CN1865323A - Multilayer pellet and method for producing the same - Google Patents
Multilayer pellet and method for producing the same Download PDFInfo
- Publication number
- CN1865323A CN1865323A CN 200610082406 CN200610082406A CN1865323A CN 1865323 A CN1865323 A CN 1865323A CN 200610082406 CN200610082406 CN 200610082406 CN 200610082406 A CN200610082406 A CN 200610082406A CN 1865323 A CN1865323 A CN 1865323A
- Authority
- CN
- China
- Prior art keywords
- thermoplastic resin
- inner core
- multilayer
- extruding part
- acid
- 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.)
- Granted
Links
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
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 the method that under the discharging of smell still less, has 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, and it is by the epitheca that comprises component (A) and 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 or more alkene are formed, described alkene is selected from: ethene, propylene or C
4-20Alpha-olefin, the ethene of described olefin copolymer, propylene and C
4-20The total number of carbon atoms of alpha-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 alpha-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): by 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 be melted by the melt that alkene-the Ji resin is formed and extrude, to form the line material of forming by the epitheca of the inner core of last melt and 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, has an excellent flowability, and has excellent dispersiveness with metal or other thermoplastic resin, and provide a kind of thermoplastic resin material, 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 invention provides a kind of multilayer pellet, the outer sheath that it comprises the inner core of first material that contains first thermoplastic resin and contains second material of second thermoplastic resin, described outer sheath is around described inner core, wherein the melt index that records under the load of 230 ℃ temperature and 21.2N 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 weight ratio of described epitheca and described inner core is 50/50 to 1/99.
In another preferred embodiment, first thermoplastic resin is the modified polyolefin resin by 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 by 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, described thermoplastic resin as raw material is a polyolefin resin.
In second aspect, the invention provides a kind of method for preparing multilayer pellet, described multilayer pellet comprises the inner core of first material that contains first thermoplastic resin and contains the outer sheath of second material of second thermoplastic resin, described epitheca is around described inner core, wherein the melt index that records under the load of 230 ℃ temperature and 21.2N 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 this method comprises:
Multilayer with die head forcing machine is provided, described die head has: by it first material is extruded as first extruding part of inner core and by 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 by first extruding part,, form the multilayer extrudate to cover first material with second material by second extruding part, and
Described multilayer extrudate is cut into predetermined length, to form multilayer pellet.
In a preferred embodiment, first thermoplastic resin be by will be as the thermoplastic resin of raw material, contain the compound of unsaturated group and polar group and organo-peroxide melt kneading 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 invention provides a kind of multilayer pellet, the outer sheath that it comprises the inner core of first material that contains first thermoplastic resin and contains second material of second 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 weight ratio of described epitheca and described inner core is 50/50 to 1/99.
In another embodiment preferred, first thermoplastic resin be by 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 by 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 modified thermoplastic resin that the organo-peroxide melt kneading of 0.001 to 20 weight part prepares.
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 invention provides a kind of method for preparing multilayer pellet, described multilayer pellet comprises the inner core of first material that contains first thermoplastic resin and contains the outer sheath of second material of second 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 this method comprises:
Multilayer with die head forcing machine is provided, described die head has: by it first material is extruded as first extruding part of inner core and by 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 by first extruding part,, form the multilayer extrudate to cover first material with second material by second extruding part, and
Described multilayer extrudate is cut into predetermined length, to form multilayer pellet.
In a preferred embodiment, first thermoplastic resin be by will be as the thermoplastic resin of raw material, contain the compound of unsaturated group and polar group and organo-peroxide melt kneading 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 of first material that contains first thermoplastic resin and contains the outer sheath of second material of second thermoplastic resin, described outer sheath is around described inner core, and wherein the melt index that records under the load of 230 ℃ temperature and 21.2N of first thermoplastic resin is 200g/10min or bigger.Here, the melt index that records under the load of 230 ℃ temperature and 21.2N 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 weight ratio of preferred described epitheca and described 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 preferred in 200 to 20000g/10min scope.
Preferred first thermoplastic resin be by 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 by using polyolefin resin to prepare as " as the thermoplastic resin of raw material ".
Preferred first thermoplastic resin be by 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 by 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 that is included in first material that constitutes 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 example that is used for second thermoplastic resin of outer sheath: polyolefin resin; Styrene resin, as polystyrene, impact polystyrene (that is, containing the polystyrene of the cross-linking products of a small amount of itself and polyhutadiene), and ABS resin; Acrylic resin is as polymethylmethacrylate; Vibrin is as polyethylene terephthalate and polybutylene terephthalate; Polycarbonate resin is as polycarbonate; Polyamide resin is as polyamide 66, polyamide 6 and polymeric amide 46; Polyacetal resin is as polyacetal copolymer and POM-H Acetal homopolymer; Engineering plastics are as polyethersulfone, polyetherimide, thermoplastic polyimide, polyetherketone, polyether-ether-ketone and polyphenylene sulfide; Derivatived cellulose is as rhodia, cellulose acetate butyrate and ethyl cellulose; Thermoplastic elastomer is as Polyurethane Thermoplastic Elastomer, 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.The example comprises Alathon, originate from the structural unit of ethene and 0.01 to 49 weight % by 51 to 99.99 weight % originates from the multipolymer that one or more can be formed with the monomeric structural unit of ethylene copolymer, and their mixture.
The example of " can with the monomer of ethylene copolymer " comprises propylene, contains alpha-olefin, acrylate, methacrylic ester and the vinyl-acetic ester of 4 to 20 carbon atoms.The example of " alpha-olefin that contains 4 to 20 carbon atoms " comprises 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene and vinyl cyclohexane.An example of " acrylate " is a methyl acrylate, and an example of " methacrylic ester " is a methyl methacrylate.
" multipolymer of ethene and as ethene with can with the monomeric multipolymer of ethylene copolymer " example comprise ethylene-propylene copolymer, ethene-alpha-olefin copolymer, ethylene-methyl methacrylate methyl terpolymer and vinyl-vinyl acetate copolymer.The example 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 alpha-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 alpha-olefin is the alpha-olefin that contains 4 to 20 carbon atoms; And their mixture.
The example that is used to prepare " alpha-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 by 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: by 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 " by 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 example of this polar group comprises carboxyl, carbalkoxy, allyloxy, amino, amide group, imide base, itrile group, epoxy group(ing), hydroxyl, isocyanate group; 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 example 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 represents aliphatic group or aromatic group,
(3) natural oil, for example, soya-bean oil, tung oil, Viscotrol C, oleum lini, hempseed oil, Oleum Gossypii semen, sesame oil, 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, methacrylic 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, clupanodonic acid, 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, propargyl alcohol, 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, as 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 by 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 by 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, preferably the organo-peroxide that 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 free 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 example that its transformation period becomes 1 minute organo-peroxide in 50 to 210 ℃ decomposition temperature scope comprises peroxidation diacyl, dialkyl peroxide, peroxy ketal, alkyl super-acid ester and percarbonate.Preferably dialkyl peroxide, peroxidation 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 of 1-, 2,2-two (4,4-two-t-butyl peroxy cyclohexyl) propane, 1, 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 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-, the tert-butyl peroxide cumyl, peroxidation two-tertiary butyl, hydroperoxidation is right-menthane and 2,5-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, as 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 mostly is 15 weight parts most, and preferably mostly is most 7 weight parts.
The outer sheath of pellet of the present invention and/or inner core can contain additive, as antioxidant, 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 one deck that forms in the inner core outside or more multi-layered outer sheath.When having two-layer or more multi-layered 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: by it first material is extruded as first extruding part of inner core and by 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 by first extruding part,, form the multilayer extrudate to cover first material with second material by second extruding part, and
Described multilayer extrudate is cut into predetermined length, to form multilayer pellet.
Be not particularly limited for the method for first material feeding that will be used for inner core to the method for first extruding part of die head and second material feeding that will be used for outer sheath to second extruding part of die head.As for being used for first material feeding to first feeder of first extruding part of die head be used for second feeder of second material feeding to second extruding part of 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, when wanting to prepare the multilayer pellet with two-layer or more multi-layered outer sheath or also contain outer sheath and during the multilayer pellet of except that the outer sheath that above-mentioned exotic materials is made a plurality of layers, this multilayer pellet can use structure to be used for preparing by extruding the multilayer forcing machine that forms other one or more layers.
The quantity of employed feeder is determined according to the number of plies that comprises in needed multilayer pellet.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 feeders.Preferably so-called die head of right angle is used as described die head." die head of right angle " of Shi Yonging is a kind of like this die head of style herein, 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 of first material that contains first thermoplastic resin and contains the outer sheath of second material of second 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 from multilayer pellet and metal or the adhering deterioration of other thermoplastic resin or prevent to produce smell that the weight ratio of preferred described epitheca and described 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 by with containing 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, 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 by 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 by with 100 weight parts.
More preferably modified thermoplastic resin by using the compound also have polar group to prepare as compound with unsaturated group.
Be used to form in the preparation of modified thermoplastic resin of inner core as the thermoplastic resin of raw material and the example that is used to form second thermoplastic resin of outer sheath and comprise: polyolefin resin; Styrene resin, as polystyrene, impact polystyrene (that is, containing the polystyrene of the cross-linking products of a small amount of itself and polyhutadiene), and ABS resin; Acrylic resin is as polymethylmethacrylate; Vibrin is as polyethylene terephthalate and polybutylene terephthalate; Polycarbonate resin is as polycarbonate; Polyamide resin is as polyamide 66, polyamide 6 and polymeric amide 46; Polyacetal resin is as polyacetal copolymer and POM-H Acetal homopolymer; Engineering plastics are as polyethersulfone, polyetherimide, thermoplastic polyimide, polyetherketone, polyether-ether-ketone and polyphenylene sulfide; Derivatived cellulose is as rhodia, cellulose acetate butyrate and ethyl cellulose; Thermoplastic elastomer is as Polyurethane Thermoplastic Elastomer, 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, the 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.The example comprises Alathon, originate from the structural unit of ethene and 0.01 to 49 weight % by 51 to 99.99 weight % originates from the multipolymer that one or more can be formed with the monomeric structural unit of ethylene copolymer, and their mixture.
The example of " can with the monomer of ethylene copolymer " comprises propylene, contains alpha-olefin, acrylate, methacrylic ester and the vinyl-acetic ester of 4 to 20 carbon atoms.The example of " alpha-olefin that contains 4 to 20 carbon atoms " comprises 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene and vinyl cyclohexane.An example of " acrylate " is a methyl acrylate, and an example of " methacrylic ester " is a methyl methacrylate.
" multipolymer of ethene and as ethene with can with the monomeric multipolymer of ethylene copolymer " example comprise ethylene-propylene copolymer, ethene-alpha-olefin copolymer, ethylene-methyl methacrylate methyl terpolymer and vinyl-vinyl acetate copolymer.The example 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 alpha-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 alpha-olefin is the alpha-olefin that contains 4 to 20 carbon atoms; And their mixture.
The example that is used to prepare " alpha-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 by 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 example of this polar group comprises carboxyl, carbalkoxy, allyloxy, amino, amide group, imide base, itrile group, epoxy group(ing), hydroxyl, isocyanate group; 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 example 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 represents aliphatic group or aromatic group,
(3) natural oil, for example, soya-bean oil, tung oil, Viscotrol C, oleum lini, hempseed oil, Oleum Gossypii semen, sesame oil, 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, methacrylic 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, clupanodonic acid, 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, propargyl alcohol, 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, as 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 by 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 by 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, preferably the organo-peroxide that 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 free 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 example that its transformation period becomes 1 minute organo-peroxide in 50 to 210 ℃ decomposition temperature scope comprises peroxidation diacyl, dialkyl peroxide, peroxy ketal, alkyl super-acid ester and percarbonate.Preferably dialkyl peroxide, peroxidation 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 of 1-, 2,2-two (4,4-two-t-butyl peroxy cyclohexyl) propane, 1, 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 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-, the tert-butyl peroxide cumyl, peroxidation two-tertiary butyl, hydroperoxidation is right-menthane and 2,5-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, as 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 mostly is 15 weight parts most, and preferably mostly is most 7 weight parts.
The outer sheath of pellet of the present invention and/or inner core can contain additive, as antioxidant, 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 one deck that forms in the inner core outside or more multi-layered outer sheath.When having two-layer or more multi-layered 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 that disclosed method prepares in the patent disclosure 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: by it first material is extruded as first extruding part of inner core and by 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 by first extruding part,, form the multilayer extrudate to cover first material with second material by second extruding part, and
Described multilayer extrudate is cut into predetermined length, to form multilayer pellet.
Be not particularly limited for the method for first material feeding that will be used for inner core to the method for first extruding part of die head and second material feeding that will be used for outer sheath to second extruding part of die head.As for being used for first material feeding to first feeder of first extruding part of die head be used for second feeder of second material feeding to second extruding part of 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, when wanting to prepare the multilayer pellet with two-layer or more multi-layered outer sheath or also contain outer sheath and during the multilayer pellet of except that the outer sheath that above-mentioned exotic materials is made a plurality of layers, this multilayer pellet can use structure to be used for preparing by extruding the multilayer forcing machine that forms other one or more layers.
The quantity of employed feeder is determined according to the number of plies that comprises in needed multilayer pellet.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 feeders.Preferably so-called die head of right angle is used as described die head." die head of right angle " of Shi Yonging is a kind of like this die head of style herein, 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, the line tectum, material of construction, agricultural, shipping industry or horticulture articles for use, the 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 as panel board, door and post, vehicle exterior part such as collision bumper.The example of electric wire comprises plastic cable and insulated wire.
Embodiment
Embodiment
Below with reference to embodiment with 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%)
Measure by following step:
(1) by preparing solution in the dimethylbenzene that 1.0g graft modification resin sample is dissolved in 10ml,
(2) by making graft modification resin redeposition in the methyl alcohol that under agitation this drips of solution is added to 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 based at 1730cm
-1The grafting ratio is determined near absorption.
Embodiment 1
Alfon (trade name: Noblene HA100E to 100 weight parts, by SumitomoChemical Co., Ltd. make, MI=300g/10min) in, the maleic anhydride that adds 5 weight parts, 0.50 peroxy dicarbonate two (hexadecyl) ester (active oxygen=2.8% of weight part, provide decomposition temperature=99 ℃ of 1min transformation period), 0.15 1 of weight part, two (t-butyl peroxy sec.-propyl) benzene (active oxygen=9.3% of 3-, provide decomposition temperature=183 ℃ of 1min transformation period), 0.05 calcium stearate of weight part (neutralizing agent) and 0.3 weight part four [methylene radical-3-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester] methane (antioxidant), 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 the alfon (trade name: Sumitomo Noblene U501E1 of epitheca, 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 resin that will be used for the blend of inner core and be used for epitheca is fed to inner core/epitheca die head (having six outlets) with inner core/epitheca ratio of 90/10 250 ℃ temperature.The six strand material of extruding are cooled off by water-bath, then with 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, the 2-hydroxyethyl methacrylate that adds 12 weight parts, the t-butyl per(oxy)benzoate of 3 weight parts (active oxygen=8.1%, provide decomposition temperature=169 ℃ of 1min transformation period), 1.2 the styrene monomer of weight part, 0.2 the Irganox 1010 that weight part is made by CibaSpecialty Chemicals, 0.2 weight part is by the Irgafos 168 of Ciba SpecialtyChemicals manufacturing 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 the alfon (trade name: Sumitomo Noblene U501E1 of epitheca, by Sumitomo Chemical Co., Ltd. make, 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 resin that will be used for the blend of inner core and be used for epitheca is fed to inner core/epitheca die head (having six outlets) with inner core/epitheca ratio of 97/3 220 ℃ temperature.The six strand material of extruding are cooled off by water-bath, then with 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, the 2-hydroxyethyl methacrylate that adds 12 weight parts, the t-butyl per(oxy)benzoate of 3 weight parts (active oxygen=8.1%, provide decomposition temperature=169 ℃ of 1min transformation period), 1.2 the styrene monomer of weight part, 0.2 the Irganox 1010 that weight part is made by CibaSpecialty Chemicals, 0.2 weight part is by the Irgafos 168 of Ciba SpecialtyChemicals manufacturing 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, the maleic anhydride that adds 15 weight parts, 2.8 peroxy dicarbonate two (hexadecyl) ester (active oxygen=2.8% of weight part, provide decomposition temperature=99 ℃ of 1min transformation period), 0.15 1 of weight part, two (t-butyl peroxy sec.-propyl) benzene (active oxygen=9.3% of 3-, provide decomposition temperature=183 ℃ of 1min transformation period), 0.05 the calcium stearate of weight part, 0.3 weight part four [methylene radical-3-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester] styrene monomer of methane (antioxidant) and 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 the alfon (trade name: Sumitomo Noblene U501E1 of epitheca, by Sumitomo Chemical Co., Ltd. make, 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 resin that will be used for the blend of inner core and be used for epitheca is fed to inner core/epitheca die head (having six outlets) with inner core/epitheca ratio of 97/3 250 ℃ temperature.The six strand material of extruding are cooled off by water-bath, then with 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, the maleic anhydride that adds 15 weight parts, 0.50 peroxy dicarbonate two (hexadecyl) ester (active oxygen=2.8% of weight part, provide decomposition temperature=99 ℃ of 1min transformation period), 0.15 1 of weight part, two (t-butyl peroxy sec.-propyl) benzene (active oxygen=9.3% of 3-, provide decomposition temperature=183 ℃ of 1min transformation period), 0.05 the calcium stearate of weight part, 0.3 weight part four [methylene radical-3-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester] styrene monomer of methane (antioxidant) and 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 (17)
1. multilayer pellet, the outer sheath that it comprises the inner core of first material that contains first thermoplastic resin and contains second material of second thermoplastic resin, described outer sheath is around described inner core, wherein the melt index that records under the load of 230 ℃ temperature and 21.2N 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.
2. multilayer pellet according to claim 1, the weight ratio of wherein said epitheca and described inner core are 50/50 to 1/99.
3. multilayer pellet according to claim 1, wherein first thermoplastic resin is the modified polyolefin resin by preparing as the polyolefin resin of raw material, the compound that contains unsaturated group and organo-peroxide melt kneading.
4. multilayer pellet according to claim 1, wherein first thermoplastic resin be by 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.
5. multilayer pellet according to claim 4, wherein said thermoplastic resin as raw material is a polyolefin resin.
6. method for preparing multilayer pellet, described multilayer pellet comprises the inner core of first material that contains first thermoplastic resin and contains the outer sheath of second material of second thermoplastic resin, described epitheca is around described inner core, wherein the melt index that records under the load of 230 ℃ temperature and 21.2N 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 described method comprises:
Multilayer with die head forcing machine is provided, described die head has: by it first material is extruded as first extruding part of inner core and by 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 by first extruding part,, form the multilayer extrudate to cover first material with second material by second extruding part, and
Described multilayer extrudate is cut into predetermined length, to form multilayer pellet.
7. method according to claim 6, wherein first thermoplastic resin be by will be as the thermoplastic resin of raw material, contain the compound of unsaturated group and polar group and organo-peroxide melt kneading simultaneously and form at first feeder.
8. method according to claim 6, wherein said die head is a die head of right angle.
9. multilayer pellet, the outer sheath that it comprises the inner core of first material that contains first thermoplastic resin and contains second material of second 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.
10. multilayer pellet according to claim 9, the wherein said compound that contains unsaturated group also contains polar group.
11. multilayer pellet according to claim 9, the weight ratio of wherein said epitheca and described inner core are 50/50 to 1/99.
12. multilayer pellet according to claim 9, wherein first thermoplastic resin be by 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.
13. multilayer pellet according to claim 9, wherein first thermoplastic resin be by 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 modified thermoplastic resin that the organo-peroxide melt kneading of 0.001 to 20 weight part prepares.
14. multilayer pellet according to claim 9, wherein the melt index that records under the load of 230 ℃ temperature and 21.2N of first thermoplastic resin is less than 200g/10min.
15. method for preparing multilayer pellet, described multilayer pellet comprises the inner core of first material that contains first thermoplastic resin and contains the outer sheath of second material of second 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 described method comprises:
Multilayer with die head forcing machine is provided, described die head has: by it first material is extruded as first extruding part of inner core and by 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 by first extruding part,, form the multilayer extrudate to cover first material with second material by second extruding part, and
Described multilayer extrudate is cut into predetermined length, to form multilayer pellet.
16. method according to claim 15, wherein first thermoplastic resin be by will be as the thermoplastic resin of raw material, contain the compound of unsaturated group and polar group and organo-peroxide melt kneading simultaneously and in first feeder, form.
17. method according to claim 15, wherein said die head is a die head of right angle.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005145044 | 2005-05-18 | ||
| JP2005145045 | 2005-05-18 | ||
| JP2005-145045 | 2005-05-18 | ||
| JP2005145045A JP2006321081A (en) | 2005-05-18 | 2005-05-18 | Multilayer pellet and its production method |
| JP2005-145044 | 2005-05-18 | ||
| JP2005145044A JP5292664B2 (en) | 2005-05-18 | 2005-05-18 | Multilayer pellet and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1865323A true CN1865323A (en) | 2006-11-22 |
| CN1865323B CN1865323B (en) | 2012-07-04 |
Family
ID=37424479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006100824064A Expired - Fee Related CN1865323B (en) | 2005-05-18 | 2006-05-16 | Multilayer pellet and method for producing the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5292664B2 (en) |
| CN (1) | CN1865323B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254858A (en) * | 2012-02-15 | 2013-08-21 | 日东电工株式会社 | Adhesive composition particle |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| EP2835246A1 (en) * | 2013-08-05 | 2015-02-11 | Ansa Termoplastici S.r.l. | Method and apparatus for producing extruded plastic elements |
| 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 |
Family Cites Families (9)
| 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 |
| US5304588A (en) * | 1989-09-28 | 1994-04-19 | Union Carbide Chemicals & Plastics Technology Corporation | Core-shell resin particle |
| 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 |
| ATE374682T1 (en) * | 1999-06-25 | 2007-10-15 | Sumika Color Company Ltd | METHOD AND DEVICE FOR PRODUCING MULTI-LAYER GRANULES |
| 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
-
2006
- 2006-05-16 CN CN2006100824064A patent/CN1865323B/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254858A (en) * | 2012-02-15 | 2013-08-21 | 日东电工株式会社 | Adhesive composition particle |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006321870A (en) | 2006-11-30 |
| JP5292664B2 (en) | 2013-09-18 |
| CN1865323B (en) | 2012-07-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11629244B2 (en) | Thermoplastic resin composition, cellulose-reinforced thermoplastic resin composition, method of producing cellulose-reinforced thermoplastic resin composition, molded article of cellulose-reinforced resin, and method of producing molded article of cellulose-reinforced resin | |
| CN1087019C (en) | High melt strength, propylene polymer, process for making it, and use thereof | |
| CN1031885C (en) | Thermoplastic elastomeric compositions | |
| CN1024514C (en) | Laminar articles made from mixtures of polyolefin and ethylene/vinyl alcohol copolymers | |
| CN1026326C (en) | Shaped resin article | |
| CN1139131A (en) | Mixture of polymers including halogen-containing polymer and compatibilized with grafted aliphatic polyester | |
| CN1167802A (en) | Coextrusion binder based on mixture of cografted polyolefins | |
| CN1175968A (en) | Mixture of polyolefin and polyamide alloy, and fabrication process | |
| CN1138827C (en) | Ethylene-ethenol copolymer constituted resin composition with good adhesiveness between layers | |
| CN1182096A (en) | Graft polymers with controlled viscosity | |
| CN1865323A (en) | Multilayer pellet and method for producing the same | |
| CN1175052C (en) | Thermoplastic resin formed article having high-rigidity and high-strength | |
| US8202613B2 (en) | Multilayer pellet and method for producing the same | |
| CN1753942A (en) | Compatibilizing agent for engineering thermoplastic/polyolefin blend | |
| CN1694921A (en) | Graft copolymer composition, thermoplastic resin composition containing the same, and molded object | |
| CN1358205A (en) | Polyolefin compositions, method for the production and use thereof | |
| TWI411610B (en) | Initiator composition comprising trioxepane, its preparation and use | |
| CN1922269A (en) | Copolymer-containing aliphatic polyester resin composition | |
| CN1202150C (en) | Graft polymer, wood-plastic material containing graft polymer and preparation method | |
| CN1182756A (en) | Impact-resistant styrenic resin compositions and moulded articles thereof | |
| JP4490658B2 (en) | Resin composition for engineering plastic modification and method for modifying polyester using the composition | |
| JP4274455B2 (en) | Process for producing modified ethylene vinylcyclohexane copolymer resin and modified ethylene vinylcyclohexane copolymer resin | |
| CN1832991A (en) | Catalyst systems for elastomeric compositions | |
| CN1723238A (en) | Scratch and mar resistant soft ethylene elastomer compositions | |
| CN1096309A (en) | Polymer composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120704 Termination date: 20190516 |