WO2006070983A1 - Silicone impact modifier with high refractive index and method for preparing the same - Google Patents

Silicone impact modifier with high refractive index and method for preparing the same Download PDF

Info

Publication number
WO2006070983A1
WO2006070983A1 PCT/KR2005/001831 KR2005001831W WO2006070983A1 WO 2006070983 A1 WO2006070983 A1 WO 2006070983A1 KR 2005001831 W KR2005001831 W KR 2005001831W WO 2006070983 A1 WO2006070983 A1 WO 2006070983A1
Authority
WO
WIPO (PCT)
Prior art keywords
cross
linked
impact modifier
polymer
alkylacrylate
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.)
Ceased
Application number
PCT/KR2005/001831
Other languages
French (fr)
Inventor
Han Su Lee
Sung Sig Min
Byung Choon Lee
Byeong Do Lee
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.)
Cheil Industries Inc
Original Assignee
Cheil Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cheil Industries Inc filed Critical Cheil Industries Inc
Priority to EP05750719A priority Critical patent/EP1841810B1/en
Priority to CN2005800455928A priority patent/CN101094882B/en
Priority to US11/323,646 priority patent/US7541401B2/en
Publication of WO2006070983A1 publication Critical patent/WO2006070983A1/en
Priority to US11/768,984 priority patent/US7956105B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—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 a halogen
    • C08F214/02—Monomers containing chlorine
    • C08F214/04—Monomers containing two carbon atoms
    • C08F214/06—Vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S525/902—Core-shell
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2998—Coated including synthetic resin or polymer

Definitions

  • the present invention relates to a silicone impact modifierwith high refractive index and method for preparing the same. More particularly, the present invention relates to a silicone impact modifier that comprises a rubber core consisting of an organosiloxane- alkylacrylate-styrenic aromatic compound cross-linked copolymer and a plastic shell consisting of a vinyl (co)polymer and provides a thermoplastic resin with excellent coloration, impact resistance, heat stability and weather resistance.
  • a polycarbonate resin has been used as an engineering plastic due to its excellence in impact strength, self-extinguish, dimension stability and heat resistance compared to other resins. Therefore, the resin has been widely applied to office automation (OA) instruments, electric or electronic goods and so on.
  • OA office automation
  • the polycarbonate resin has poor flowability due to its high melting point, so that the resin requires high processing temperature. Such high processing temperature causes a problem that the resultant molded product suffers from deterioration of impact resistance. For this reason, the polycarbonate resin is blended with various impact modifiers to improve impact resistance.
  • the present inventors have developed an impact modifier which provides a thermoplastic resin with excellent coloration, impact resistance, heat stability and weather resistance which is obtained by preparing a rubber core through cross-polymerization of an alkylacrylate-styrenic aromatic compound in presence of an organosiloxane cross-linked (co)polymer having a specific particle size and a refractive index and graft (co)polymerizing a vinyl monomer onto the rubber core thereby forming a plastic shell.
  • the refractive index of the impact modifier of the present invention is higher than the value of 1.45-1.47 that of the conventional silicone impact modifier has.
  • An object of the present invention is to provide an impact modifier that can improve a coloration property of polycarbonate resin without degradation of other intrinsic properties.
  • Another object of the present invention is to provide an impact modifier that can provide a polycarbonate with good heat stability, impact resistance at a low temperature and weather resistance.
  • the present invention relates to the silicone impact modifier that comprises (A) a rubber core consisting of (a ) an organosiloxane cross-linked (co)polymer with a particle size of 50-400 nm and (a ) an alkylacrylate-styrenic aromatic compound cross-linked copolymer; and (B) a plastic shell consisting of a vinyl (co)polymer, and the refractive indexof the silicone impact modifier is 1.49-1.59.
  • the present invention relates to the silicone impact modifier that comprises
  • A a rubber core consisting of (a ) an organosiloxane cross-linked (co)polymer with a particle size of 50—400 nm and (a ) an alkylacrylate cross-linked polymer; and (B) a plastic shell consisting of a vinyl (co)polymer and having the refractive indexof 1.49-1.59.
  • the rubber core comprises (a ) an organosiloxane cross-linked (co)polymer and (a ) an alkylacrylate-styrenic aromatic compound cross-linked copolymer.
  • the organosiloxane cross-linked (co)polymer has a refractive indexof 1.41 - 1.50 and a particle size of 50-400 nm. If the refractive indexof organosiloxane cross-linked (co)polymer is less than 1.41, the refractive index of the impact modifier cannot reach the level of 1.49, and if the refractive indexof organosiloxane cross-linked (co)polymer is more than 1.50, the glass transition temperature of the organosiloxane polymer becomes higher, so that the affinity for the organic solvents is increased, which incurs deterioration of other properties. Therefore, the preferable range of the refractive index of organosiloxane cross-linked (co)polymer is 1.41-1.50, more preferably 1.41-1.45 in view of physical property balance.
  • the particle size of the organosiloxane cross-linked (co)polymer is less than 50 nm or more than 400 nm, the impact modifying effect is reduced. So, it is preferable that the range of the particle size of the organosiloxane cross-linked (co)polymer is 50-400 nm.
  • the rubber core comprises (a ) an organosiloxane cross-linked (co)polymer with a particle size of 50-400 nm and (a ) an alkylacrylate cross-linked polymer.
  • the rubber core comprises the organosiloxane cross-linked (co)polymer and the alkylacrylate cross-linked polymer without any styrenic aromatic compound, the refractive indexof organosiloxane cross- linked (co)polymer is 1.44-1.55.
  • the refractive index of the impact modifier cannot reach the level of 1.49.
  • the organosiloxane cross-linked (co)polymer (a ) of the present invention is the organosiloxane (co)polymer which has a cross-linked structure.
  • the organosiloxane cross-linked (co)polymer include polydimethylsiloxane, poly- methylphenylsiloxane, polydiphenylsiloxane, and so forth.
  • the organosiloxane (co)polymer of the present invention is cross-linked. If the organosiloxane (co)polymer is not cross-linked, it undesirably loses rubber properties, which results in degradation of impact resistance, and the coloration property is also deteriorated due to the diffusion of organosiloxane (co)polymer into the surface of product.
  • Degree of crosslinking can be determined by solubility of the organosiloxane cross- linked (co)polymer in an organic solvent. The higher the degree of crosslinking, the lower the solubility in organic solvent.
  • organic solvent acetone or toluene may be used. Thus it is preferable to have an insoluble portion in toluene or acetone.
  • the content of an insoluble portion of the organosiloxane cross-linked (co)polymer in toluene is preferably more than 30%.
  • alkyl acrylate examples include methyl acrylate, ethyl acrylate, n-butyl acrylate and the like. Most preferable example is n-butyl acrylate, since it has a low glass transition temperature.
  • styrenic aromatic compound examples include styrene, ⁇ -methylstyrene, di- vinylbenzene, vinyltoluene and the like. Among them, styrene is preferably used.
  • the alkylacrylate-styrenic aromatic compound cross-linked copolymer is prepared by copolymerizing an alkylacrylate with a styrenic aromatic compound in the presence of cross-linking agent.
  • the weight ratio of (a ) the organosiloxane cross-linked (co)polymer to (a ) the alkylacrylate-styrenic aromatic compound cross-linked copolymer or the alkylacrylate cross-linked copolymer is preferably 1 : 6-6 : 1.
  • the weight ratio of the organosiloxane cross-linked (co)polymer(a ) to the alkylacrylate-styrenic aromatic compound cross-linked copolymer(a ) is less than 1 : 6, the impact modifying effect at low temperature is reduced, and if the weight ratio is more than 6 : 1, the content of organosiloxane cross-linked (co)polymer is relatively increased, which causes the affinity between resin and impact modifier to be decreased, so that the impact modifying effect is reduced and higher production cost is needed.
  • the weight ratio of the alkylacrylate to the styrenic aromatic compound in the alkylacrylate-styrenic aromatic compound cross-linked copolymer (a ) is preferably 1 : 1-20 : 1.
  • the weight ratio of the alkylacrylate to the styrenic aromatic compound is less than 1 : 1, the glass transition temperature of the alkylacrylate becomes extremely increased, so that the impact modifying effect is reduced, and if the weight ratio is more than 20 : 1, the refractive index and coloration property are deteriorated.
  • the plastic shell of the present invention is a vinyl (co)polymer and is formed on the surface of the rubber core by graft (co)polymerizing a vinyl monomer onto the rubber core.
  • Examples of the vinyl monomer include alkylmethacrylate, acrylate and ethylenically unsaturated aromatic compound and so forth.
  • alkylmethacrylate acrylate and ethylenically unsaturated aromatic compound and so forth.
  • methyl- methacylate, styrene, acrylonitrile or a mixture of two or more thereof is preferable.
  • (B) is 5 : 5-9 : 1.
  • the weight ratio of the rubber core (A) to the plastic shell (B) is less than 5 : 5, the rubber content is relatively reduced, so that the effect for the improvement of the impact strength becomes lowered. If the ratio is more than 9 : 1, the compatibility between resin and impact modifier is decreased, so that the impact modifying effect is also reduced and it causes higher production cost.
  • the impact modifier of the present invention has a refractive index within the range from 1.49 to 1.59, preferably from 1.50 to 1.57. If the refractive index is less than 1.49, the difference in refractive index between the impact modifier and the polycarbonate become increased, so that the coloration property is deteriorated.
  • the method of preparing of the silicone impact modifier of the present invention comprises preparing a rubber core through cross-polymerization by adding an alkylacrylate and a styrenic aromatic compound to an organosiloxane cross-linked (co)polymer having a particle size of 50—400 nm and a refractive indexof 1.41-1.50; and graft (co)polymerizing a vinyl monomer onto the rubber core thereby forming a plastic shell.
  • the method of preparing of the silicone impact modifier of the present invention comprises preparing a rubber core through cross-polymerization by adding an alkylacrylate to an organosiloxane cross- linked (co)polymer having a particle size of 50—400 nm and a refractive indexof 1.44-1.55; and graft (co)polymerizing a vinyl monomer onto the rubber core thereby forming a plastic shell.
  • the organosiloxane cross-linked (co)polymer is used in a dispersed state (called "silicone latex") prepared by dispersing the organosiloxane cross-linked (co)polymer into ion-exchanged water in the presence of an emulsifier.
  • the organosiloxane is selected from the group consisting of dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane, and a mixture or a copolymer thereof.
  • the organosiloxane cross-linked (co)polymer of the present invention is used in an amount of 5-90 parts by weight, preferably 10-50 parts by weight based on the total weight of reactants.
  • anionic emulsifier such as sodium, potassium, or ammonium salt of alkylsulfate containing from 4 to 30 carbon atoms can be used.
  • the emulsifier include sodium dodecyl sulfate, sodium dodecylbenzene sulfate and the like. Among them, sodium dodecylbenzene sulfate is more preferable for its versatility in a wide range of pH.
  • the emulsifier is used in an amount of 0.1-5 parts by weight, preferably 0.1-2 parts by weight based on the total weight of reactants.
  • an alkyl acrylate monomer, a styrenic aromatic compound and a crosslinking agent are added under nitrogen stream, and heated to 50-100 °C.
  • the organosiloxane cross-linked (co)polymer is swelled by alkyl acrylate monomer, a styrenic aromatic compound and a crosslinking agent. And then the polymerization is carried out at 50-100 °C by adding a polymerization initiator to obtain the rubber core.
  • Examples of the alkyl acrylate monomer include methyl acrylate, ethyl acrylate, n- butyl acrylate and the like. Most preferable example is n-butyl acrylate having a low glass transition temperature.
  • the alkyl acrylate monomer is used in an amount of 5-90 parts by weight, preferably 10-50 parts by weight based on the total weight of reactants.
  • styrenic aromatic compound examples include styrene, ⁇ -methylstyrene, di- vinylbenzene, vinyltoluene and the mixture thereof. Among them, styrene is preferably used.
  • the styrenic aromatic compound is used in an amount of 0.01-50 parts by weight, preferably 1-30 parts by weight based on the total weight of reactants.
  • crosslinking agent examples include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene and the like. Among them, allyl methacrylate and triallyl isocyanurate is preferred.
  • the crosslinking agent is used in an amount of 0.1-10 parts by weight, preferably 0.1-5 parts by weight based on the total weight of reactants.
  • Suitable polymerization initiators comprise potassium persulfate, magnesium persulfate, benzoyl peroxide, hydrogen peroxide, dibenzyl peroxide, cumene hydroperoxide, tert - butyl hydroperoxide and the like. Among them, water-soluble initiator such as potassium persulfate is preferred.
  • the polymerization initiator is used in an amount of 0.1-5 parts by weight, preferably 0.1-2 parts by weight.
  • a polymerization initiator and a vinyl monomer is added dropwise continuously at 50-100 °C to form a plastic shell, followed by coagulation by means of the addition of a coagulating agent and filtration to prepare a silicone impact modifierwith high refractive index.
  • Examples of the vinyl monomer include alkylmethacrylate, acrylate and ethylenically unsaturated aromatic compound and so forth. Among them, methyl- methacylate, styrene, acrylonitrile or a mixture of two or more thereof is preferable.
  • the vinyl monomer of the present invention is used in an amount of 5-90 parts by weight, preferably 10-50 parts by weight based on the total weight of reactants.
  • metal salt such as magnesium chloride, calcium chloride, magnesium sulfate, calcium sulfate or the like can be used.
  • the impact modifier thus obtained has a high refractive indexof 1.49-1.59.
  • the impact modifier of the present invention can provide a thermoplastic resin with good heat stability, impact resistance even at low temperatures, weather resistance, and excellent coloration.
  • the thermoplastic resin that can be used in the present invention is not particularly limited. Examples of the thermoplastic resin include a vinyl chloride resin, a styrenic resin, a styrene-acrylonitrile resin, an acrylic resin, a polyester resin, an ABS resin, a polycarbonate resin, and so forth. Especially, when the impact modifier of the present invention is used in polycarbonate resin for housings of electronic instrument, the effect is magnified.
  • thermoplastic resin is a polycarbonate resin
  • silicone impact modifier of the present invention is blended into the composition in an amount of 0.5-30 parts by weight, per 100 parts by weight of the polycarbonate resin.
  • Comparative Example 3 was conducted in the same manner as in Example 1 except that 90 g of dimethylsiloxane-diphenylsiloxane linear copolymer having a refractive index of 1.43, a particle size of 220 nm and less than 5% of an insoluble portion in toluene was used instead of dimethylsiloxane-diphenylsiloxane cross-linked copolymer. The conversion was 94.6%.
  • the impact modifiers of Examples 1-4 show higher refractive index (more than 1.49) and better coloration property without deterioration of impact strength than those of Comparative Examples 1-2.
  • the impact modifier of Comparative Example 3 which employs linear organosiloxane copolymer shows poor impact strength and bad coloration property even it has high refractive index of 1.500.

Landscapes

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

Abstract

The silicone impact modifierwith high refractive indexaccording to the present invention comprises (A) a rubber core consisting of (a ) an organosiloxane cross-linked (co)polymer with a particle size of 50-400 nm and (a ) an alkylacrylate-styrene aromatic compound cross-linked copolymer; and (B) a plastic shell consisting of a vinyl (co)polymer. The refractive indexof the silicone impact modifier of the present invention is 1.49-1.59.

Description

Description
SILICONE IMPACT MODIFIER WITH HIGH REFRACTIVE INDEX AND METHOD FOR PREPARING THE SAME
Technical Field
[1] The present invention relates to a silicone impact modifierwith high refractive index and method for preparing the same. More particularly, the present invention relates to a silicone impact modifier that comprises a rubber core consisting of an organosiloxane- alkylacrylate-styrenic aromatic compound cross-linked copolymer and a plastic shell consisting of a vinyl (co)polymer and provides a thermoplastic resin with excellent coloration, impact resistance, heat stability and weather resistance.
[2]
Background Art
[3] In general, a polycarbonate resin has been used as an engineering plastic due to its excellence in impact strength, self-extinguish, dimension stability and heat resistance compared to other resins. Therefore, the resin has been widely applied to office automation (OA) instruments, electric or electronic goods and so on.
[4] However, the polycarbonate resin has poor flowability due to its high melting point, so that the resin requires high processing temperature. Such high processing temperature causes a problem that the resultant molded product suffers from deterioration of impact resistance. For this reason, the polycarbonate resin is blended with various impact modifiers to improve impact resistance.
[5] Although these impact modifiers improve impact strength of the polycarbonate resin, the use of such impact modifiers further causes problems. For instance, a butadiene rubber-based impact modifier commonly used in polycarbonate tends to be degraded or scorched during over 300 °C of molding process, which results in deterioration of heat stability and weather resistance, so the application has been restricted. In case of an acrylate rubber-based impact modifier, it may provide good heat stability and weather resistance, but the coloration property and impact resistance at low temperature are poor.
[6] U.S. patent Nos. 4,994,522 and 5,132,359 disclose silicone impact modifiers for vinyl chloride resins. However, when these impact modifiers are used in polycarbonate resin, the coloration property is still deteriorated.
[7] Accordingly, the present inventors have developed an impact modifier which provides a thermoplastic resin with excellent coloration, impact resistance, heat stability and weather resistance which is obtained by preparing a rubber core through cross-polymerization of an alkylacrylate-styrenic aromatic compound in presence of an organosiloxane cross-linked (co)polymer having a specific particle size and a refractive index and graft (co)polymerizing a vinyl monomer onto the rubber core thereby forming a plastic shell. The refractive index of the impact modifier of the present invention is higher than the value of 1.45-1.47 that of the conventional silicone impact modifier has. [8]
Disclosure of Invention Technical Problem
[9] An object of the present invention is to provide an impact modifier that can improve a coloration property of polycarbonate resin without degradation of other intrinsic properties. [10] Another object of the present invention is to provide an impact modifier that can provide a polycarbonate with good heat stability, impact resistance at a low temperature and weather resistance. [11] Other objects and advantages of this invention will be apparent from the ensuing disclosure and appended claims. [12]
Technical Solution
[13] The present invention relates to the silicone impact modifier that comprises (A) a rubber core consisting of (a ) an organosiloxane cross-linked (co)polymer with a particle size of 50-400 nm and (a ) an alkylacrylate-styrenic aromatic compound cross-linked copolymer; and (B) a plastic shell consisting of a vinyl (co)polymer, and the refractive indexof the silicone impact modifier is 1.49-1.59.
[14] Further, the present invention relates to the silicone impact modifier that comprises
(A) a rubber core consisting of (a ) an organosiloxane cross-linked (co)polymer with a particle size of 50—400 nm and (a ) an alkylacrylate cross-linked polymer; and (B) a plastic shell consisting of a vinyl (co)polymer and having the refractive indexof 1.49-1.59.
[15]
Best Mode for Carrying Out the Invention
[16] (A) Rubber Core
[17]
[18] In one embodiment of the present invention, the rubber core comprises (a ) an organosiloxane cross-linked (co)polymer and (a ) an alkylacrylate-styrenic aromatic compound cross-linked copolymer.
[ 19] The organosiloxane cross-linked (co)polymer has a refractive indexof 1.41 - 1.50 and a particle size of 50-400 nm. If the refractive indexof organosiloxane cross-linked (co)polymer is less than 1.41, the refractive index of the impact modifier cannot reach the level of 1.49, and if the refractive indexof organosiloxane cross-linked (co)polymer is more than 1.50, the glass transition temperature of the organosiloxane polymer becomes higher, so that the affinity for the organic solvents is increased, which incurs deterioration of other properties. Therefore, the preferable range of the refractive index of organosiloxane cross-linked (co)polymer is 1.41-1.50, more preferably 1.41-1.45 in view of physical property balance.
[20] Further, if the particle size of the organosiloxane cross-linked (co)polymer is less than 50 nm or more than 400 nm, the impact modifying effect is reduced. So, it is preferable that the range of the particle size of the organosiloxane cross-linked (co)polymer is 50-400 nm.
[21] In another embodiment of the present invention, the rubber core comprises (a ) an organosiloxane cross-linked (co)polymer with a particle size of 50-400 nm and (a ) an alkylacrylate cross-linked polymer. When the rubber core comprises the organosiloxane cross-linked (co)polymer and the alkylacrylate cross-linked polymer without any styrenic aromatic compound, the refractive indexof organosiloxane cross- linked (co)polymer is 1.44-1.55.
[22] If the refractive indexof the organosiloxane cross-linked (co)polymer is less than
1.44, the refractive index of the impact modifier cannot reach the level of 1.49.
[23] The organosiloxane cross-linked (co)polymer (a ) of the present invention is the organosiloxane (co)polymer which has a cross-linked structure. Examples of the organosiloxane cross-linked (co)polymer include polydimethylsiloxane, poly- methylphenylsiloxane, polydiphenylsiloxane, and so forth. By copolymerizing two or more kinds of organosiloxane monomer/oligomer, it is possible to adjust the refractive index of the organosiloxane cross-linked copolymer to 1.41-1.50. Preferably, the organosiloxane (co)polymer of the present invention is cross-linked. If the organosiloxane (co)polymer is not cross-linked, it undesirably loses rubber properties, which results in degradation of impact resistance, and the coloration property is also deteriorated due to the diffusion of organosiloxane (co)polymer into the surface of product.
[24] Degree of crosslinking can be determined by solubility of the organosiloxane cross- linked (co)polymer in an organic solvent. The higher the degree of crosslinking, the lower the solubility in organic solvent. As the organic solvent, acetone or toluene may be used. Thus it is preferable to have an insoluble portion in toluene or acetone. The content of an insoluble portion of the organosiloxane cross-linked (co)polymer in toluene is preferably more than 30%.
[25] Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, n-butyl acrylate and the like. Most preferable example is n-butyl acrylate, since it has a low glass transition temperature.
[26] Examples of the styrenic aromatic compound include styrene, α-methylstyrene, di- vinylbenzene, vinyltoluene and the like. Among them, styrene is preferably used.
[27] The alkylacrylate-styrenic aromatic compound cross-linked copolymer is prepared by copolymerizing an alkylacrylate with a styrenic aromatic compound in the presence of cross-linking agent.
[28] The weight ratio of (a ) the organosiloxane cross-linked (co)polymer to (a ) the alkylacrylate-styrenic aromatic compound cross-linked copolymer or the alkylacrylate cross-linked copolymer is preferably 1 : 6-6 : 1.
[29] If the weight ratio of the organosiloxane cross-linked (co)polymer(a ) to the alkylacrylate-styrenic aromatic compound cross-linked copolymer(a ) is less than 1 : 6, the impact modifying effect at low temperature is reduced, and if the weight ratio is more than 6 : 1, the content of organosiloxane cross-linked (co)polymer is relatively increased, which causes the affinity between resin and impact modifier to be decreased, so that the impact modifying effect is reduced and higher production cost is needed.
[30] The weight ratio of the alkylacrylate to the styrenic aromatic compound in the alkylacrylate-styrenic aromatic compound cross-linked copolymer (a ) is preferably 1 : 1-20 : 1.
[31] If the weight ratio of the alkylacrylate to the styrenic aromatic compound is less than 1 : 1, the glass transition temperature of the alkylacrylate becomes extremely increased, so that the impact modifying effect is reduced, and if the weight ratio is more than 20 : 1, the refractive index and coloration property are deteriorated.
[32]
[33] (B) Plastic Shell
[34]
[35] The plastic shell of the present invention is a vinyl (co)polymer and is formed on the surface of the rubber core by graft (co)polymerizing a vinyl monomer onto the rubber core.
[36] Examples of the vinyl monomer include alkylmethacrylate, acrylate and ethylenically unsaturated aromatic compound and so forth. For example, methyl- methacylate, styrene, acrylonitrile or a mixture of two or more thereof is preferable.
[37] In the present invention, the weight ratio of the rubber core(A) to the plastic shell
(B) is 5 : 5-9 : 1.
[38] If the weight ratio of the rubber core (A) to the plastic shell (B) is less than 5 : 5, the rubber content is relatively reduced, so that the effect for the improvement of the impact strength becomes lowered. If the ratio is more than 9 : 1, the compatibility between resin and impact modifier is decreased, so that the impact modifying effect is also reduced and it causes higher production cost.
[39] The impact modifier of the present invention has a refractive index within the range from 1.49 to 1.59, preferably from 1.50 to 1.57. If the refractive index is less than 1.49, the difference in refractive index between the impact modifier and the polycarbonate become increased, so that the coloration property is deteriorated.
[40] The method of preparing the silicone impact modifier of the present invention will now be described in detail.
[41] In one embodiment of the present invention, the method of preparing of the silicone impact modifier of the present invention comprises preparing a rubber core through cross-polymerization by adding an alkylacrylate and a styrenic aromatic compound to an organosiloxane cross-linked (co)polymer having a particle size of 50—400 nm and a refractive indexof 1.41-1.50; and graft (co)polymerizing a vinyl monomer onto the rubber core thereby forming a plastic shell.
[42] In another embodiment of the present invention, the method of preparing of the silicone impact modifier of the present invention comprises preparing a rubber core through cross-polymerization by adding an alkylacrylate to an organosiloxane cross- linked (co)polymer having a particle size of 50—400 nm and a refractive indexof 1.44-1.55; and graft (co)polymerizing a vinyl monomer onto the rubber core thereby forming a plastic shell.
[43] In the present invention, the organosiloxane cross-linked (co)polymer is used in a dispersed state (called "silicone latex") prepared by dispersing the organosiloxane cross-linked (co)polymer into ion-exchanged water in the presence of an emulsifier.
[44] The organosiloxane is selected from the group consisting of dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane, and a mixture or a copolymer thereof. The organosiloxane cross-linked (co)polymer of the present invention is used in an amount of 5-90 parts by weight, preferably 10-50 parts by weight based on the total weight of reactants.
[45] As the emulsifier, anionic emulsifier such as sodium, potassium, or ammonium salt of alkylsulfate containing from 4 to 30 carbon atoms can be used. Examples of the emulsifier include sodium dodecyl sulfate, sodium dodecylbenzene sulfate and the like. Among them, sodium dodecylbenzene sulfate is more preferable for its versatility in a wide range of pH. The emulsifier is used in an amount of 0.1-5 parts by weight, preferably 0.1-2 parts by weight based on the total weight of reactants.
[46] To the silicone latex, an alkyl acrylate monomer, a styrenic aromatic compound and a crosslinking agent are added under nitrogen stream, and heated to 50-100 °C. The organosiloxane cross-linked (co)polymer is swelled by alkyl acrylate monomer, a styrenic aromatic compound and a crosslinking agent. And then the polymerization is carried out at 50-100 °C by adding a polymerization initiator to obtain the rubber core. [47] Examples of the alkyl acrylate monomer include methyl acrylate, ethyl acrylate, n- butyl acrylate and the like. Most preferable example is n-butyl acrylate having a low glass transition temperature. The alkyl acrylate monomer is used in an amount of 5-90 parts by weight, preferably 10-50 parts by weight based on the total weight of reactants.
[48] Examples of the styrenic aromatic compound include styrene, α-methylstyrene, di- vinylbenzene, vinyltoluene and the mixture thereof. Among them, styrene is preferably used. The styrenic aromatic compound is used in an amount of 0.01-50 parts by weight, preferably 1-30 parts by weight based on the total weight of reactants.
[49] Examples of the crosslinking agent include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene and the like. Among them, allyl methacrylate and triallyl isocyanurate is preferred. The crosslinking agent is used in an amount of 0.1-10 parts by weight, preferably 0.1-5 parts by weight based on the total weight of reactants.
[50] As the polymerization initiator, free-radical initiators that generate free-radicals through thermal decomposition or oxidation-reduction reaction can be used. Suitable polymerization initiators comprise potassium persulfate, magnesium persulfate, benzoyl peroxide, hydrogen peroxide, dibenzyl peroxide, cumene hydroperoxide, tert - butyl hydroperoxide and the like. Among them, water-soluble initiator such as potassium persulfate is preferred. The polymerization initiator is used in an amount of 0.1-5 parts by weight, preferably 0.1-2 parts by weight.
[51] To the rubber core, a polymerization initiator and a vinyl monomer is added dropwise continuously at 50-100 °C to form a plastic shell, followed by coagulation by means of the addition of a coagulating agent and filtration to prepare a silicone impact modifierwith high refractive index.
[52] Examples of the vinyl monomer include alkylmethacrylate, acrylate and ethylenically unsaturated aromatic compound and so forth. Among them, methyl- methacylate, styrene, acrylonitrile or a mixture of two or more thereof is preferable. The vinyl monomer of the present invention is used in an amount of 5-90 parts by weight, preferably 10-50 parts by weight based on the total weight of reactants.
[53] As the coagulating agent, metal salt such as magnesium chloride, calcium chloride, magnesium sulfate, calcium sulfate or the like can be used.
[54] The impact modifier thus obtained has a high refractive indexof 1.49-1.59. The impact modifier of the present invention can provide a thermoplastic resin with good heat stability, impact resistance even at low temperatures, weather resistance, and excellent coloration. The thermoplastic resin that can be used in the present invention is not particularly limited. Examples of the thermoplastic resin include a vinyl chloride resin, a styrenic resin, a styrene-acrylonitrile resin, an acrylic resin, a polyester resin, an ABS resin, a polycarbonate resin, and so forth. Especially, when the impact modifier of the present invention is used in polycarbonate resin for housings of electronic instrument, the effect is magnified.
[55] When the thermoplastic resin is a polycarbonate resin, the silicone impact modifier of the present invention is blended into the composition in an amount of 0.5-30 parts by weight, per 100 parts by weight of the polycarbonate resin.
[56]
[57] The present invention may be better understood by reference to the following examples that are intended for the purpose of illustration and are not to be construed as in any way limiting the scope of the present invention, which is defined in the claims appended hereto.
[58]
Mode for the Invention
[59] Examples
[60]
[61] Example 1
[62]
[63] 9Og of dimethylsiloxane-diphenylsiloxane cross-linked copolymer having a refractive index of 1.43, a particle size of 170 nm and 65% of an insoluble portion in toluene and 1.4 g of sodium dodecylbenzene sulfate were dispersed into 760 g ion- exchanged water to obtain a silicone latex. To the silicone latex, 190 g of n- butylacrylate, 36 g of styrene and 9 g of triallyl isocyanurate were added and mixed at room temperature. To the mixture was added 1.8 g of potassium persulfate maintaining the temperature at 75 °C and the polymerization was carried out for 4 hours. And thereto was further added 0.7 g potassium persulfate followed by adding dropwise a mixed solution consisting of 101.25 g of styrene and 33.75 g of acrylonitrile for 15 minutes. After reacting for 4 hours at 75 °C, the system was cooled to room temperature. The conversion was 97.4%. The obtained latex was coagulated in a 1.5% aqueous MgSO 4 solution maintained at 75 °C, and then the coagulated latex was washed and dried to obtain an impact modifier in a powder form.
[64]
[65] Example 2
[66]
[67] 112.5 g of dimethylsiloxane-diphenylsiloxane cross-linked copolymer having a refractive index of 1.45, a particle size of 210 nm and 60% of an insoluble portion in toluene and 2.7 g of sodium dodecylbenzene sulfate were dispersed into 980 g of ion- exchanged water to obtain a silicone latex. To the silicone latex, 112.5 g of n- butylacrylate, 90 g of styrene and 9 g of triallyl isocyanurate were added and mixed at room temperature. The subsequent procedure was conducted in the same manner as in Example 1 to obtain an impact modifier in a powder form. The conversion was 95.8%.
[68]
[69] Example 3
[70]
[71] 112.5 g of dimethylsiloxane-diphenylsiloxane cross-linked copolymer having a refractive index of 1.49, a particle size of 130 nm and 55% of an insoluble portion in toluene and 2.7 g of sodium dodecylbenzene sulfate were dispersed into 980 g of ion- exchanged water to obtain a silicone latex. To the silicone latex, 107.8 g of n- butylacrylate, 90 g of styrene and 4.7 g of allyl methacrylate were added and mixed at room temperature. The subsequent procedure was conducted in the same manner as in Example 1 to obtain an impact modifier in a powder form. The conversion was 95.2%.
[72]
[73] Example 4
[74]
[75] 67.5 g of dimethylsiloxane cross-linked polymer having a refractive index of 1.41, a particle size of 250 nm and 68% of an insoluble portion in toluene and 3.2 g of sodium dodecylbenzene sulfate were dispersed into 980 g ion-exchanged water to obtain a silicone latex. To the silicone latex, 171 g of n-butylacrylate, 76.5 g of styrene and 4.5 g of allyl methacrylate were added and mixed at room temperature. To the mixture was added 1.8 g of potassium persulfate maintaining the temperature at 75 °C and the polymerization was carried out for 4 hours. And thereto was further added 0.68 g potassium persulfate followed by adding dropwise a mixed solution consisting of 49.5 g of styrene, 36 g of acrylonitrile and 49.5 g of methylmethacrylate for 15 minutes. The subsequent procedure was conducted in the same manner as in Example 1 to obtain an impact modifier in a powder form. The conversion was 95.2%.
[76]
[77] Comparative Example 1
[78]
[79] 157.5 g of dimethylsiloxane cross-linked polymer having a refractive index of 1.41, a particle size of 300 nm and 69% of an insoluble portion in toluene and 3.15 g of sodium dodecylbenzene sulfate were dispersed into 976 g of ion-exchanged water to obtain a silicone latex. To the silicone latex, 153 g of n-butylacrylate and 4.5 g of allyl methacrylate were added and mixed at room temperature. The subsequent procedure was conducted in the same manner as in Example 1 to obtain an impact modifier in a powder form. The conversion was 97.6%. [81] Comparative Example 2
[82] [83] Metablen SRK-200(product name) manufactured by Mitsubishi Rayon Company of Japan was used as a silicone impact modifier.
[84] [85] Comparative Example 3 [86] [87] Comparative Example 3 was conducted in the same manner as in Example 1 except that 90 g of dimethylsiloxane-diphenylsiloxane linear copolymer having a refractive index of 1.43, a particle size of 220 nm and less than 5% of an insoluble portion in toluene was used instead of dimethylsiloxane-diphenylsiloxane cross-linked copolymer. The conversion was 94.6%.
[88] [89] The physical properties of the silicone impact modifiers obtained in the above Examples and Comparative Examples were measured as follow:
[90] (1) Refractive Index: Using samples prepared by hot pressing the resulting impact modifier to the thickness of 1 mm, the refractive index was measured by using a light of laser wave length 632.8 nm by a prism coupler type laser refractometer (product name: SPA-4000) made by Sairon Tech. company.
[91] (2) Coloration Property: The coloration property was evaluated using molded samples prepared by mixing polycarbonate, impact modifier and carbon black in proportion of 97 : 3 : 0.2 by observing it with naked eyes. Also, brightness (L ) of the molded sample was measured by means of a spectrophotometer (CM-3600d) manufactured by Konica Minota Company.
[92] (3) Impact Resistance: Polycarbonate, impact modifier and carbon black were mixed in proportion of 97 : 3 : 0.2 and extruded through a twin screw extruder with Φ=45 mm in pellets. The pellets were dried at 110 °C over 3 hours and then molded using a 10 oz injection molding machine at 260—330 °C and barrel temperature of 60~100 °C into 1/8" Izod test bars and plate test specimens (thickness : 3 mm) respectively. The impact resistance was evaluated by Izod impact resistance test in accordance with ASTM D-256 and by falling ball impact test.
[93] [94] Table 1
Figure imgf000010_0001
Figure imgf000011_0001
[95] a) The lower the brightness(L ), the better the coloration property.
[96] [97] As shown above, the impact modifiers of Examples 1-4 show higher refractive index (more than 1.49) and better coloration property without deterioration of impact strength than those of Comparative Examples 1-2. In particular, the impact modifier of Comparative Example 3 which employs linear organosiloxane copolymer shows poor impact strength and bad coloration property even it has high refractive index of 1.500.
[98] [99] The present invention can be easily carried out by an ordinary skilled person in the art. Many modifications and changes may be deemed to be with the scope of the present invention as defined in the following claims.
[100]

Claims

Claims
[1] A silicone impact modifier comprising:
(A) a rubber core consisting of (a ) an organosiloxane cross-linked (co)polymer with a particle size of 50-400 nm and (a ) an alkylacrylate-styrene aromatic compound cross-linked copolymer; and
(B) a plastic shell consisting of a vinyl (co)polymer; wherein the refractive indexof the silicone impact modifier is 1.49-1.59.
[2] The silicone impact modifier as defined in claim 1, wherein the refractive index of said organosiloxane cross-linked (co)polymer (a ) is 1.41-1.50.
[3] A silicone impact modifier comprising:
(A) a rubber core consisting of (a ) an organosiloxane cross-linked (co)polymer with a particle size of 50—400 nm and (a ) an alkylacrylate cross-linked polymer; and
(B) a plastic shell consisting of a vinyl (co)polymer; wherein the refractive indexof the silicone impact modifier is 1.49-1.59.
[4] The silicone impact modifier as defined in claim 3, wherein the refractive index of said organosiloxane cross-linked (co)polymer (a ) is 1.44-1.55.
[5] The silicone impact modifier as defined in claim 1 or 3, the weight ratio of (a ) the organosiloxane cross-linked (co)polymer to (a ) the alkylacrylate-styrenic aromatic compound cross-linked copolymer or the alkylacrylate cross-linked copolymer is 1 : 6-6 : 1 ; and the weight ratio of the alkylacrylate to the styrenic aromatic compound in said alkylacrylate-styrenic aromatic compound cross- linked copolymer(a ) is 1 : 1-20 : 1.
[6] The silicone impact modifier as defined in claim 1 or 3, the weight ratio of the rubber core (A) to the plastic shell (B) is 5 : 5-9 : 1.
[7] A method of preparing the silicone impact modifier comprising: preparing a rubber core through cross-polymerization by adding an alkylacrylate and a styrenic aromatic compound to an organosiloxane cross-linked
(co)polymer having a particle size of 50~400 nm; and graft (co)polymerizing a vinyl monomer onto the rubber core to form a plastic shell.
[8] A method of preparing the silicone impact modifier comprising: preparing a rubber core through cross-polymerization by adding an alkylacrylate to an organosiloxane cross-linked (co)polymer having a particle size of 50~400 nm; and graft (co)polymerizing a vinyl monomer onto the rubber core to form a plastic shell.
[9] The method of preparing the silicone impact modifier as defined in claim 7 or 8, wherein said organosiloxane is selected from the group consisting of dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane and a mixture or a copolymer thereof; said alkylacrylate is n-butylacrylate; said styrenic aromatic compound is selected from the group consisting of styrene, α-methylstyrene, di- vinylbenzene, vinyltoluene and the mixture thereof; said vinyl monomer is selected from the group consisting of methylmethacylate, styrene, acrylonitrile and a mixture thereof.
[10] The method of preparing the silicone impact modifier as defined in claim 7 or 8, wherein said cross-polymerization is conducted by using allyl methacrylate or triallyl isocyanurate as a crosslinking agent.
[11] The method of preparing the silicone impact modifier as defined in claim 7 or 8, wherein the amount of the organosiloxane cross-linked (co)polymer is 5-90 parts by weight, the amount of the alkyl acrylate is 5-90 parts by weight, the amount of the styrenic aromatic compound is 0.01-50 parts by weight, and the amount of the vinyl monomer is 5-90 parts by weight.
[12] A thermoplastic resin composition comprising the silicone impact modifier of claim 1 or 3 and a thermoplastic resin.
[13] The thermoplastic resin composition as defined in claim 12, wherein said thermoplastic resin is selected from the group consisting of a vinyl chloride resin, a styrenic resin, a styrene-acrylonitrile resin, an acrylic resin, a polyester resin, an ABS resin and a polycarbonate resin.
[14] The thermoplastic resin composition as defined in claim 13, wherein said thermoplastic resin is a polycarbonate resin, and the impact strength modifier is blended into the composition in an amount of 0.5-30 parts by weight, per 100 parts by weight of the polycarbonate resin.
PCT/KR2005/001831 2004-12-31 2005-06-15 Silicone impact modifier with high refractive index and method for preparing the same Ceased WO2006070983A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP05750719A EP1841810B1 (en) 2004-12-31 2005-06-15 Silicone impact modifier with high refractive index and method for preparing the same
CN2005800455928A CN101094882B (en) 2004-12-31 2005-06-15 Silicone impact modifier with high refractive index and preparation method thereof
US11/323,646 US7541401B2 (en) 2004-12-31 2005-12-28 Impact modifier for a polymer composition and method for preparing the same
US11/768,984 US7956105B2 (en) 2004-12-31 2007-06-27 Silicone impact modifier with high refractive index and method for preparing the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2004-0117912 2004-12-31
KR20040117912 2004-12-31

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/768,984 Continuation-In-Part US7956105B2 (en) 2004-12-31 2007-06-27 Silicone impact modifier with high refractive index and method for preparing the same

Publications (1)

Publication Number Publication Date
WO2006070983A1 true WO2006070983A1 (en) 2006-07-06

Family

ID=36615076

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2005/001831 Ceased WO2006070983A1 (en) 2004-12-31 2005-06-15 Silicone impact modifier with high refractive index and method for preparing the same

Country Status (5)

Country Link
US (1) US7956105B2 (en)
EP (2) EP2399950B1 (en)
KR (1) KR100568092B1 (en)
CN (3) CN101906191A (en)
WO (1) WO2006070983A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1832613A4 (en) * 2004-12-28 2009-09-02 Kaneka Corp Graft copolymer, method for producing same and resin composition containing such graft copolymer
US7956105B2 (en) 2004-12-31 2011-06-07 Cheil Industries Inc. Silicone impact modifier with high refractive index and method for preparing the same

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100708993B1 (en) * 2005-06-07 2007-04-18 주식회사 엘지화학 Polymeric lubricant having multi layer structure and manufacturing method thereof
KR20140086729A (en) * 2012-12-28 2014-07-08 제일모직주식회사 Pransparent thermoplastic resin composition and molded article using the same
KR101747592B1 (en) 2013-06-28 2017-06-14 미쯔비시 케미컬 주식회사 Polyorganosiloxane-containing graft copolymer, thermoplastic resin composition, and molded article
CN110709437B (en) * 2017-06-06 2022-07-05 三菱化学株式会社 Polyorganosiloxane-containing graft copolymer, thermoplastic resin composition, and molded article
CN107266849B (en) * 2017-08-04 2019-07-19 上海跃贝新材料科技股份有限公司 A kind of low temperature resistant plating PC/ABS alloy material drawn cruelly and preparation method
EP3774957A1 (en) 2018-03-29 2021-02-17 Rohm and Haas Company Modified styrene-acrylonitrile
CN111801364B (en) 2018-03-29 2024-03-26 罗门哈斯公司 Three stage polymer particles
BR112020026761A2 (en) 2018-07-27 2021-03-30 Rohm And Haas Company POLYMERIC PARTICLE, AND, POLYMER COMPOSITION
KR102802870B1 (en) 2018-07-27 2025-05-07 다우 실리콘즈 코포레이션 Polymerization of silicone and acrylic monomers
CN112384544B (en) 2018-07-27 2024-03-12 罗门哈斯公司 Bimodal silicone-acrylic polymer particles
KR102363986B1 (en) 2018-11-16 2022-02-16 주식회사 엘지화학 Core-shell copolymer, method for preparing the core-shell copolymer and thermoplastic resin composition comprising the core-shell copolymer
CN115505223B (en) * 2022-06-30 2023-08-18 南京工业大学 Low-temperature impact-resistant rigid polyvinyl chloride sheet for packaging and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5132359A (en) * 1988-01-25 1992-07-21 Mitsubishi Rayon Company, Ltd. Vinyl chloride resin composition
JPH09157484A (en) * 1995-12-01 1997-06-17 Mitsubishi Rayon Co Ltd Thermoplastic resin composition
US6153694A (en) * 1997-07-29 2000-11-28 Kaneka Corporation Graft copolymer particles and thermoplastic resin compositions
KR20040095402A (en) * 2003-04-28 2004-11-15 주식회사 엘지화학 Crashing Reinforcing Agent and the Resin Composition Containing the Same
KR20050015088A (en) * 2003-08-02 2005-02-21 주식회사 엘지화학 Acryl-silicones Complex Impact-Modifier and Method for Preparing the Same, and Vinyl Chloride Resin Composition Having the Same
KR20050049127A (en) * 2003-11-21 2005-05-25 제일모직주식회사 Polycarbonate resin composition having excellent flow and impact-resistance
KR20050060604A (en) * 2003-12-17 2005-06-22 주식회사 엘지화학 Impact modifier having multi-layer structure and thermoplastic resin composition containing the same

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3617267A1 (en) * 1986-05-23 1987-11-26 Bayer Ag NOTCH IMPACT TOE GRAFT POLYMERISATE
EP0307963B1 (en) * 1987-09-21 1995-02-15 Mitsubishi Rayon Co., Ltd. Polycarbonate resin composition
JP2608439B2 (en) * 1988-01-25 1997-05-07 三菱レイヨン株式会社 Impact resistant resin composition
US5106908A (en) * 1988-11-14 1992-04-21 General Electric Company Polyorganosiloxane/polyvinyl-based graft (meth)acrylate polymers
JP3163180B2 (en) 1992-10-05 2001-05-08 三菱レイヨン株式会社 Impact resistant resin composition
EP0647677B1 (en) * 1993-10-06 2001-12-05 Ticona GmbH Polymer alloy
US6169149B1 (en) * 1998-12-04 2001-01-02 General Electric Company Emulsion polymerized silicone-acrylate rubber impact modifiers thermoplastic blends, and methods for making
JP2000290482A (en) * 1999-04-06 2000-10-17 Mitsubishi Rayon Co Ltd Polyester resin composition
JP2001059006A (en) 1999-08-23 2001-03-06 Mitsubishi Rayon Co Ltd Graft copolymer and thermoplastic resin composition containing the same
JP2002020443A (en) 2000-07-06 2002-01-23 Mitsubishi Rayon Co Ltd Graft copolymer, thermoplastic resin composition containing the same, and molded article thereof
US20020111428A1 (en) * 2000-12-14 2002-08-15 General Electric Company Transparent polycarbonate polyester composition and process
TWI317749B (en) 2002-02-15 2009-12-01 Kaneka Corp Graft copolymers and impact-resistant flame-retardant resin compositions containing the same
JP4112421B2 (en) 2003-05-01 2008-07-02 三菱レイヨン株式会社 Graft copolymer and thermoplastic resin composition using the same
KR20050049973A (en) 2003-11-24 2005-05-27 삼성전자주식회사 Method for controlling store of mobile storage and terminal using this
EP2399950B1 (en) 2004-12-31 2013-04-17 Cheil Industries Inc. Silicone impact modifier with high refractive index and method for preparing the same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5132359A (en) * 1988-01-25 1992-07-21 Mitsubishi Rayon Company, Ltd. Vinyl chloride resin composition
JPH09157484A (en) * 1995-12-01 1997-06-17 Mitsubishi Rayon Co Ltd Thermoplastic resin composition
US6153694A (en) * 1997-07-29 2000-11-28 Kaneka Corporation Graft copolymer particles and thermoplastic resin compositions
KR20040095402A (en) * 2003-04-28 2004-11-15 주식회사 엘지화학 Crashing Reinforcing Agent and the Resin Composition Containing the Same
KR20050015088A (en) * 2003-08-02 2005-02-21 주식회사 엘지화학 Acryl-silicones Complex Impact-Modifier and Method for Preparing the Same, and Vinyl Chloride Resin Composition Having the Same
KR20050049127A (en) * 2003-11-21 2005-05-25 제일모직주식회사 Polycarbonate resin composition having excellent flow and impact-resistance
KR20050060604A (en) * 2003-12-17 2005-06-22 주식회사 엘지화학 Impact modifier having multi-layer structure and thermoplastic resin composition containing the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1841810A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1832613A4 (en) * 2004-12-28 2009-09-02 Kaneka Corp Graft copolymer, method for producing same and resin composition containing such graft copolymer
US7956105B2 (en) 2004-12-31 2011-06-07 Cheil Industries Inc. Silicone impact modifier with high refractive index and method for preparing the same

Also Published As

Publication number Publication date
CN1803867A (en) 2006-07-19
CN101094882B (en) 2012-05-09
CN101094882A (en) 2007-12-26
KR100568092B1 (en) 2006-04-05
EP1841810A1 (en) 2007-10-10
CN100595217C (en) 2010-03-24
EP1841810A4 (en) 2009-09-02
EP2399950A1 (en) 2011-12-28
US7956105B2 (en) 2011-06-07
EP2399950B1 (en) 2013-04-17
US20080097007A1 (en) 2008-04-24
CN101906191A (en) 2010-12-08
EP1841810B1 (en) 2012-05-09

Similar Documents

Publication Publication Date Title
US7956105B2 (en) Silicone impact modifier with high refractive index and method for preparing the same
JP2005534775A (en) Thermoplastic composition having low gloss appearance
KR20210033419A (en) Thermoplastic resin composition, method for preparing the same and article prepared therefrom
US4631307A (en) Heat-resistant high impact styrene resin, process for production thereof, and resin composition comprising said styrene resin
WO2008032907A1 (en) Transparent abs resin composition having excellent impact strength and flowability
JP2002530494A (en) Emulsion-polymerized polyacrylate rubber, impact modifier, blend obtained therefrom, and production method
JPS62106915A (en) Transparency and impact property modifier for polyvinyl chloride
JPS58210951A (en) Polyblend of polyglutalimide-styrene-acrylonitrile copolymer
KR101053833B1 (en) (Meth) acrylate copolymer and thermoplastic resin composition comprising the same
US7541401B2 (en) Impact modifier for a polymer composition and method for preparing the same
CA2437701A1 (en) Impact modifier for thermoplastic resin and resin composition containing the same
CN114269847B (en) Thermoplastic resin composition, method for producing the same, and molded article comprising the same
JPH02115251A (en) Compatible polymer mixture and polymer composition made of said mixture
GB2228942A (en) Multi-layer structure polymer and resin composition
JP2003020378A (en) Transparent sliding thermoplastic resin composition
KR100656971B1 (en) High refractive index impact modifier excellent in coloring property and low temperature impact resistance and manufacturing method
JPH0725971B2 (en) Methyl methacrylate-α-methylstyrene copolymer resin composition
TWI288764B (en) Silicone impact modifier with high refractive index and method for preparing the same
KR100762740B1 (en) Silicone Impact Modifier Having High Refractive Index and Good Thermal Stability and Method for Preparing the Same
JP3438833B2 (en) Manufacturing method of impact-resistant thermoplastic resin
JPH04146910A (en) Multilayer graft copolymer
JPH02294348A (en) Thermoplastic resin composition
JP3311137B2 (en) Thermoplastic resin composition
JP3432591B2 (en) Chemical resistant resin composition
JPH0723442B2 (en) Impact resistant thermoplastic resin composition

Legal Events

Date Code Title Description
DPE2 Request for preliminary examination filed before expiration of 19th month from priority date (pct application filed from 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 11768984

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 200580045592.8

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2005750719

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2005750719

Country of ref document: EP