CN1865323B - Multilayer pellet and method for producing the same - Google Patents
Multilayer pellet and method for producing the same Download PDFInfo
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- CN1865323B CN1865323B CN2006100824064A CN200610082406A CN1865323B CN 1865323 B CN1865323 B CN 1865323B CN 2006100824064 A CN2006100824064 A CN 2006100824064A CN 200610082406 A CN200610082406 A CN 200610082406A CN 1865323 B CN1865323 B CN 1865323B
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Abstract
Disclosed are multilayer pellets comprising a core of a first material comprising a first thermoplastic resin and a sheath layer of a second material comprising a second thermoplastic resin, the sheath layer surrounding the core, wherein (i) the first thermoplastic resin has a melt index, measured at a temperature of 230 DEG C. and a load of 21.2 N, of 200 g/10 min or more, provided that the melt index of the second thermoplastic resin measured at a temperature of 230 DEG C. and a load of 21.2 N is different from that of the first thermoplastic resin or (ii) the first thermoplastic resin is a modified thermoplastic resin having a structure originating in a compound having an unsaturated group.
Description
Technical field
The present invention relates to multi-layer thermoplastic resin granular material that comprises inner core and outer sheath and preparation method thereof.
Particularly, the present invention relates in metal or other polymkeric substance, to have excellent flowability, dispersiveness, and have the excellent mechanical property and the multilayer pellet of paintability, and the method with this multilayer pellet of preparation of good workability and production efficiency.
In addition; The invention still further relates to metal or other polymkeric substance and have excellent adhesivity; And have the excellent mechanical property and a multilayer pellet of paintability, and under the discharging of smell still less, has the method for this multilayer pellet of preparation of good workability and production efficiency
Background technology
Japanese unexamined patent publication No.2003-48991 discloses a kind of multilayer pellet, its by the epitheca that comprises component (A) with comprise that the inner core of component (B) and/or component (C) forms, wherein
Component (A): crystalline polyolefin resin (A),
Component (B): by the olefin copolymer that two kinds or more kinds of alkene are formed, described alkene is selected from: ethene, propylene or C
4-20Terminal olefin, the ethene of described olefin copolymer, propylene and C
4-20The total number of carbon atoms of terminal olefin is 6 or bigger, and satisfies inequality (1):
[y/(x+y)]≥0.30(1)
Wherein x is the content (mol%) of ethene, and y is C
4-20The content of terminal olefin (mol%), component (C): (C-1) and/or (C-2)
(C-1): the multipolymer of forming by vinyl aromatic compounds and conjugated diene compound
(C-2): hydrogenated products (C-1).
Europe not unexamined patent announces that 1063070 A2 disclose a kind of method for preparing multilayer pellet; Described multilayer pellet has inner core-epitheca structure; Wherein moulding material forms epitheca, and described epitheca covers around the periphery of the inner core that another moulding material forms, and this method comprises:
(a): inner core material and sheath materials be supplied to have a plurality ofly extrude the die head devices that form parts along what circumference was settled,
(b): through covering and extrude a plurality of multilayer line material around the periphery of inner core material with one heart from extruding to form the parts with sheath materials, and
(c): with the multilayer line material cutting of extruding, with the preparation multilayer pellet.
Japanese unexamined patent publication No.59-81121 discloses a kind of method for preparing multilayer pellet; This method comprises: will comprise at least a olefin copolymer that is selected from alkene-vinyl alcohol copolymer, ionomer and the resin in the linear polyamidoamine resin and mainly melted by the melt that alkene-the Ji resin is formed and extrude; To form the line material of forming by the inner core of last melt and the epitheca of back one melt; Cool off this line grain, cut this line material then, form pellet.
Summary of the invention
Summary of the invention
One object of the present invention is to provide a kind of thermoplastic resin material with good mechanical properties and good paintability; A kind of thermoplastic resin material particularly is provided; It has excellent mechanical property and paintability; And when moulding, have excellent flowability, and have excellent dispersiveness with metal or other thermoplastic resin, and a kind of thermoplastic resin material is provided; It has excellent mechanical property and paintability, and has excellent adhesivity with metal or other thermoplastic resin.
Another object of the present invention is to be provided for preparing the method for these thermoplastic resin materials.
In first aspect; The present invention provides a kind of multilayer pellet; It comprises the inner core and the outer sheath that contains second material of second thermoplastic resin of first material that contains first thermoplastic resin; Described outer sheath is around described inner core; Wherein the melt index that under the load of 230 ℃ temperature and 21.2N, records of first thermoplastic resin is 200g/10min or bigger, and the condition melt index that to be second thermoplastic resin record under the load of 230 ℃ temperature and 21.2N is different from the melt index of first thermoplastic resin.
In a preferred embodiment, the wt ratio of described epitheca and said inner core is 50/50 to 1/99.
In another preferred embodiment, first thermoplastic resin is the modified polyolefin resin through preparing as the polyolefin resin of raw material, the compound that contains unsaturated group and organo-peroxide melt kneading.
In another embodiment preferred, first thermoplastic resin be through will be as the thermoplastic resin of raw material, contain the compound of unsaturated group and polar group and the modified thermoplastic resin that the organo-peroxide melt kneading prepares simultaneously; And in a more particular embodiment, said thermoplastic resin as raw material is a polyolefin resin.
In second aspect; The present invention provides a kind of method for preparing multilayer pellet; Described multilayer pellet comprises the inner core and the outer sheath that contains second material of second thermoplastic resin of first material that contains first thermoplastic resin; Described epitheca is around described inner core; Wherein the melt index that under the load of 230 ℃ temperature and 21.2N, records of first thermoplastic resin is 200g/10min or bigger, and the condition melt index that to be second thermoplastic resin record under the load of 230 ℃ temperature and 21.2N is different from the melt index of first thermoplastic resin, and this method comprises:
Multilayer with die head forcing machine is provided; Described die head has: through it first material is extruded as first extruding part of inner core and through it second material is extruded as second extruding part of epitheca, settle second extruding part with around first extruding part; Be used for first feeder with first material feeding to the first extruding part; With second feeder that is used for second material feeding to the second extruding part,
First material is fed to first extruding part from first feeder,
Second material is fed to second extruding part from second feeder,
Extrude first material and extrude second material through first extruding part,, form the multilayer extrudate to cover first material with second material through second extruding part, and
Described multilayer extrudate is cut into predetermined length, to form multilayer pellet.
In a preferred embodiment, first thermoplastic resin be through will be as the thermoplastic resin of raw material, contain compound and the organo-peroxide melt kneading of unsaturated group and polar group simultaneously and in first feeder, form.
In another preferred embodiment, described die head is a die head of right angle.
In the third aspect; The present invention provides a kind of multilayer pellet; It comprises the inner core and the outer sheath that contains second material of second thermoplastic resin of first material that contains first thermoplastic resin; Described outer sheath is around described inner core, and wherein first thermoplastic resin is the modified thermoplastic resin with the structure that originates from the compound that contains unsaturated group.
In a preferred embodiment, described modified thermoplastic resin has the structure derived from the compound that contains unsaturated group and polar group simultaneously.
In another preferred embodiment, the wt ratio of described epitheca and said inner core is 50/50 to 1/99.
In another embodiment preferred, first thermoplastic resin be through will be as the thermoplastic resin of raw material, contain the compound of unsaturated group and polar group and the modified thermoplastic resin that the organo-peroxide melt kneading prepares simultaneously.
In another embodiment preferred, first thermoplastic resin be through with 100 weight parts as the thermoplastic resin of raw material, 0.01 weight part or more contain the modified thermoplastic resin that the organo-peroxide melt kneading of compound and 0.001 to 20 weight part of unsaturated group and polar group prepares simultaneously.
In another embodiment preferred, the melt index that first thermoplastic resin records under the load of 230 ℃ temperature and 21.2N is less than 200g/10min.
In fourth aspect; The present invention provides a kind of method for preparing multilayer pellet; Described multilayer pellet comprises the inner core and the outer sheath that contains second material of second thermoplastic resin of first material that contains first thermoplastic resin; Described epitheca is around described inner core, and wherein first thermoplastic resin is the modified thermoplastic resin with the structure that originates from the compound that contains unsaturated group, and this method comprises:
Multilayer with die head forcing machine is provided; Described die head has: through it first material is extruded as first extruding part of inner core and through it second material is extruded as second extruding part of epitheca, settle second extruding part with around first extruding part; Be used for first feeder with first material feeding to the first extruding part; With second feeder that is used for second material feeding to the second extruding part,
First material is fed to first extruding part from first feeder,
Second material is fed to second extruding part from second feeder,
Extrude first material and extrude second material through first extruding part,, form the multilayer extrudate to cover first material with second material through second extruding part, and
Described multilayer extrudate is cut into predetermined length, to form multilayer pellet.
In a preferred embodiment, first thermoplastic resin be through will be as the thermoplastic resin of raw material, contain compound and the organo-peroxide melt kneading of unsaturated group and polar group simultaneously and in first feeder, form.
In another preferred embodiment, described die head is a die head of right angle.
DESCRIPTION OF THE PREFERRED
At first, explained later first and second aspects of the present invention.
Multilayer pellet of the present invention comprises the inner core and the outer sheath that contains second material of second thermoplastic resin of first material that contains first thermoplastic resin; Described outer sheath is around described inner core, and wherein the melt index that under the load of 230 ℃ temperature and 21.2N, records of first thermoplastic resin is 200g/10min or bigger.Here, the melt index that under the load of 230 ℃ temperature and 21.2N, records of second thermoplastic resin is different from the melt index of first thermoplastic resin.
Consider at the fusing multilayer pellet and the flowability and the melt tension of material in the process of its moulding, the wt ratio of preferred described epitheca and said inner core is 50/50 to 1/99, and more preferably 30/70 to 1/99.
Being included in the melt index that first thermoplastic resin in first material of the inner core that constitutes multilayer pellet records under the load of 230 ℃ temperature and 21.2N is 200g/10min or bigger, and preferably in 200 to 20000g/10min scope.
Preferred first thermoplastic resin be through will be as the thermoplastic resin of raw material, contain the compound of unsaturated group and polar group and grafting-modified thermoplastic resin that the organo-peroxide melt kneading prepares simultaneously; And more preferably first thermoplastic resin is the modified polyolefin resin through using polyolefin resin to prepare as " as the thermoplastic resin of raw material ".
Preferred first thermoplastic resin be through will be as the thermoplastic resin of raw material, contain the compound of unsaturated group and polar group and the modified thermoplastic resin that the organo-peroxide melt kneading prepares simultaneously; And be more preferably modified polyolefin through using polyolefin resin to prepare as " as the thermoplastic resin of raw material ".
As for second thermoplastic resin that is included in second material that constitutes outer sheath; Select thermoplastic resin, be different from first thermoplastic resin in first material that is included in the formation inner core aspect its melt index that under the load of 230 ℃ temperature and 21.2N, records.The melt index that second thermoplastic resin records under the load of 230 ℃ temperature and 21.2N preferably is lower than 200g/10min, more preferably in 0.1 to 150g/10min scope.
First thermoplastic resin that is used for inner core comprises with the instance that is used for second thermoplastic resin of outer sheath: polyolefin resin; Styron, like PS, impact polystyrene (that is, containing the PS of the cross-linking products of a small amount of itself and polyhutadiene), and ABS resin; Acrylics is like polymethylmethacrylate; Vibrin is like polyethylene terephthalate and polybutylene terephthalate; Polycarbonate resin is like polycarbonate; Polyamide resin is like polyamide 66, polyamide 6 and polymeric amide 46; Polyacetal resin is like polyacetal copolymer and POM-H Acetal homopolymer; Engineering plastics are like polyethersulfone, polyetherimide, TPI, polyetherketone, polyetheretherketone and polyphenylene sulfide; Derivatived cellulose is like rhodia, cellulose acetate butyrate and TKK 021; Thermoplastic elastomer is like TPUE, thermoplastic styrene-butadiene elastomer, thermoplastic polyester elastomer, thermoplasticity vinylchlorid elastomerics and thermoplastic polyamide elastomer; Fluoro-resin; And their modified product.
First thermoplastic resin that is used for inner core is polyolefin resin (for example, vinyl polymerization resin, propylene polymer resin preferably; The butene polymerization resin, ethene, aromatic vinyl compound (for example, vinylbenzene) and conjugated diolefine is (for example; The hydrogen affixture of multipolymer 1,3-butadiene)); And more preferably vinyl polymerization resin and propylene polymer resin; And propylene polymer resin more preferably again.
First thermoplastic resin both can be single thermoplastic resin of planting, and also can be the mixture of two or more thermoplastic resins.Similarly, second thermoplastic resin both can be single thermoplastic resin of planting, and also can be the mixture of two or more thermoplastic resins.
" vinyl polymerization resin " used herein is the monomeric polymerisate of mainly being made up of ethene.Structural unit and 0.01 to the 49 weight % that the example comprises Alathon, originate from ethene by 51 to 99.99 weight % originates from one or more multipolymers that can form with the monomeric structural unit of ethylene copolymer, and their mixture.
The instance of " can with the monomer of ethylene copolymer " comprises propylene, contains terminal olefin, propenoate, methacrylic ester and the vinyl-acetic ester of 4 to 20 carbon atoms.The instance of " terminal olefin that contains 4 to 20 carbon atoms " comprises 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene and vinyl cyclohexane.An instance of " propenoate " is a methyl acrylate, and an instance of " methacrylic ester " is a TEB 3K.
" multipolymer of ethene and as ethene with can with the monomeric multipolymer of ethylene copolymer " instance comprise ethylene-propylene copolymer, ethene-alpha-olefin copolymer, ethylene-methyl methacrylate methyl terpolymer and vinyl-vinyl acetate copolymer.The instance of " ethene-alpha-olefin copolymer " comprises ethene-butene-1 copolymer, ethene-1-pentene copolymer, ethene-1-hexene copolymer, ethene-1-octene copolymer and ethene-1-decene multipolymer.
" propylene polymer resin " used herein is the monomeric polymerisate of mainly being made up of propylene.The example comprises alfon; Originate from the propylene-ethylene random copolymers that the structural unit of propylene and structural unit that 0.01 to 49 weight % originates from ethene are formed by 51 to 99.99 weight %; The structural unit and 0.01 to the 49 weight % that are originated from propylene by 51 to 99.99 weight % originate from the propylene-alpha-olefin random copolymers that one or more structural units that contain the terminal olefin of 4 to 20 carbon atoms are formed; Be included as first segment of alfon part and be the propylene-ethylene random copolymers second segmental propylene-ethylene block copolymer partly; Be included as first segment of alfon part and be the propylene-alpha-olefin random copolymers second segmental propylene-alpha-olefin segmented copolymer partly, wherein said terminal olefin is the terminal olefin that contains 4 to 20 carbon atoms; And their mixture.
The instance that is used to prepare " terminal olefin that contains 4 to 20 carbon atoms " of propylene-alpha-olefin random copolymers and propylene-alpha-olefin segmented copolymer comprises 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene and vinyl cyclohexane.Preferred 1-butylene.
The preferred embodiment of propylene-alpha-olefin random copolymers comprises propylene-1-butylene random copolymers.The preferred embodiment of propylene-alpha-olefin segmented copolymer comprises propylene-1-butylene segmented copolymer.
Propylene-ethylene block copolymer and propylene-alpha-olefin segmented copolymer are normally through using a kind of step (i) and step method preparation (ii) of comprising; Step (i) preparation will become the first segmental alfon, and preparation will become the second segmental multipolymer in the presence of the alfon that step (ii) prepares in step (i).
The preferred embodiment that is included in first thermoplastic resin in first material that constitutes inner core comprises: through the modified thermoplastic resin that will prepare as the thermoplastic resin of raw material, the compound that contains unsaturated group and organo-peroxide melt kneading.Particularly, the modified polyolefin resin that preferably prepares as " as the thermoplastic resin of raw material " through the use polyolefin resin.
At the compound that contains unsaturated group that is used for preparing modified thermoplastic resin, unsaturated group can preferably contain the group of carbon-to-carbon double bond or contain the group of carbon-to-carbon triple bond.The group that especially preferably contains carbon-to-carbon double bond.
The compound that preferably contains unsaturated group also contains polar group.The instance of this polar group comprises carboxyl, carbalkoxy, allyloxy, amino, carboxamido-group, imide base, itrile group, epoxy group(ing), hydroxyl, NCO; The functional group of derived from carboxylic acid, acid amides, acid azide, carboxylic acid halides, acid anhydrides 、 oxazoline etc.; And the functional group of derived from carboxylic acid salt, amide salt, the salt of acid azide, the salt of carboxylic acid halides etc.
The examples for compounds that contains unsaturated group comprises: unsaturated carboxylic acid, olefinically unsaturated carboxylic acid derivatives, unsaturated epoxy compound, unsaturated alcohol, unsaturated amine and unsaturated isocyanate.
The more specifically instance that contains the compound of unsaturated group comprises:
(1) toxilic acid, maleic anhydride, fumaric acid, maleimide, Regulox, methyl norbornene dioic anhydride, dichloro-maleic anhydride, maleinamide, methylene-succinic acid, itaconic anhydride, (methyl) glycidyl acrylate, 2-hydroxyethyl methacrylate and allyl glycidyl ether
(2) reaction product of maleic anhydride and diamines, the compound that for example has the structure of following formula:
Wherein R representes aliphatic group or aromatic group,
(3) natural oil, for example, soya-bean oil, tung oil, Viscotrol C, oleum lini, hempseed oil, Oleum Gossypii semen, til, rapeseed oil, peanut oil, Camellia oil, sweet oil, Oleum Cocois and sardine oil,
(4) epoxidised natural oil
(5) unsaturated carboxylic acid for example; Vinylformic acid; Butenoic acid; Ba Dousuan; Vinylacetic acid; Methylacrylic acid; Pentenoic acid; Angelicic acid; Tiglic acid; The 2-pentenoic acid; The 3-pentenoic acid; α-Yi Jibingxisuan; β-Jia Jibadousuan; The 4-pentenoic acid; The 2-hexenoic acid; 2-methyl-2-pentenoic acid; 3-methyl-2-pentenoic acid; α-ethyl crotonic acid; 2; 2-dimethyl--3-butenoic acid; The 2-heptenoic acid; The 2-octylenic acid; The 4-decylenic acid; The 9-undecylenic acid; The 10-undecylenic acid; The 4-dodecenoic acid; Linderic acid; The 4-tetradecenoic acid; The 9-tetradecenoic acid; Palmitoleic acid; The 2-octadecenoic acid; The 9-octadecenoic acid; Eicosenoic acid; Decosahedaenoic acid; Erucic acid; Tetracosenoic acid; Mycolipenic acid; 2; The 4-Sorbic Acid; Diallyl acetate; Herba Erodii (Herba Geranii) acid (geranium acid); 2; The 4-decadienoic acid; 2; The 4-dodecadienoic acid; 9; The 12-hexadecadienoic acid; 9; The 12-octadecadienoic acid; Hiragonic acid; Eicosadienoic acid; Eicosatrienoic acid; Eicosatetraenoic acid; Ricinolic acid; Eleostearic acid; Oleic acid; Pentacosa alkene acid; Erucic acid; Two dodecadienoic acids (docosadienoic acid); Docosatrienoic acid; Docosatetratenoic acid; DPA; Hexacosenoic acid; Hexacosandienoic acid; Two octadecenoic acids (octacosenoic acid) and 40 carbon enoic acids (tetracontenoic acid)
(6) ester cpds of above-mentioned unsaturated carboxylic acid, amide compound or acid anhydride,
(7) vinyl carbinol, crotyl alcohol, methyl ethylene methyl alcohol, vinyl-ethyl alcohol, methylpropenyl methyl alcohol, 4-amylene-1-ol, 10-undecene-1-alcohol, propynol, 1; 4-pentadiene-3-alcohol, 1,4-hexadiene-3-alcohol, 3,5-hexadiene-2-pure and mild 2; 4-hexadiene-1-alcohol
(8) unsaturated alcohol, like the 3-butene-1,2-glycol, 2,5-dimethyl--3-hexene-2,5-glycol, 1,5-hexadiene-3,4-two is pure and mild 2,6-octadiene-4, the 5-glycol,
(9) usefulness-NH
2Group replaces the OH group of above-mentioned unsaturated alcohol and the unsaturated amine that obtains,
(10) adduct of the oligopolymer (for example, number-average molecular weight is about 500 to about 10000 polymkeric substance) of the maleic anhydride of phenol and divinyl, isoprene etc.,
(11) superpolymer of the maleic anhydride of phenol and divinyl, isoprene etc. (for example, number-average molecular weight be 10000 or bigger polymkeric substance) adduct,
(12) material that obtains through the oligopolymer (for example, number-average molecular weight is about 500 to about 10000 polymkeric substance) that amino, carboxyl, hydroxyl, epoxide group etc. is introduced into divinyl, isoprene etc.,
(13) superpolymer through amino, carboxyl, hydroxyl, epoxide group etc. being introduced into divinyl, isoprene etc. (for example, number-average molecular weight be 10000 or bigger polymkeric substance) material that obtains,
(14) allyl isocyanate.
The compound that contains unsaturated group is preferably selected from: maleic anhydride, toxilic acid, fumaric acid, itaconic anhydride, methylene-succinic acid, (methyl) glycidyl acrylate and 2-hydroxyethyl methacrylate.
The compound that contains unsaturated group can contain the unsaturated group of two or more identical or different types.When the compound that contains unsaturated group also contained polar group, it can contain the polar group of two or more identical or different types.
Consider the grafting ratio of the compound that contains unsaturated group and thermoplastic resin and by the paintability of the rosin products of multilayer pellet preparation of the present invention; Based on the thermoplastic resin of 100 weight parts as raw material; The usage quantity that contains the compound of unsaturated group typically is 0.01 to 30 weight part, and is preferably 0.1 to 20 weight part.
Consider the grafting ratio of the compound that contains unsaturated group and thermoplastic resin and avoid decomposition as the thermoplastic resin of raw material, the organo-peroxide that preferably uses with the compound that contains unsaturated group be in 50 to 210 ℃ decomposition temperature scope its transformation period become 1 minute organo-peroxide.Preferably such organo-peroxide, it has the effect as extraction proton the thermoplastic resin of raw material and generation radical after decomposing.The active oxygen amount of organo-peroxide is preferably 1 to 11%, and more preferably 2 to 20%.In addition, the active oxygen amount is defined by following formula:
Active oxygen amount (%)=[(quantity of peroxide bond in organo-peroxide molecule) * 16)] * (purity of organo-peroxide (%))/(molecular weight of organo-peroxide)
Wherein peroxide bond is meant-the O-O-key.
The instance that its transformation period becomes 1 minute organo-peroxide in 50 to 210 ℃ decomposition temperature scope comprises peroxo-diacyl, dialkyl peroxide, peroxy ketal, alkyl super-acid ester and percarbonate.Preferably dialkyl peroxide, peroxo-diacyl, percarbonate and alkyl super-acid ester.
The specific examples of organo-peroxide comprises: peroxy dicarbonate two (hexadecyl) ester, peroxy dicarbonate (two-3-methoxyl group fourth) ester, peroxide carbonic acid (two-2-ethyl is own) ester, two (the 4-tertiary butyl hexamethylene) esters of peroxy dicarbonate, di-isopropyl peroxydicarbonate, tert-butyl peroxy isopropyl carbonate, peroxide carbonic acid two myristins, 1; 1,3,3-tetramethyl butyl neodecanoic acid ester, α-cumyl peroxide neodecanoic acid ester, the peroxide neodecanoic acid tert-butyl ester, 1; Two (t-butyl peroxy) hexanaphthenes, 2 of 1-; Two (4, the 4-two-t-butyl peroxy cyclohexyl) propane, 1 of 2-, two (t-butyl peroxy) cyclododecanes of 1-, uncle's hexyl peroxy isopropyl base one carbonic ether, t-butyl peroxy-3; 5; 5-tri-methyl hexanoic acid ester, the peroxide LAURIC ACID 99 MIN tert-butyl ester, 2,5-dimethyl--2,5-two (benzoyl peroxide) hexane, tert-butyl peroxy acetate, 2; Two (t-butyl peroxy) butylene of 2-, t-butyl per(oxy)benzoate, normal-butyl-4; Two (t-butyl peroxy) valerates of 4-, two-t-butyl peroxy isophthalic acid ester, dicumyl peroxide, α, α '-two (t-butyl peroxy--sec.-propyl) benzene, 2,5-dimethyl--2; 5-two-(t-butyl peroxy) hexane, 1; Two (t-butyl peroxy sec.-propyl) benzene of 3-, tert-butyl peroxide cumyl, peroxo-two-tertiary butyl, hydroperoxidation are right-menthane and 2, and 5-dimethyl--2,5-two-(t-butyl peroxy) hexin-3.
Based on the thermoplastic resin of 100 weight parts as raw material, the usage quantity of organo-peroxide is 0.001 to 20 weight part, and is preferably 0.003 to 10 weight part.
In the presence of compound that is containing unsaturated group and organo-peroxide; Will be as the thermoplastic resin melt kneading of raw material during with the preparation modified thermoplastic resin; Can add aromatic vinyl compound; Like vinylbenzene and Vinylstyrene, so that modified thermoplastic resin has the structure that originates from aromatic vinyl compound.Based on the thermoplastic resin of 100 weight parts as raw material, the usage quantity of aromatic vinyl compound is at most 15 weight parts, and preferably is at most 7 weight parts.
The outer sheath of pellet of the present invention and/or inner core can contain additive, like inhibitor, neutralizing agent, lubricant, static inhibitor, nucleator, ultraviolet inhibitor, fire retardant, filler, softening agent, whipping agent, frothing aid, dispersion agent, antitack agent, anti-clouding agent, antiseptic-germicide, linking agent, crosslinking coagent, organic voluminous powder and pigment.
First material that constitutes inner core comprises first thermoplastic resin.The content of first thermoplastic resin in first material typically is 50 to 100 weight %, and is preferably 70 to 100 weight %.
Second material that constitutes outer sheath comprises second thermoplastic resin.The content of second thermoplastic resin in second material typically is 50 to 100 weight %, and is preferably 70 to 100 weight %.
Multilayer pellet of the present invention has inner core and the one deck that forms in inner core outside or multiwalled outer sheath more.When existing two-layer or more during the multiwalled outer sheath, one deck outer sheath must satisfy above-mentioned requirements at least, and can have one or more layers that does not satisfy these requirements.
The length of multilayer pellet of the present invention typically is 1 to 30mm, and thickness is 0.5 to 20mm, is preferably 2 to 8mm.
Multilayer pellet of the present invention can use in Europe not unexamined patent to disclose that disclosed method prepares among 1063070 A2.
Particularly, they can be prepared by a kind of like this method, and this method comprises:
Multilayer with die head forcing machine is provided; Described die head has: through it first material is extruded as first extruding part of inner core and through it second material is extruded as second extruding part of epitheca, settle second extruding part with around first extruding part; Be used for first feeder with first material feeding to the first extruding part; With second feeder that is used for second material feeding to the second extruding part,
First material is fed to first extruding part from first feeder,
Second material is fed to second extruding part from second feeder,
Extrude first material and extrude second material through first extruding part,, form the multilayer extrudate to cover first material with second material through second extruding part, and
Described multilayer extrudate is cut into predetermined length, to form multilayer pellet.
For the method for first extruding part of first material feeding to the die head that will be used for inner core with will be used for the not special restriction of method of second extruding part of second material feeding to the die head of outer sheath.As for be used for first feeder of first extruding part of first material feeding to die head be used for second feeder with second extruding part of second material feeding to die head; Can use conventional forcing machine, for example FR forcing machine (feeder ruders), cold feed forcing machine and twin screw taper forcing machine.Forcing machine both can be a single screw extrusion machine, also can be twin screw extruder.
Aforesaid method typically is applied to prepare the double-deck pellet of being made up of inner core and one deck outer sheath.But; Have multilayer pellet two-layer or more multiwalled outer sheath or also contain outer sheath and during the multilayer pellet of except that the outer sheath that above-mentioned exotic materials is processed a plurality of layers when wanting to prepare, this multilayer pellet can use structure to be used for preparing through extruding the multilayer forcing machine that forms other one or more layers.
The quantity of employed feeder is confirmed according to the number of plies that in needed multilayer pellet, comprises.When forming the double-layer structure of forming by inner core and one deck outer sheath, use two or more feeders.Under the situation of the three-decker of forming by inner core, one deck outer sheath and another layer, use three or more a plurality of feeder.Preferably so-called die head of right angle is used as described die head." die head of right angle " that use is a kind of like this die head of style here, makes to rotate local flow direction, to intersect with the direction of extruding of material.A preferred embodiment with die head of right angle of this structure is not examine in Europe to announce detailed disclosed die head of right angle among 1063070 A2.
By suitable method such as water cooling and air cooling, can cooling multiplayer extrudate (multilayer line material).For the multilayer extrudate is cut into predetermined length, can use routine to be used to prepare the cutting unit of resin granular material.
Then, explained later third and fourth aspect of the present invention.
Multilayer pellet of the present invention comprises the inner core and the outer sheath that contains second material of second thermoplastic resin of first material that contains first thermoplastic resin; Described outer sheath is around described inner core, and first thermoplastic resin is the modified thermoplastic resin with the structure that originates from the compound that contains unsaturated group.
Consider to prevent multilayer pellet and metal or the adhering deterioration of other thermoplastic resin or prevent to produce smell that the wt ratio of preferred described epitheca and said inner core is 50/50 to 1/99 by multilayer pellet, and more preferably 30/70 to 1/99.
In multilayer pellet of the present invention; First thermoplastic resin that is included in first material that constitutes inner core is the modified thermoplastic resin with the structure that originates from the compound that contains unsaturated group, and the modified thermoplastic resin that preferably has the structure that originates from the compound that contains unsaturated group and polar group simultaneously.
First thermoplastic resin; It is the modified thermoplastic resin with the structure that originates from the compound that contains unsaturated group; Be to contain thermoplastic resin that prepare and the thermoplastic resin that have so a kind of structure of the compound treatment of unsaturated group as raw material through using, the structure that wherein will originate from the compound that contains unsaturated group is introduced in the thermoplastic resin as raw material as the part of molecular structure.
The melt index that first thermoplastic resin records under the load of 230 ℃ temperature and 21.2N is preferably less than 200g/10min, and more preferably in 0.1 to 150g/10min scope.
On the other hand, be included in melt index that second thermoplastic resin in second material that constitutes outer sheath records under the load of 230 ℃ temperature and 21.2N preferably less than 200g/10min, and more preferably in 0.1 to 150g/10min scope.
Preferred first thermoplastic resin is the modified polyolefin resin through preparing as the thermoplastic resin of raw material, the compound that contains unsaturated group and organo-peroxide melt kneading; And more preferably it is the modified polyolefin resin for preparing as the organo-peroxide melt kneading of the thermoplastic resin of raw material, 0.01 weight part or higher compound that contains unsaturated group and 0.001 to 20 weight part through with 100 weight parts.
The modified thermoplastic resin that more preferably prepares through the compound that uses the compound conduct that also has polar group to have unsaturated group.
Be used to form that the thermoplastic resin as raw material comprises with the instance that is used to form second thermoplastic resin of outer sheath in the preparation of modified thermoplastic resin of inner core: polyolefin resin; Styron, like PS, impact polystyrene (that is, containing the PS of the cross-linking products of a small amount of itself and polyhutadiene), and ABS resin; Acrylics is like polymethylmethacrylate; Vibrin is like polyethylene terephthalate and polybutylene terephthalate; Polycarbonate resin is like polycarbonate; Polyamide resin is like polyamide 66, polyamide 6 and polymeric amide 46; Polyacetal resin is like polyacetal copolymer and POM-H Acetal homopolymer; Engineering plastics are like polyethersulfone, polyetherimide, TPI, polyetherketone, polyetheretherketone and polyphenylene sulfide; Derivatived cellulose is like rhodia, cellulose acetate butyrate and TKK 021; Thermoplastic elastomer is like TPUE, thermoplastic styrene-butadiene elastomer, thermoplastic polyester elastomer, thermoplasticity vinylchlorid elastomerics and thermoplastic polyamide elastomer; Fluoro-resin; And their modified product.
Be used to form in the preparation of modified thermoplastic resin of inner core that preferably polyolefin resin is (for example as the thermoplastic resin of raw material and second thermoplastic resin that is used to form outer sheath; The vinyl polymerization resin, propylene polymer resin, butene polymerization resin; Ethene, aromatic vinyl compound are (for example; Vinylbenzene) and the hydrogen affixture of the multipolymer of conjugated diolefine (for example, 1,3-butadiene)); And more preferably vinyl polymerization resin and propylene polymer resin; And propylene polymer resin more preferably again.
First thermoplastic resin both can be single thermoplastic resin of planting, and also can be the mixture of two or more thermoplastic resins.Similarly, second thermoplastic resin both can be single thermoplastic resin of planting, and also can be the mixture of two or more thermoplastic resins.
" vinyl polymerization resin " used herein is the monomeric polymerisate of mainly being made up of ethene.Structural unit and 0.01 to the 49 weight % that the example comprises Alathon, originate from ethene by 51 to 99.99 weight % originates from one or more multipolymers that can form with the monomeric structural unit of ethylene copolymer, and their mixture.
The instance of " can with the monomer of ethylene copolymer " comprises propylene, contains terminal olefin, propenoate, methacrylic ester and the vinyl-acetic ester of 4 to 20 carbon atoms.The instance of " terminal olefin that contains 4 to 20 carbon atoms " comprises 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene and vinyl cyclohexane.An instance of " propenoate " is a methyl acrylate, and an instance of " methacrylic ester " is a TEB 3K.
" multipolymer of ethene and as ethene with can with the monomeric multipolymer of ethylene copolymer " instance comprise ethylene-propylene copolymer, ethene-alpha-olefin copolymer, ethylene-methyl methacrylate methyl terpolymer and vinyl-vinyl acetate copolymer.The instance of " ethene-alpha-olefin copolymer " comprises ethene-butene-1 copolymer, ethene-1-pentene copolymer, ethene-1-hexene copolymer, ethene-1-octene copolymer and ethene-1-decene multipolymer.
" propylene polymer resin " used herein is the monomeric polymerisate of mainly being made up of propylene.The example comprises alfon; Originate from the propylene-ethylene random copolymers that the structural unit of propylene and structural unit that 0.01 to 49 weight % originates from ethene are formed by 51 to 99.99 weight %; The structural unit and 0.01 to the 49 weight % that are originated from propylene by 51 to 99.99 weight % originate from the propylene-alpha-olefin random copolymers that one or more structural units that contain the terminal olefin of 4 to 20 carbon atoms are formed; Be included as first segment of alfon part and be the propylene-ethylene random copolymers second segmental propylene-ethylene block copolymer partly; Be included as first segment of alfon part and be the propylene-alpha-olefin random copolymers second segmental propylene-alpha-olefin segmented copolymer partly, wherein said terminal olefin is the terminal olefin that contains 4 to 20 carbon atoms; And their mixture.
The instance that is used to prepare " terminal olefin that contains 4 to 20 carbon atoms " of propylene-alpha-olefin random copolymers and propylene-alpha-olefin segmented copolymer comprises 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene and vinyl cyclohexane.Preferred 1-butylene.
The preferred embodiment of propylene-alpha-olefin random copolymers comprises propylene-1-butylene random copolymers.The preferred embodiment of propylene-alpha-olefin segmented copolymer comprises propylene-1-butylene segmented copolymer.
Propylene-ethylene block copolymer and propylene-alpha-olefin segmented copolymer are normally through using a kind of step (i) and step method preparation (ii) of comprising; Step (i) preparation will become the first segmental alfon, and preparation will become the second segmental multipolymer in the presence of the alfon that step (ii) prepares in step (i).
At the compound that contains unsaturated group of the modified thermoplastic resin that is used for preparing the inner core that is used to form multilayer pellet of the present invention, unsaturated group can preferably contain the group of carbon-to-carbon double bond or contain the group of carbon-to-carbon triple bond.The group that especially preferably contains carbon-to-carbon double bond.
The compound that preferably contains unsaturated group also contains polar group.The instance of this polar group comprises carboxyl, carbalkoxy, allyloxy, amino, carboxamido-group, imide base, itrile group, epoxy group(ing), hydroxyl, NCO; The functional group of derived from carboxylic acid, acid amides, acid azide, carboxylic acid halides, acid anhydrides 、 oxazoline etc.; And the functional group of derived from carboxylic acid salt, amide salt, the salt of acid azide, the salt of carboxylic acid halides etc.
The examples for compounds that contains unsaturated group comprises: unsaturated carboxylic acid, olefinically unsaturated carboxylic acid derivatives, unsaturated epoxy compound, unsaturated alcohol, unsaturated amine and unsaturated isocyanate.
The more specifically instance that contains the compound of unsaturated group comprises:
(1) toxilic acid, maleic anhydride, fumaric acid, maleimide, Regulox, methyl norbornene dioic anhydride, dichloro-maleic anhydride, maleinamide, methylene-succinic acid, itaconic anhydride, (methyl) glycidyl acrylate, 2-hydroxyethyl methacrylate and allyl glycidyl ether
(2) reaction product of maleic anhydride and diamines, the compound that for example has the structure of following formula:
Wherein R representes aliphatic group or aromatic group,
(3) natural oil, for example, soya-bean oil, tung oil, Viscotrol C, oleum lini, hempseed oil, Oleum Gossypii semen, til, rapeseed oil, peanut oil, Camellia oil, sweet oil, Oleum Cocois and sardine oil,
(4) epoxidised natural oil
(5) unsaturated carboxylic acid for example; Vinylformic acid; Butenoic acid; Ba Dousuan; Vinylacetic acid; Methylacrylic acid; Pentenoic acid; Angelicic acid; Tiglic acid; The 2-pentenoic acid; The 3-pentenoic acid; α-Yi Jibingxisuan; β-Jia Jibadousuan; The 4-pentenoic acid; The 2-hexenoic acid; 2-methyl-2-pentenoic acid; 3-methyl-2-pentenoic acid; α-ethyl crotonic acid; 2; 2-dimethyl--3-butenoic acid; The 2-heptenoic acid; The 2-octylenic acid; The 4-decylenic acid; The 9-undecylenic acid; The 10-undecylenic acid; The 4-dodecenoic acid; Linderic acid; The 4-tetradecenoic acid; The 9-tetradecenoic acid; Palmitoleic acid; The 2-octadecenoic acid; The 9-octadecenoic acid; Eicosenoic acid; Decosahedaenoic acid; Erucic acid; Tetracosenoic acid; Mycolipenic acid; 2; The 4-Sorbic Acid; Diallyl acetate; Herba Erodii (Herba Geranii) acid; 2; The 4-decadienoic acid; 2; The 4-dodecadienoic acid; 9; The 12-hexadecadienoic acid; 9; The 12-octadecadienoic acid; Hiragonic acid; Eicosadienoic acid; Eicosatrienoic acid; Eicosatetraenoic acid; Ricinolic acid; Eleostearic acid; Oleic acid; Pentacosa alkene acid; Erucic acid; Two dodecadienoic acids; Docosatrienoic acid; Docosatetratenoic acid; DPA; Hexacosenoic acid; Hexacosandienoic acid; Two octadecenoic acids and 40 carbon enoic acids
(6) ester cpds of above-mentioned unsaturated carboxylic acid, amide compound or acid anhydride,
(7) vinyl carbinol, crotyl alcohol, methyl ethylene methyl alcohol, vinyl-ethyl alcohol, methylpropenyl methyl alcohol, 4-amylene-1-ol, 10-undecene-1-alcohol, propynol, 1; 4-pentadiene-3-alcohol, 1,4-hexadiene-3-alcohol, 3,5-hexadiene-2-pure and mild 2; 4-hexadiene-1-alcohol
(8) unsaturated alcohol, like the 3-butene-1,2-glycol, 2,5-dimethyl--3-hexene-2,5-glycol, 1,5-hexadiene-3,4-two is pure and mild 2,6-octadiene-4, the 5-glycol,
(9) usefulness-NH
2Group replaces the OH group of above-mentioned unsaturated alcohol and the unsaturated amine that obtains,
(10) adduct of the oligopolymer (for example, number-average molecular weight is about 500 to about 10000 polymkeric substance) of the maleic anhydride of phenol and divinyl, isoprene etc.,
(11) superpolymer of the maleic anhydride of phenol and divinyl, isoprene etc. (for example, number-average molecular weight be 10000 or bigger polymkeric substance) adduct,
(12) material that obtains through the oligopolymer (for example, number-average molecular weight is about 500 to about 10000 polymkeric substance) that amino, carboxyl, hydroxyl, epoxide group etc. is introduced into divinyl, isoprene etc.,
(13) superpolymer through amino, carboxyl, hydroxyl, epoxide group etc. being introduced into divinyl, isoprene etc. (for example, number-average molecular weight be 10000 or bigger polymkeric substance) material that obtains,
(14) allyl isocyanate.
The compound that contains unsaturated group is preferably selected from: maleic anhydride, toxilic acid, fumaric acid, itaconic anhydride, methylene-succinic acid, (methyl) glycidyl acrylate and 2-hydroxyethyl methacrylate.
The compound that contains unsaturated group can contain the unsaturated group of two or more identical or different types.When the compound that contains unsaturated group also contained polar group, it can contain the polar group of two or more identical or different types.
Consider the grafting ratio of the compound that contains unsaturated group and thermoplastic resin and by the paintability of the rosin products of multilayer pellet preparation of the present invention; Based on the thermoplastic resin of 100 weight parts as raw material; The usage quantity that contains the compound of unsaturated group typically is 0.01 to 30 weight part, and is preferably 0.1 to 20 weight part.
Consider the grafting ratio of the compound that contains unsaturated group and thermoplastic resin and avoid decomposition as the thermoplastic resin of raw material, the organo-peroxide that preferably uses with the compound that contains unsaturated group be in 50 to 210 ℃ decomposition temperature scope its transformation period become 1 minute organo-peroxide.Preferably such organo-peroxide, it has the effect as extraction proton the thermoplastic resin of raw material and generation radical after decomposing.The active oxygen amount of organo-peroxide is preferably 1 to 11%, and more preferably 2 to 20%.In addition, the active oxygen amount is defined by following formula:
Active oxygen amount (%)=[(quantity of peroxide bond in organo-peroxide molecule) * 16)] * (purity of organo-peroxide (%))/(molecular weight of organo-peroxide)
Wherein peroxide bond is meant-the O-O-key.
The instance that its transformation period becomes 1 minute organo-peroxide in 50 to 210 ℃ decomposition temperature scope comprises peroxo-diacyl, dialkyl peroxide, peroxy ketal, alkyl super-acid ester and percarbonate.Preferably dialkyl peroxide, peroxo-diacyl, percarbonate and alkyl super-acid ester.
The specific examples of organo-peroxide comprises: peroxy dicarbonate two (hexadecyl) ester, peroxy dicarbonate (two-3-methoxyl group fourth) ester, peroxide carbonic acid (two-2-ethyl is own) ester, two (the 4-tertiary butyl hexamethylene) esters of peroxy dicarbonate, di-isopropyl peroxydicarbonate, tert-butyl peroxy isopropyl carbonate, peroxide carbonic acid two myristins, 1; 1,3,3-tetramethyl butyl neodecanoic acid ester, α-cumyl peroxide neodecanoic acid ester, the peroxide neodecanoic acid tert-butyl ester, 1; Two (t-butyl peroxy) hexanaphthenes, 2 of 1-; Two (4, the 4-two-t-butyl peroxy cyclohexyl) propane, 1 of 2-, two (t-butyl peroxy) cyclododecanes of 1-, uncle's hexyl peroxy isopropyl base one carbonic ether, t-butyl peroxy-3; 5; 5-tri-methyl hexanoic acid ester, the peroxide LAURIC ACID 99 MIN tert-butyl ester, 2,5-dimethyl--2,5-two (benzoyl peroxide) hexane, tert-butyl peroxy acetate, 2; Two (t-butyl peroxy) butylene of 2-, t-butyl per(oxy)benzoate, normal-butyl-4; Two (t-butyl peroxy) valerates of 4-, two-t-butyl peroxy isophthalic acid ester, dicumyl peroxide, α, α '-two (t-butyl peroxy--sec.-propyl) benzene, 2,5-dimethyl--2; 5-two-(t-butyl peroxy) hexane, 1; Two (t-butyl peroxy sec.-propyl) benzene of 3-, tert-butyl peroxide cumyl, peroxo-two-tertiary butyl, hydroperoxidation are right-menthane and 2, and 5-dimethyl--2,5-two-(t-butyl peroxy) hexin-3.
Based on the thermoplastic resin of 100 weight parts as raw material, the usage quantity of organo-peroxide is 0.001 to 20 weight part, and is preferably 0.003 to 10 weight part.
In the presence of compound that is containing unsaturated group and organo-peroxide; Will be as the thermoplastic resin melt kneading of raw material during with the preparation modified thermoplastic resin; Can add aromatic vinyl compound; Like vinylbenzene and Vinylstyrene, so that modified thermoplastic resin has the structure that originates from aromatic vinyl compound.Based on the thermoplastic resin of 100 weight parts as raw material, the usage quantity of aromatic vinyl compound is at most 15 weight parts, and preferably is at most 7 weight parts.
The outer sheath of pellet of the present invention and/or inner core can contain additive, like inhibitor, neutralizing agent, lubricant, static inhibitor, nucleator, ultraviolet inhibitor, fire retardant, filler, softening agent, whipping agent, frothing aid, dispersion agent, antitack agent, anti-clouding agent, antiseptic-germicide, linking agent, crosslinking coagent, organic voluminous powder and pigment.
First material that constitutes inner core comprises first thermoplastic resin.The content of first thermoplastic resin in first material typically is 50 to 100 weight %, and is preferably 70 to 100 weight %.
Second material that constitutes outer sheath comprises second thermoplastic resin.The content of second thermoplastic resin in second material typically is 50 to 100 weight %, and is preferably 70 to 100 weight %.
Multilayer pellet of the present invention has inner core and the one deck that forms in inner core outside or multiwalled outer sheath more.When existing two-layer or more during the multiwalled outer sheath, one deck outer sheath must satisfy above-mentioned requirements at least, and can have one or more layers that does not satisfy these requirements.
Typically, the length of multilayer pellet of the present invention is 1 to 30mm, and thickness is 0.5 to 20mm, is preferably 2 to 8mm.
Multilayer pellet of the present invention can use before Europe examination patent to disclose that disclosed method prepares in 1063070.
Particularly, they can be prepared by a kind of like this method, and this method comprises:
Multilayer with die head forcing machine is provided; Described die head has: through it first material is extruded as first extruding part of inner core and through it second material is extruded as second extruding part of epitheca, settle second extruding part with around first extruding part; Be used for first feeder with first material feeding to the first extruding part; With second feeder that is used for second material feeding to the second extruding part,
First material is fed to first extruding part from first feeder,
Second material is fed to second extruding part from second feeder,
Extrude first material and extrude second material through first extruding part,, form the multilayer extrudate to cover first material with second material through second extruding part, and
Described multilayer extrudate is cut into predetermined length, to form multilayer pellet.
For the method for first extruding part of first material feeding to the die head that will be used for inner core with will be used for the not special restriction of method of second extruding part of second material feeding to the die head of outer sheath.As for be used for first feeder of first extruding part of first material feeding to die head be used for second feeder with second extruding part of second material feeding to die head; Can use conventional forcing machine, for example FR forcing machine, cold feed forcing machine and twin screw taper forcing machine.Forcing machine both can be a single screw extrusion machine, also can be twin screw extruder.
Aforesaid method typically is applied to prepare the double-deck pellet of being made up of inner core and one deck outer sheath.But; Have multilayer pellet two-layer or more multiwalled outer sheath or also contain outer sheath and during the multilayer pellet of except that the outer sheath that above-mentioned exotic materials is processed a plurality of layers when wanting to prepare, this multilayer pellet can use structure to be used for preparing through extruding the multilayer forcing machine that forms other one or more layers.
The quantity of employed feeder is confirmed according to the number of plies that in needed multilayer pellet, comprises.When forming the double-layer structure of forming by inner core and one deck outer sheath, use two or more feeders.Under the situation of the three-decker of forming by inner core, one deck outer sheath and another layer, use three or more a plurality of feeder.Preferably so-called die head of right angle is used as described die head." die head of right angle " that use is a kind of like this die head of style here, makes to rotate local flow direction, to intersect with the direction of extruding of material.A preferred embodiment with die head of right angle of this structure is not examine in Europe to announce detailed disclosed die head of right angle among 1063070 A2.
By suitable method such as water cooling and air cooling, can cooling multiplayer extrudate (multilayer line material).For the multilayer extrudate is cut into predetermined length, can use routine to be used to prepare the cutting unit of resin granular material.
Can be with multilayer pellet of the present invention as the raw material that forms various rosin productss.For example it can be used as following raw material: vehicle parts, the part of electric or electronic machine, electric wire, line tectum; Material of construction, agricultural, shipping industry or horticulture articles for use, chemical industry articles for use, civil engineering material; Furniture, stationery, daily necessities, clothes; Container and wrapping material, toy, leisure article and medical science articles for use.
The particular example of vehicle parts comprises: the interior of motor vehicles part, and like panel board, door and post, vehicle exterior part such as collision bumper.The instance of electric wire comprises plastic cable and insulated wire.
Embodiment
Embodiment
Following reference implementation is routine and relatively further describe the present invention, but the invention is not restricted to these embodiment.
< physical property measurement >
1. melt index (MI, unit: g/10min)
According to JIS K7210, under 230 ℃, the load of 21.2N, measure.
2. grafting ratio (unit: wt%)
Step through following is measured:
(1) through preparing solution in the YLENE that 1.0g graft modification resin sample is dissolved in 10ml,
(2) make graft modification resin redeposition through under agitation this drips of solution being added in the methyl alcohol of 300ml,
(3) the graft modification resin of collecting precipitation,
(4) the graft modification resin (80 ℃, 8 hours) of vacuum-drying collection
(5) with the hot pressing of exsiccant graft modification resin, be the film of 100 μ m to form thickness, and
(6) infrared absorption spectrum of MEASUREMENTS OF THIN, and be based on 1730cm
-1The grafting ratio is confirmed near absorption.
Embodiment 1
Alfon (trade name: Noblene HA100E to 100 weight parts; By SumitomoChemical Co.; Ltd. make, MI=300g/10min) in, add the maleic anhydride of 5 weight parts, peroxy dicarbonate two (hexadecyl) ester (active oxygen=2.8% of 0.50 weight part; Decomposition temperature=99 ℃ of 1min transformation period are provided), 0.15 weight part 1; Two (t-butyl peroxy sec.-propyl) benzene of 3-(active oxygen=9.3% provides decomposition temperature=183 ℃ of 1min transformation period), the calcium stearate (neutralizing agent) of 0.05 weight part and four [methylene radical-3-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester] methane (inhibitor) of 0.3 weight part; And, obtain blend at the room temperature thorough mixing.
This blend is fed to the twin screw extruder that is used for inner core, and (PCM46 is made by IKEGAI Ltd.; Screw design: diameter=46mm; L/D=38.5) in, and will be used for epitheca alfon (trade name: Sumitomo Noblene U501E1, by Sumitomo Chemical Co.; Ltd. make; MI=120g/10min) be fed to single screw extrusion machine (VS40, make by IKEGAI Ltd.: 40mm φ, L/D=25).From these forcing machines, the blend that will be used for inner core and the resin that is used for epitheca are fed to inner core/epitheca die head (having six outlets) with inner core/epitheca ratio of 90/10 250 ℃ temperature.Make the six strand material extruded through the water-bath cooling, then with the tablets press cutting, obtain diameter and be 2 to 3mm and length be 3 to 4mm double-deck pellet.The MI of the double-deck pellet that obtains is 1500g/10min.The polyacrylic grafting ratio that forms the modified by maleic acid anhydride graft of inner core is that 0.2 weight % and MI are 3000g/10min.
Embodiment 2
Alfon (trade name: Noblene HA100E to 100 weight parts; By SumitomoChemical Co.; Ltd. make; MI=300g/10min) in, add the 2-hydroxyethyl methacrylate of 12 weight parts, the t-butyl per(oxy)benzoate of 3 weight parts (active oxygen=8.1% provides decomposition temperature=169 ℃ of 1min transformation period); 1.2 the Irgafos 168 that Irganox 1010,0.2 weight part that the styrene monomer of weight part, 0.2 weight part are made by CibaSpecialty Chemicals is made by Ciba SpecialtyChemicals and organic voluminous powder (trade name=MP-1000 of 5 weight parts; Make by MEMBRANA), and, obtain blend at the room temperature thorough mixing.
This blend is fed to the twin screw extruder that is used for inner core, and (PCM46 is made by IKEGAI Ltd.; Screw design: diameter=46mm; L/D=38.5) in; And will be used for epitheca alfon (trade name: Sumitomo Noblene U501E1, by Sumitomo Chemical Co., Ltd. makes; MI=120g/10min) (VS40 is made by IKEGAI Ltd. to be fed to single screw extrusion machine; Screw design: diameter=40mm, L/D=25).From these forcing machines, the blend that will be used for inner core and the resin that is used for epitheca are fed to inner core/epitheca die head (having six outlets) with inner core/epitheca ratio of 97/3 220 ℃ temperature.Make the six strand material extruded through the water-bath cooling, then with the tablets press cutting, obtain diameter and be 2 to 3mm and length be 3 to 4mm double-deck pellet.The MI of the double-deck pellet that obtains is 1000g/10min.The polyacrylic grafting ratio that forms (the 2-hydroxyethyl methacrylate)-graft modification of inner core is that 3.5 weight % and MI are 1400g/10min.
Comparative example 1
Alfon (trade name: Noblene HA100E to 100 weight parts; By SumitomoChemical Co.; Ltd. make; MI=300g/10min) in, add the 2-hydroxyethyl methacrylate of 12 weight parts, the t-butyl per(oxy)benzoate of 3 weight parts (active oxygen=8.1% provides decomposition temperature=169 ℃ of 1min transformation period); 1.2 the Irgafos 168 that Irganox 1010,0.2 weight part that the styrene monomer of weight part, 0.2 weight part are made by CibaSpecialty Chemicals is made by Ciba SpecialtyChemicals and organic voluminous powder (trade name=MP-1000 of 5 weight parts; Make by MEMBRANA), and, obtain blend at the room temperature thorough mixing.
This blend is fed to the twin screw extruder that is used for inner core, and (PCM46 is made by IKEGAI Ltd.; Screw design: diameter=46mm, L/D=38.5) in, the temperature at 220 ℃ is fed to inner core/epitheca die head (having six outlets) from this forcing machine then.The melt tension of the six strand material of being extruded of only being made up of inner core is low, so is difficult to the draw line material, and does not obtain pellet.
Embodiment 3
To the ethylene-propylene random copolymer of 100 weight parts (by Sumitomo Chemical Co.; Ltd. make; MI=0.5g/10min, ethylene content=0.3 weight %) in, add the maleic anhydride of 15 weight parts, peroxy dicarbonate two (hexadecyl) ester (active oxygen=2.8% of 2.8 weight parts; Decomposition temperature=99 ℃ of 1min transformation period are provided), 0.15 weight part 1; Two (t-butyl peroxy sec.-propyl) benzene of 3-(active oxygen=9.3% provides decomposition temperature=183 ℃ of 1min transformation period), the calcium stearate of 0.05 weight part, four [methylene radical-3-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester] methane (inhibitor) of 0.3 weight part and the styrene monomer of 3 weight parts; And, obtain blend at the room temperature thorough mixing.
This blend is fed to the twin screw extruder that is used for inner core, and (PCM46 is made by IKEGAI Ltd.; Screw design: diameter=46mm; L/D=38.5) in; And will be used for epitheca alfon (trade name: Sumitomo Noblene U501E1, by Sumitomo Chemical Co., Ltd. makes; MI=120g/10min) (VS40 is made by IKEGAI Ltd. to be fed to single screw extrusion machine; Screw design: diameter=40mm, L/D=25).From these forcing machines, the blend that will be used for inner core and the resin that is used for epitheca are fed to inner core/epitheca die head (having six outlets) with inner core/epitheca ratio of 97/3 250 ℃ temperature.Make the six strand material extruded through the water-bath cooling, then with the tablets press cutting, obtain diameter and be 2 to 3mm and length be 3 to 4mm double-deck pellet.The MI of the double-deck pellet that obtains is 5g/10min.The grafting ratio of the ethylene-propylene random copolymer of the modified by maleic acid anhydride graft of formation inner core is 2.4 weight %.
Comparative example 2
To the ethylene-propylene random copolymer of 100 weight parts (by Sumitomo Chemical Co.; Ltd. make; MI=0.5g/10min, ethylene content=0.3 weight %) in, add the maleic anhydride of 15 weight parts, peroxy dicarbonate two (hexadecyl) ester (active oxygen=2.8% of 0.50 weight part; Decomposition temperature=99 ℃ of 1min transformation period are provided), 0.15 weight part 1; Two (t-butyl peroxy sec.-propyl) benzene of 3-(active oxygen=9.3% provides decomposition temperature=183 ℃ of 1min transformation period), the calcium stearate of 0.05 weight part, four [methylene radical-3-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester] methane (inhibitor) of 0.3 weight part and the styrene monomer of 3 weight parts; And, obtain blend at the room temperature thorough mixing.
This blend is fed to the twin screw extruder that is used for inner core, and (PCM46 is made by IKEGAI Ltd.; Screw design: diameter=46mm, L/D=38.5) in, from this forcing machine, extrude then 250 ℃ temperature.Owing to send the intensive smell, be difficult to carry out granulation, thereby do not obtain pellet.
Claims (15)
1. multilayer pellet; It comprises the inner core and the outer sheath that contains second material of second thermoplastic resin of first material that contains first thermoplastic resin; Described outer sheath is around described inner core; Wherein the melt index that under the load of 230 ℃ temperature and 21.2N, records of first thermoplastic resin is 200g/10min or bigger; The condition melt index that to be second thermoplastic resin record under the load of 230 ℃ temperature and 21.2N is different from the melt index of first thermoplastic resin; Wherein first thermoplastic resin is through mediating the thermoplastic resin of the grafting-modification for preparing as the thermoplastic resin of raw material, the compound that contains unsaturated group and organo-peroxide fusing
Wherein said " thermoplastic resin " is propylene polymer resin,
The described compound that contains unsaturated group is selected from maleic anhydride, toxilic acid, fumaric acid, itaconic anhydride, methylene-succinic acid, (methyl) glycidyl acrylate and 2-hydroxyethyl methacrylate, and
Based on the thermoplastic resin of 100 weight parts as raw material, the usage quantity that contains the compound of unsaturated group is 0.01 to 30 weight part.
2. multilayer pellet according to claim 1, the wt ratio of wherein said epitheca and said inner core are 50/50 to 1/99.
3. multilayer pellet according to claim 1, the compound that wherein contains unsaturated group also has polar group.
4. method for preparing multilayer pellet; Described multilayer pellet comprises the inner core and the outer sheath that contains second material of second thermoplastic resin of first material that contains first thermoplastic resin; Described epitheca is around described inner core; Wherein the melt index that under the load of 230 ℃ temperature and 21.2N, records of first thermoplastic resin is 200g/10min or bigger; The condition melt index that to be second thermoplastic resin record under the load of 230 ℃ temperature and 21.2N is different from the melt index of first thermoplastic resin, and wherein said " thermoplastic resin " is propylene polymer resin, and this method comprises:
Multilayer with die head forcing machine is provided; Described die head has: extrude as first extruding part of first material of inner core with through it through it and extrude second extruding part as second material of epitheca, settle second extruding part with around first extruding part; Be used for first feeder with first material feeding to the first extruding part; With second feeder that is used for second material feeding to the second extruding part,
First material is fed to first extruding part from first feeder,
Second material is fed to second extruding part from second feeder,
Extrude first material and extrude second material through first extruding part,, form the multilayer extrudate to cover first material with second material through second extruding part, and
Described multilayer extrudate is cut into predetermined length, to form multilayer pellet.
5. method according to claim 4, wherein first thermoplastic resin is to mediate and form at first feeder through the compound and the organo-peroxide fusing of will be as the thermoplastic resin of raw material, containing unsaturated group and polar group simultaneously.
6. method according to claim 4, wherein said die head are the pinblock die heads.
7. multilayer pellet; It comprises the inner core and the outer sheath that contains second material of second thermoplastic resin of first material that contains first thermoplastic resin; Described outer sheath is around described inner core; Wherein first thermoplastic resin is the modified thermoplastic resin with the structure that originates from the compound that contains unsaturated group
Wherein said thermoplastic resin is a propylene polymer resin,
The described compound that contains unsaturated group is selected from maleic anhydride, toxilic acid, fumaric acid, itaconic anhydride, methylene-succinic acid, (methyl) glycidyl acrylate and 2-hydroxyethyl methacrylate, and
Based on the thermoplastic resin of 100 weight parts as raw material, the usage quantity that contains the compound of unsaturated group is 0.01 to 30 weight part.
8. multilayer pellet according to claim 7, the wherein said compound that contains unsaturated group also contains polar group.
9. multilayer pellet according to claim 7, the wt ratio of wherein said epitheca and said inner core are 50/50 to 1/99.
10. multilayer pellet according to claim 7, wherein first thermoplastic resin is to mediate the modified thermoplastic resin for preparing through the compound and the organo-peroxide fusing of will be as the thermoplastic resin of raw material, containing unsaturated group and polar group simultaneously.
11. multilayer pellet according to claim 7, wherein first thermoplastic resin be through with 100 weight parts as the thermoplastic resin of raw material, 0.01 weight part or more contain the compound of unsaturated group and polar group simultaneously and the modified thermoplastic resin for preparing is mediated in the organo-peroxide fusing of 0.001 to 20 weight part.
12. multilayer pellet according to claim 7, wherein the melt index that under the load of 230 ℃ temperature and 21.2N, records of first thermoplastic resin is less than 200g/10min.
13. method for preparing multilayer pellet; Described multilayer pellet comprises the inner core and the outer sheath that contains second material of second thermoplastic resin of first material that contains first thermoplastic resin; Described epitheca is around described inner core; Wherein first thermoplastic resin is the modified thermoplastic resin with the structure that originates from the compound that contains unsaturated group, and wherein said thermoplastic resin is a propylene polymer resin, and the described compound that contains unsaturated group is selected from maleic anhydride, toxilic acid, fumaric acid, itaconic anhydride, methylene-succinic acid, (methyl) glycidyl acrylate and 2-hydroxyethyl methacrylate; And; Based on the thermoplastic resin of 100 weight parts as raw material, the usage quantity that contains the compound of unsaturated group is 0.01 to 30 weight part
This method comprises:
Multilayer with die head forcing machine is provided; Described die head has: extrude as first extruding part of first material of inner core with through it through it and extrude second extruding part as second material of epitheca, settle second extruding part with around first extruding part; Be used for first feeder with first material feeding to the first extruding part; With second feeder that is used for second material feeding to the second extruding part,
First material is fed to first extruding part from first feeder,
Second material is fed to second extruding part from second feeder,
Extrude first material and extrude second material through first extruding part,, form the multilayer extrudate to cover first material with second material through second extruding part, and
Described multilayer extrudate is cut into predetermined length, to form multilayer pellet.
14. method according to claim 13, wherein first thermoplastic resin is to mediate and in first feeder, form through the compound and the organo-peroxide fusing of will be as the thermoplastic resin of raw material, containing unsaturated group and polar group simultaneously.
15. method according to claim 13, wherein said die head are the pinblock die heads.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005145044 | 2005-05-18 | ||
| JP2005-145045 | 2005-05-18 | ||
| JP2005-145044 | 2005-05-18 | ||
| JP2005145044A JP5292664B2 (en) | 2005-05-18 | 2005-05-18 | Multilayer pellet and method for producing the same |
| JP2005145045 | 2005-05-18 | ||
| JP2005145045A JP2006321081A (en) | 2005-05-18 | 2005-05-18 | Multilayer pellet and its production method |
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| Publication Number | Publication Date |
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| CN1865323A CN1865323A (en) | 2006-11-22 |
| CN1865323B true CN1865323B (en) | 2012-07-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2006100824064A Expired - Fee Related CN1865323B (en) | 2005-05-18 | 2006-05-16 | Multilayer pellet and method for producing the same |
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| Country | Link |
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| JP (1) | JP5292664B2 (en) |
| CN (1) | CN1865323B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2835246A1 (en) * | 2013-08-05 | 2015-02-11 | Ansa Termoplastici S.r.l. | Method and apparatus for producing extruded plastic elements |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103254858A (en) * | 2012-02-15 | 2013-08-21 | 日东电工株式会社 | Adhesive composition particle |
| JP6079346B2 (en) * | 2013-03-21 | 2017-02-15 | 住友化学株式会社 | Propylene resin composition production method and molded article comprising the propylene resin composition |
| JP6089839B2 (en) * | 2013-03-21 | 2017-03-08 | 住友化学株式会社 | Propylene resin composition production method and molded article comprising the propylene resin composition |
| JP2015105369A (en) * | 2013-12-02 | 2015-06-08 | 住化カラー株式会社 | Two-layer structure olefin based resin pellet and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1079234A (en) * | 1992-05-21 | 1993-12-08 | 联合碳化化学品及塑料技术公司 | The production method of sticky polymers |
| EP1063070A2 (en) * | 1999-06-25 | 2000-12-27 | Sumika Color Company Limited | Process for manufacturing multilayer pellets and use of the multilayer pellets |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5981121A (en) * | 1982-11-01 | 1984-05-10 | Toyo Seikan Kaisha Ltd | Manufacture of multilayer pellet |
| JPS5981120A (en) * | 1982-11-01 | 1984-05-10 | Toyo Seikan Kaisha Ltd | Molding cover resin pellet and manufacture thereof |
| US5627218A (en) * | 1995-03-20 | 1997-05-06 | Bradt; Rexford H. | Compartmented thermoplastic pellets |
| JP2001009833A (en) * | 1999-06-25 | 2001-01-16 | Sumika Color Kk | Thermoplastic polyester resin having good drying promotability, method for drying it, and its manufacture |
| JP2003136529A (en) * | 2001-11-02 | 2003-05-14 | Sumitomo Chem Co Ltd | Resin modifier and modified thermoplastic resin composition |
| JP4207549B2 (en) * | 2002-11-28 | 2009-01-14 | 三菱化学株式会社 | Laminated body |
| JP2006321081A (en) * | 2005-05-18 | 2006-11-30 | Sumitomo Chemical Co Ltd | Multilayer pellet and its production method |
-
2005
- 2005-05-18 JP JP2005145044A patent/JP5292664B2/en not_active Expired - Fee Related
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1079234A (en) * | 1992-05-21 | 1993-12-08 | 联合碳化化学品及塑料技术公司 | The production method of sticky polymers |
| EP1063070A2 (en) * | 1999-06-25 | 2000-12-27 | Sumika Color Company Limited | Process for manufacturing multilayer pellets and use of the multilayer pellets |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2835246A1 (en) * | 2013-08-05 | 2015-02-11 | Ansa Termoplastici S.r.l. | Method and apparatus for producing extruded plastic elements |
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| JP2006321870A (en) | 2006-11-30 |
| JP5292664B2 (en) | 2013-09-18 |
| CN1865323A (en) | 2006-11-22 |
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