CN103917566A - Polymers based on grafted polyolefins - Google Patents

Polymers based on grafted polyolefins Download PDF

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Publication number
CN103917566A
CN103917566A CN201280054061.5A CN201280054061A CN103917566A CN 103917566 A CN103917566 A CN 103917566A CN 201280054061 A CN201280054061 A CN 201280054061A CN 103917566 A CN103917566 A CN 103917566A
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Prior art keywords
polymkeric substance
composition
compound
component
polyolefine
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Chinese (zh)
Inventor
S·施洛
R·范德米尔
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BASF SE
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BASF SE
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Priority to EP11188421.9 priority Critical
Priority to EP11188421 priority
Application filed by BASF SE filed Critical BASF SE
Priority to PCT/EP2012/072025 priority patent/WO2013068395A1/en
Publication of CN103917566A publication Critical patent/CN103917566A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • C08F8/14Esterification
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Abstract

The present invention relates to a polymer (P1) obtainable by reaction of at least one component a) with at least one component b), wherein a) is at least one polyolefin (A), which is grafted with at least one compound (G), and b) is at least one compound (B) containing at least two epoxy groups.

Description

Based on the polymkeric substance of graft polyolefin
Invention is described
The present invention relates to a kind of polymkeric substance (P1), it can be by making at least one graft polyolefin react and obtain with the compound that contains at least two epoxy group(ing).The invention further relates to a kind of composition, it comprises described polymkeric substance (P1) and at least one other polymkeric substance (P2).Preferably described composition is processed.The invention still further relates to one prepares method and the one of polymkeric substance (P1) and prepares the method containing the composition of polymkeric substance (P1) and polymkeric substance (P2).In addition, the present invention relates to described polymkeric substance (P1) in the purposes reducing in melt flow rate (MFR) (MFR), especially in recovery polyolefine.
Polyolefine, polypropylene (PP) is the known polymer classification that can be used for many different field especially.Polyolefinic advantage is the recyclable product of being made up of polyolefine.But, between polyolefine processing period, polyolefine, especially reclaiming polyolefinic loss of molecular weight is known problem.Melt strength in the article that the loss of (molecule) amount causes being made up of polyolefine during processing (especially by extruding application) reduces (its consequence is to record melt flow rate (MFR) to improve).The polyolefinic processing problems of the melt flow rate (MFR) with raising has been proposed in document.
WO00/26286 relates to a kind of method and a kind of composition that comprises polyolefine and multi-functional epoxy's compound that changes polyolefin molecular weight.Described polyolefinic molecular weight changes by adding at least one compound (A), and described compound (A) contains at least one epoxy group(ing) and at least one alkenyl.In addition,, except compound (A), also add free radical forming agent as superoxide and/or perchlorate.The shortcoming of described method is the uncontrolled side reaction that causes due to splitting of chain and/or due to the crosslinked gel formation causing (this effect is mainly by using superoxide and/or perchlorate to cause).
WO97/30112 relates to a kind of method of stabilization of polyolefins regenerant, a kind of stabilizer blend and a kind of recovery polyolefine that can obtain by described method.Make polyolefine regenerant stable to oxidation, heat or photoinduced degraded by add at least one secondary aromatic amine and at least one multi-functional epoxy's compound in polyolefine regenerant.
US-B6,884,851 relate to and a kind ofly prepare the polyolefinic method with specific rheological property and increase-volume performance, and the polyolefine of gained and purposes thereof.The polyolefine obtaining by described method is graft polyolefin, and it is compared from the polyolefine of not grafting and demonstrates different melt strength performances.The polyolefine for the treatment of grafting can be normal olefine based on containing 2-8 carbon atom as homopolymer or the multipolymer of ethene, propylene or 1-octene.Grafting is selected from the functional group of carbonyl and acid anhydrides and has can carrying out by grafted monomer of vinyl unsaturated group with having at least one.But, US-B6,884,851 graftomer is not further reaction after grafting.
EP-A0 269 275 relates to a kind of composition for thermoplastic elastomer, and it has excellent Thermoadhesive and have high rubber-like elasticity and good mouldability various resins and metal.Described composition for thermoplastic elastomer comprises: a) peroxide crosslinking olefin copolymer rubber, b) olefin plastic(s) with c) a) compare with amount b) with component, be less than 10% unsaturated epoxy monomer or unsaturated carboxylic monomer.Described composition for thermoplastic elastomer is partial cross-linked.Rubber components is not a) containing any grafting alkene.Described unsaturated epoxy monomer can be the glycidyl ester of for example unsaturated monocarboxylic, as glycidyl acrylate or glycidyl methacrylate.Described composition is by by described component blend, and under organo-peroxide exists described in Dynamic heat-treatment blend prepare to obtain partial cross-linked.
US-A2004/0138381 relates to chainextender, the polymer composition of being made up of epoxide-functional monomer and the goods of being made up of it.Described chainextender comprises a) at least one epoxy functionalized (methyl) acrylic monomer and the b) polymerisate of at least one styrene monomer and/or (methyl) acrylic monomer.Described chainextender must meet other parameters, according to appointment the epoxy equivalent (weight) of 180-approximately 2800.Described chainextender can be used in chain-extension polymerization compositions, and described composition comprises (except described chainextender) at least one polycondensate.In described composition, at least a portion of described chainextender reacts to prepare the polycondensate through chain extension with a part for described polycondensate.Polycondensate used is selected from for example polyester, polymeric amide or urethane.
To reducing polyolefine, especially reclaim polyolefine and still have very large market interest as the sane technology that reclaims polypropylene or poly melt flow rate (MFR).Potential problems of the present invention are to provide new type polyolefin.Described new type polyolefin is for (difference) polymkeric substance, in particular in (recovery) polyolefine time, should be able to reduce melt flow rate (MFR).
According to the present invention, described object by one can by make at least one component a) with at least one components b) react the polymkeric substance (P1) that obtains and realize, wherein:
A) be at least one polyolefine (A), it is grafted with at least one compound (G), and
B) be at least one compound that contains at least two epoxy group(ing) (B).
By graft polyolefin is used as to component a) to obtain polymkeric substance (P1), can find of the present invention one large advantage.Due to grafting and the functionality keeping, chain extension can be realized by simple reaction mode, thereby causes compound (B) stable keys to be connected on component polyolefine a).Because compound (B) contains at least two epoxy group(ing), therefore component at least two (independent) graft polyolefins a) can be linked together.Consequently obtain novel and stable polymkeric substance (P1), it,, compared with the common polyolefine of not grafting, has the molecular weight enlarging markedly.In addition, according to component a), described new polymers (P1) is compared with conventional polymer, and moment of torsion improves.
Compared with (recovery) polyolefine described in WO00/26286 for example, the additional advantages of polymkeric substance (P1) be when by make at least one component a) with at least one components b) react while preparing polymkeric substance (P1), do not use radical initiator.The method of WO00/26286 need to be used radical initiator (free radical forming agent is as superoxide), and otherwise described multi-functional epoxy's compound can not be connected with polyolefine.But, by the method for WO00/26286, but only use graft polyolefin of the present invention can obtain uncontrolled the increasing of polyolefine of the molecular weight with increase.Consequently, in polymkeric substance of the present invention (P1), can find not have completely or significantly reduced because splitting of chain causes not controlled side reaction and/or due to the crosslinked gel formation causing.
Polymkeric substance of the present invention (P1) can be successfully and different polymkeric substance, especially with polyolefine, particularly uses together with reclaiming polyolefine.Due to stable keyed jointing and because the controlled of high molecular polyolefine of polymkeric substance of the present invention (P1) increases, polyolefine, especially reclaims polyolefine because the molecular weight reduction that machining causes can be compensated.This means reclaim polyolefinic quality/performance can by add at least a certain amount of have with grafting not and/or not compared with the common polyolefine of chain extension the new polymers (P1) of the molecular weight of increase significantly improve.
Below be further elaborated the present invention.
First, in more detail definition can by component a) with b) react obtain polymkeric substance (P1).The composition that definition comprises at least one polymkeric substance (P1) and at least one other polymkeric substance (P2) hereinafter after a while and the method for preparing described polymkeric substance (P1) or comprising described polymkeric substance (P1) and described composition (P2).
The component that is used for obtaining polymkeric substance (P1) a) comprises at least one polyolefine that is grafted with at least one compound (G) (A).Polyolefine (A) itself (not considering compound (G)) can be any polyolefine known to the person skilled in the art and not grafting.For example be described in WO00/26286 as the suitable polyolefins of polyolefine (A).Described polyolefine can be for example by radical polymerization or catalyzed polymerization preparation.Polyolefine can be homopolymer or the multipolymer based at least two kinds of different alkene.Polyolefine (A) is preferably the normal olefine that contains 2-8 carbon atom based on (at least one) as the polymkeric substance of ethene, propylene, 1-butylene, 1-amylene, 1-hexene and 1-octene.At multipolymer, especially in the situation of polypropylene copolymer, comonomer (except above-mentioned normal olefine) is additionally selected from 4 vinyl cyclohexene, Dicyclopentadiene (DCPD), methene norbornene and ethylidene norbornene, 1,3-butadiene, isoprene and 1,3-pentadiene.
More preferably, polyolefine (A) is selected from polypropylene (PP), PP multipolymer, polyethylene (PE), or metallocene based polyolefins.Polyethylene is preferably Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE) or high density polyethylene(HDPE) (HDPE).PP multipolymer and metallocene based polyolefins based on last two the described identical monomers of leading portion.Most preferably, component polyolefine (A) a) is polypropylene (PP) or polyethylene (PE).
The compound (G) grafting at least one polyolefine (A) can be the known any compound that can be used for grafting on polyolefine of those skilled in the art.Described compound (G) has at least one functional group, and it is grafting at least one polyolefine (A) still existence afterwards.In addition, described functional group can with the epoxy reaction of compound (B) hereinafter described.This compounds is described in for example US-B6, in 884,851.Preferably, compound (G) can be there is at least one functional group that is selected from carbonyl and acid anhydrides can grafted monomer.Such can grafted monomer example be unsaturated monocarboxylic or dicarboxylic acid and derivative and unsaturated monocarboxylic acid anhydride or dicarboxylic anhydride and derivative thereof.Compound (G) can preferably contain 3-20 carbon atom by grafted monomer.
In addition, other can grafted monomer can be used as with the mixture of at least one compound (G) and use.Described other can have vinyl unsaturated group and optional one or more aromatic rings by grafted monomer.As representative instance, can mention 1-dodecylene, vinylbenzene, vinyl pyridine, Vinylstyrene, Isosorbide-5-Nitrae-hexadiene and composition thereof.These other can grafted monomer in, the most particularly preferably vinylbenzene.
More preferably, component compound (G) a) is a kind of compound that is selected from vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid, β-crotonic acid, citraconic acid, maleic anhydride, itaconic anhydride, crotonic anhydride or citraconic anhydride.Most preferably, component compound (G) a) is maleic anhydride.
Polyolefine is carried out to grafting and be known to the person skilled in the art and be disclosed in for example US-B6 to obtain method a) of the compounds of this invention, in 884,851.Due to the preferred definition of polyolefine mentioned above (A) and compound (G), therefore component of the present invention a) most preferably is the polypropylene or the polyethylene that are grafted with maleic anhydride.
Be used for obtaining the components b of polymkeric substance (P1)) be at least one compound that contains at least two epoxy group(ing) (B).This compounds is known to the person skilled in the art and is described in for example US-A2004/0138381 or WO00/26286.Components b)/compound (B) can be considered the chainextender function having with respect to component (a).The compounds of this invention (B) itself can be polymkeric substance or oligopolymer, and condition is for example to prepare compound (B) afterwards by polymerization, and described compound (B) still contains at least two epoxy group(ing).
Preferably, components b) compound (B) polymerisate that is following material:
B1) at least one epoxy functionalized (methyl) acrylic monomer, and
B2) at least one styrenic and/or (methyl) acrylic monomer.
Contain at least two epoxy group(ing) and as components b) the example of this polymerisate be vinylbenzene-(methyl) acrylic copolymer with at least two epoxy group(ing), its by least one epoxy functionalized (methyl) acrylic monomer and the styrenic of at least one non-sense and/or the monomer (according to components b 1) of (methyl) acrylic monomer and b2)) preparation.
Term used herein " (methyl) acrylic monomer " comprises acrylic monomer and methacrylic monomer, and relate to the corresponding esters (acrylate and methacrylic ester) of acrylic or methacrylic acid, as methyl acrylate and methyl methacrylate.Suitable acrylic acid or the like used and methacrylic monomer in the context of the invention (as components b 1-have nothing to do with epoxy functionalities-or as components b 2)) include but not limited to methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, n-butyl acrylate, the just own ester of vinylformic acid, vinylformic acid n-octyl, cyclohexyl acrylate, isobornyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n propyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methyl methacrylate base cyclohexyl and isobornyl methacrylate.
Therefore, in the present invention as components b 1) the example of epoxy functionalized (methyl) acrylic monomer include but not limited to contain those of 1,2-epoxy group(ing), as glycidyl acrylate and glycidyl methacrylate.Other suitable epoxide-functional monomer comprise glycidyl allyl ether, ethyl propylene acid glycidyl ester and glycidyl itoconate.
In the present invention as b2) styrene monomer include but not limited to the mixture of vinylbenzene, alpha-methyl styrene, Vinyl toluene, p-methylstyrene, t-butyl styrene, chloro styrene, vinyl pyridine and these materials.In certain embodiments, the present invention's styrene monomer used is vinylbenzene and alpha-methyl styrene.
Components b 2) preferred monomers be vinylbenzene, alpha-methyl styrene and non-functional acrylate or the non-sense methacrylate monomer that is selected from the just own ester of methyl acrylate, n-butyl acrylate, vinylformic acid, cyclohexyl acrylate, isobornyl acrylate, methyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, cyclohexyl methacrylate and isobornyl methacrylate and combination thereof.
Preferably, compound defined above (B) has the about 2800[g/mol of about 180-] epoxy equivalent (weight) (EEW value), be less than approximately 30 Efn value, approximately 140 Efw value, is less than 25000[g/mol at the most] M wvalue and be less than 6000[g/mol] M nvalue.Efn means several equal epoxy functionalities (every polymer chain), and Efw means weight average epoxy functionalities (every polymer chain), M wmean weight-average molecular weight and M nmean number-average molecular weight.Described value and the method for measuring described value are known to the person skilled in the art and are for example described in US-A2004/138381.
Most preferably, components b of the present invention) the compound that contains at least two epoxy group(ing) (B) at least one is selected from the monomer of glycidyl acrylate and glycidyl methacrylate and at least one and is selected from the polymerisate of the monomer of the just own ester of vinylbenzene, methyl acrylate, n-butyl acrylate, vinylformic acid and methyl methacrylate.
The example that contains at least two epoxy group(ing) and commercially available preferred compound (B) is Joncryl ADR series, as aDR4368-CS (BASF SE, Ludwigshafen, Germany).
In a preferred embodiment of the invention, polymkeric substance (P1) can be by making component a) with b) react and obtain, and wherein makes component a) via being selected from the functional group of acid anhydrides (CO-O-CO-) ,-COOH ,-OH or its salt and the epoxy reaction of compound (B) to obtain polymkeric substance (P1).Term " its salt " only relate to functional group-COOH and-OH.Suitable salt is for example corresponding Na salt, as-COO -na +.Because compound (B) contains at least two epoxy group(ing), therefore preferably make in those epoxy group(ing) at least two with component a), preferably with fall into compound a) two kinds of independent polymer reactions in the range of definition.
In another preferred embodiment of the present invention, described reaction does not exist any free radical forming agent (radical initiator) to carry out under as superoxide and/or perchlorate.
Another theme of the present invention is a kind of composition, and it comprises at least one according to polymkeric substance defined above (P1) and at least one other polymkeric substance (P2).Polymkeric substance (P2) can be any any polymkeric substance not falling in above-mentioned polymkeric substance (P1) range of definition known to the person skilled in the art.Polymkeric substance (P2) is preferably polyolefine (C).Compared with the component of polymkeric substance (P1) polyolefine (A) a), polyolefine (C) can have identical or different definition.This means preferably not grafting of polyolefine (C).More preferably, polyolefine (C) has the definition identical with the component of polymkeric substance (P1) polyolefine (A) a).
Even more preferably, polyolefine (C) is selected from polypropylene (PP), PP multipolymer, polyethylene (PE) or metallocene based polyolefins.Polyethylene is preferably Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE) or high density polyethylene(HDPE) (HDPE).PP multipolymer and metallocene based polyolefins based on above with regard to the described identical monomer of polyolefine (A).Most preferably, component polyolefine (C) a) is polypropylene (PP) or polyethylene (PE).
The present composition can contain at least one polymkeric substance (P1) and at least one other polymkeric substance (P2) with any suitable ratio known to the person skilled in the art.It is 0.2-10 % by weight that described composition preferably contains with respect to the amount of polymkeric substance (P2), more preferably the polymkeric substance of 1-5 % by weight (P1).
The present composition, except at least one polymkeric substance (P1) and at least one other polymkeric substance (P2), also can contain other components known to the person skilled in the art.In the situation that described composition contains other components, described component is preferably selected from stablizer, antioxidant, UV absorption agent, metal passivator, metal quencher, phosphorous acid ester, azanol, nucleator, filler, toughener, softening agent, lubricant, emulsifying agent, pigment, catalyzer, flow improver additive, white dyes or static inhibitor, and the amount of wherein said other components is 0.1-50 % by weight with respect to polymkeric substance (P1) and summation (P2).Preferred filler is mineral filler, more preferably talcum.Preferred toughener is glass fibre.
Preferably, composition of the present invention is the composition through processing, and preferably the described composition through processing is composition compound and that optionally transform subsequently.The processing of described composition, is especially compoundly preferably undertaken by extruding.Procedure of processing is as compound or transform and will below just prepare polymkeric substance (P1) or comprise at least one polymkeric substance (P1) and the composition of at least one other polymkeric substance (P2) is described in more detail.
In a preferred embodiment of the invention, described composition comprises:
I) at least one polymkeric substance (P1), it can a) with b) react and obtain by making:
A) at least one is selected from the polyolefine (A) of polypropylene (PP), PP multipolymer, Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene(HDPE) (HDPE) or metallocene based polyolefins, described polyolefine (A) is grafted with at least one compound that is selected from vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid, β-crotonic acid, citraconic acid, maleic anhydride, itaconic anhydride, crotonic anhydride or citraconic anhydride (G)
B) at least one compound that contains at least two epoxy group(ing) (B), the polymerisate that wherein compound (B) is following material:
B1) at least one epoxy functionalized (methyl) acrylic monomer, and
B2) at least one styrenic and/or (methyl) acrylic monomer,
Ii) at least one other polymkeric substance (P2), it is for being selected from the polyolefine (C) of polypropylene (PP), PP multipolymer, Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene(HDPE) (HDPE) or metallocene based polyolefins.
Described composition is preferably the composition through processing, and preferably the described composition through processing is composition compound and that optionally transform subsequently.The processing of described composition, is especially compoundly preferably undertaken by extruding.Described composition can optionally comprise other components, preferably talc.
Another theme of the present invention is that one is prepared above method and the one of defined polymkeric substance (P1) and prepared the method for the defined composition that comprises at least one polymkeric substance (P1) and at least one other polymkeric substance (P2) above.
The method of preparing polymkeric substance (P1) is known to the person skilled in the art.Polymkeric substance (P1) can exist or not exist any other polymkeric substance to obtain as polymkeric substance (P2) is lower.In the situation that polymkeric substance (P1) should obtain with unpack format (this means not exist any other polymkeric substance), make above defined component a) with defined components b above) react by method known to those skilled in the art.Described reaction does not preferably exist any free radical forming agent (radical initiator) to carry out under as superoxide and/or any perchlorate.Can process the polymkeric substance of gained (P1), preferably have or do not exist the compound and optionally conversion subsequently as lower in polymkeric substance (P2) of any other polymkeric substance.
But, the in the situation that of preparing polymkeric substance (P1) under other polymkeric substance of existence, obtaining composition of the present invention, described composition comprises at least one polymkeric substance (P1) and at least one other polymkeric substance (P2).Preferably the described reaction of preparing polymkeric substance (P1) is carried out under the existence of at least one other polymkeric substance (P2), thereby obtains described composition.But, also can be by separately preparing at least one polymkeric substance (P1) and at least one other polymkeric substance (P2), and after corresponding preparation or polymerization process, mix described polymkeric substance and obtain the present composition.The preparation of described composition does not preferably exist any free radical forming agent (radical initiator) to carry out under as superoxide and/or any perchlorate.
The present composition is preferably according to following method preparation, wherein prepare polymkeric substance (P1) before above defined component a) and/or components b) be scattered in polymkeric substance (P2).
Even more preferably the present composition is processed, preferably compound and optionally conversion subsequently.Most preferably, the preparation of the processing of described composition and polymkeric substance (P1) is carried out simultaneously, particularly during composite steps, carries out simultaneously.
The processing of composition is technology known to the person skilled in the art.Processing generally includes the compound and optional step transforming through compound polymkeric substance subsequently.Very commonly, after implementing polymerization procedure, described polymkeric substance obtains as resin and/or powder.Processing mean by described resin or powder granulation (due to composite steps) or even more particularly product (article) as blown film or plastic paste (due to optional step of converting subsequently).Conventionally in composite steps, carry out together as the step of stablizer or additive to adding some extra compounds in described resin or powder.
According to the present invention, compound (step) preferably undertaken by extruding.Extruding in composite steps can be used any available forcing machine well known by persons skilled in the art to carry out.The preferred type of forcing machine is twin screw extruder, but the single screw extrusion machine with barrier element is also possible.Composition through extruding preferably obtains as particle.
Optionally, after composite steps, available composition of the present invention is implemented step of converting, and described composition preferably provided with (independent) particle shape before step of converting.Described conversion (step) can carry out obtaining specific product (article) as blown film or plastic paste by any method known to the person skilled in the art.Described conversion is preferably by extruding or injection-molded carrying out.Extruding technology in described step comprises film blowing, casting, extrusion-blown modling molding, section bar extrusion, sheet heat forming and sheet material foaming.
In another embodiment of the present invention, described composition is prepared by the following method, wherein polymkeric substance (P2) and component mixture a) are processed, preferably compound by extruding, and add components b between the described processing period of polymkeric substance (P2) and component mixture a)) to prepare polymkeric substance (P1), wherein component a) and b) has above-mentioned definition.
Another theme of the present invention be according to polymkeric substance defined above (P1) reduce polymkeric substance, especially reclaim the purposes in polyolefinic melt flow rate (MFR) (MFR).
Hereinafter set forth the present invention by embodiment.
Embodiment 1
In embodiment below, polymkeric substance of the present invention (P1) is prepared under the existence of a kind of other polymkeric substance (P2).CO-PP relates to described polymkeric substance (P2), and PRIEX25050 and PRIEX25090 relate to above defined component a), and Joncryl ADR4370-S relates to defined components b above).Consequently, PRIEX25095 reacts to obtain polymkeric substance (P1) with Joncryl ADR4370-S.Whole commercially available acquisitions of described polymkeric substance or component and being described as follows:
CO-PP: available from the random PP (R520Y) of SK company
PRIEX25095 and PRIEX25050: available from the polypropylene that is grafted with maleic anhydride (PP-g-MAH) of Dutch Addcomp Holland B.V..Aspect the maleic anhydride amount of grafting, there are different (PRIEX25095:0.465% in described two kinds of PRIEX polymkeric substance; PRIEX25050:0.1%).
Joncryl ADR4370S (BASF SE, Ludwigshafen, Germany): (methyl) acrylic monomer that at least one is epoxy functionalized and the polymerisate of at least one styrene monomer, described polymerisate contains at least two epoxy group(ing).Joncryl ADR4370S has 285[g/mol] EEW value and 6800[g/mol] M wvalue.
Table 1: preparation is through the details of processing compositions
The desired temperature in the heated in sequence district that *) described temperature is forcing machine, it starts until the region (this is the head of forcing machine) after next-door neighbour's feeder from mouth mould (composition leaves the forcing machine end of described forcing machine).Does not heat the first area that raw material is fallen in described forcing machine.
The concentration of sample:
Sample 1:CO-PP (contrast)
Sample 2:CO-PP+0.50%PRIEX25095+0.05%Joncryl ADR4370S
Sample 3:CO-PP+1.50%PRIEX25095+0.15%Joncryl ADR4370S
Sample 4:CO-PP+2.50%PRIEX25095+0.25%Joncryl ADR4370S
Sample 5:CO-PP+0.50%PRIEX25050+0.05%Joncryl ADR4370S
Sample 6:CO-PP+0.25%PRIEX25050+0.0125%Joncryl ADR4370S
Sample 7:CO-PP+0.25%PRIEX25050+0.025%Joncryl ADR4370S
Sample 8:CO-PP+0.25%PRIEX25050+0.01%Joncryl ADR4370S
Sample 9:CO-PP+0.10%PRIEX25050+0.01%Joncryl ADR4370S
The detailed data of table 2:CO-PP
Project Value Unit Test method
MFR 1.8 G/10 minute ASTM?D1238
VICAT test 132 ASTM?D1525
HDT 82 ASTM?D648
Tensile strength@productive rate 290 Kg/cm 2 ASTM?D638
Elongation >500 ASTM?D638
IZOD (breach, 23 ℃) 10 Kg·cm/cm ASTM?D256
Melt flow rate (MFR) (MFR) test:
● test condition:
-load: 2.16kg, temperature: 230 ℃, mouthful mould type: 8/2 (length is 8mm, and diameter is 2mm)
● test result is in table 3:
Table 3:
Sample ? 1 2 3 4
MFR value (g/10 minute) ? 2.17 1.81 1.97 2.09
Sample 5 6 7 8 9
MFR value (g/10 minute) 1.74 1.84 1.70 1.72 1.69
Compared with control sample, the MFR value that the composition exhibiting that contains polymkeric substance of the present invention (P1) goes out to reduce.
Embodiment 2
As shown in Figure 1, as two samples at 15cm 3the function of time on DSM conical double-screw micro-mixer is measured moment of torsion.Experiment condition is as follows: spiro rod rate: 80rpm, and processing temperature: 220 ℃, the total residence time in forcing machine: 2 minutes.Described sample is in not dry lower use in advance.
Sample is: 1.PRIEX15005 (reference: only component a)), and 2.PRIEX15005+0.6%Joncryl ADR4368-CS (polymkeric substance (P1)).
Priex15005 is the LDPE available from Addcomp Holland B.V., is grafted with 0.45% maleic anhydride on it. aDR4368-CS (BASF SE, Ludwigshafen, Germany) is the polymerisate of at least one epoxy functionalized (methyl) acrylic monomer and at least one styrene monomer, and described polymerisate contains at least two epoxy group(ing).Joncryl ADR4368-CS has 285[g/mol] EEW value and 6800[g/mol] M wvalue.
Article two, curve display is added compd B in component polymkeric substance a)) improve very significantly moment of torsion, this means the corresponding raising of viscosity.

Claims (18)

1. a polymkeric substance (P1), its can by make at least one component a) with at least one components b) react and obtain, wherein:
A) be at least one polyolefine (A), it is grafted with at least one compound (G), and
B) be at least one compound that contains at least two epoxy group(ing) (B).
2. according to the polymkeric substance of claim 1 (P1), wherein:
Component polyolefine (A) a) is selected from polypropylene (PP), PP multipolymer, polyethylene (PE) or metallocene based polyolefins, wherein polyethylene (PE) is preferably Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE) or high density polyethylene(HDPE) (HDPE), and/or
Component compound (G) a) is selected from vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid, β-crotonic acid, citraconic acid, maleic anhydride, itaconic anhydride, crotonic anhydride or citraconic anhydride.
3. according to the polymkeric substance (P1) of claim 1 or 2, wherein components b) compound (B) polymerisate that is following material:
B1) at least one epoxy functionalized (methyl) acrylic monomer, and
B2) at least one styrenic and/or (methyl) acrylic monomer.
4. according to the polymkeric substance (P1) of any one in claim 1-3, wherein component is a) via being selected from the functional group of acid anhydrides (CO-O-CO-) ,-COOH ,-OH or its salt and the epoxy reaction of compound (B) to obtain polymkeric substance (P1).
5. a composition, it comprises:
At least one is according to the polymkeric substance (P1) of any one in claim 1-4, and
At least one other polymkeric substance (P2).
6. according to the composition of claim 5, wherein polymkeric substance (P2) is polyolefine (C), and preferred polyolefm (C) has the definition identical with the component of polymkeric substance (P1) polyolefine (A) a).
7. according to the composition of claim 5 or 6, it comprises with respect to the amount of polymkeric substance (P2) is the polymkeric substance (P1) of 0.2-10 % by weight.
8. according to the composition of claim 7, it comprises other components that are selected from stablizer, antioxidant, UV absorption agent, metal passivator, metal quencher, phosphorous acid ester, azanol, nucleator, filler, toughener, softening agent, lubricant, emulsifying agent, pigment, catalyzer, flow improver additive, white dyes or static inhibitor, and the amount of wherein said other components is 0.1-50 % by weight with respect to polymkeric substance (P1) with (P2) sum.
9. according to the composition of any one in claim 5-8, it is the composition through processing, and preferred described processing compositions is through composition compound and that optionally transform subsequently.
10. prepare according to a method for the polymkeric substance (P1) of any one in claim 1-4, wherein make component a) with components b) react.
11. according to the method for claim 10, and wherein said reaction carries out obtaining the composition according to any one in claim 5-9 under the existence of at least one other polymkeric substance (P2).
Prepare according to the method for the composition of any one in claim 5-9 for 12. 1 kinds, wherein at least one polymkeric substance (P1) is mixed with at least one other polymkeric substance (P2).
13. prepare according to a method for the composition of any one in claim 5-9, wherein preparing polymkeric substance (P1) before, by according to the component of claim 1 a) and/or components b) be dispersed in polymkeric substance (P2).
14. according to the method for any one in claim 11-13, wherein described composition is processed, preferably compound and optionally conversion subsequently.
15. according to the method for claim 14, and the preparation of the processing of wherein said composition and polymkeric substance (P1) is carried out simultaneously, especially during composite steps, carries out simultaneously.
16. according to the method for claims 14 or 15, is wherein compoundly undertaken by extruding.
17. prepare according to the method for the composition of any one in claim 5-9 for one kind, wherein polymkeric substance (P2) and component mixture a) are processed, preferably compound by extruding, and add components b between the described processing period of polymkeric substance (P2) and component mixture a)) to prepare polymkeric substance (P1), wherein component a) and b) has the definition according to claim 1.
18. according to the polymkeric substance (P1) of any one in claim 1-4 reduce polymkeric substance, especially reclaim the purposes in polyolefinic melt flow rate (MFR) (MFR).
CN201280054061.5A 2011-11-09 2012-11-07 Polymers based on grafted polyolefins Pending CN103917566A (en)

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US20050261422A1 (en) * 2004-05-21 2005-11-24 National Research Council Of Canada Primer composition and uses thereof

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