isolated out as solids and suspended in the water. The solids were separated, dewatered with an extruding-desiccation machine, and devolatilized in a dry box, to give styrene/butadiene copolymer 9.
  • the copolymer was found to have a molecular weight of 145,000 (M n ).
  • This polymer was combined with DCP, a flowing agent, talc powder, zinc stearate, and zinc oxide. Then the combined materials were added into an internal mixer, mixed therein below 75° C. for 10 minutes, and then pelletized through a single screw extruder below 110° C. The resulting pellets were injected below 110° C. into a mould at 180° C. to be foamed.
  • the foamed product could be used as an external thermal-insulation material of piping.
  • the reaction was allowed to continue for further 20 minutes, and 0.825 mmol of silicon tetrachloride as a coupling agent was then added thereto. After allowing the coupling reaction to continue for 30 minutes, 5 ml of water was added to terminate the reaction. 0.2 wt % of Antioxidant 1076 and 0.4 wt % of Antioxidant 168, based on the weight of the polymer, were added to the reaction mixture and stirred for 5 minutes. Finally, the product was added to a mixture of steam and water, whereby the solvent was evaporated, and the polymer isolated out as solids and suspended in the water.
  • the solids were separated, dewatered with an extruding-desiccation machine, and devolatilized in a dry box, to give a star-shaped styrene/isoprene copolymer.
  • This star-shaped polymer was found to have a molecular weight per arm of 118,000 (Mn), an average number of arms of 3.72, and a polymer molecular weight of 438,900 (Mn).
  • This polymer could be foamed in a mould at 185° C. in a compression moulding manner. The foamed product could be used as a vehicle interior decorative material.

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