CN101016400A - Thermoplastic resin composition - Google Patents

Thermoplastic resin composition Download PDF

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Publication number
CN101016400A
CN101016400A CN 200710087791 CN200710087791A CN101016400A CN 101016400 A CN101016400 A CN 101016400A CN 200710087791 CN200710087791 CN 200710087791 CN 200710087791 A CN200710087791 A CN 200710087791A CN 101016400 A CN101016400 A CN 101016400A
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mma
resin
segmented copolymer
group
weight
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金田丰
千叶健
日色知树
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Kanegafuchi Chemical Industry Co Ltd
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Kanegafuchi Chemical Industry Co Ltd
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Abstract

A thermoplastic resin composition which comprises a thermoplastic resin (a) and a block copolymer (b) comprising a methacrylic polymer block (A) and an acrylic polymer block (B).

Description

The thermoplastic resin composition
The application is that national applications number is 02809807.2 (international application no is PCT/JP02/04667) denomination of invention dividing an application for " thermoplastic resin composition " application.
Technical field
The present invention relates in balance of physical properties, especially shock-resistance balance aspect thermoplastic resin excellent composition.In addition, the present invention relates to, especially snappiness balance aspect thermoplastic resin excellent composition in balance of physical properties.
More particularly, the present invention relates to the thermoplastic resin composition, the segmented copolymer that it comprises thermoplastic resin and comprises methacrylic polymer and acrylic polymers, and it is in balance of physical properties, and especially shock-resistance balance aspect is excellent.
In addition, more particularly, the present invention relates to the thermoplastic resin composition, the segmented copolymer that it comprises crystalline thermoplastic resin and comprises methacrylic polymer and acrylic polymers, and it is being excellent aspect snappiness and the heat-resistant deforming.
Background technology
Usually, thermoplastic resin is used for various fields, and in the time can not obtaining enough performances by the resin of this homogeneous, attempts the method that is used in combination with other resin or the like.Particularly, improving shock-resistance in most cases, the polymer materials that will have elastomerics shape characteristic is used in combination with it.The polymer materials that is used for above-mentioned purpose is called impact modifying agent.
Proposed already to pass through following material in conjunction with the composition that obtains, for example, vinyl chloride resin and chlorinatedpolyethylene, ethylene-vinyl acetate copolymer, MBS (MBS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), butyl acrylate-methylmethacrylate copolymer or the like; Methacrylic resin and BA-St-methylmethacrylate copolymer or the like; Polycarbonate resin and acrylonitrile-butadiene-styrene copolymer (ABS resin), butyl acrylate-methylmethacrylate copolymer or the like; With poly-(butylene terephthalate) resin and acrylonitrile-butadiene-styrene copolymer (ABS resin), epoxide modified ethylene-propylene copolymer or the like.Have many in these compositions in industrial use.
In these impact modifying agents, MBS (MBS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin) and butyl acrylate-methylmethacrylate copolymer are in the presence of cross-linked rubbery particle (formation core segment), graft copolymerization by vinyl monomer (form shell part) obtains, and they are called as based on the core-shell graft copolymer of grain pattern and can be used as impact modifying agent.In these core-shell graft copolymer, MBS resin and ABS resin that the copolymerization by divinyl obtains because unsaturated double-bond is stayed in the main chain of polymkeric substance, therefore the weathering resistance problem will occur.Therefore, when requiring weathering resistance, usually select butyl acrylate-methylmethacrylate copolymer.Yet, although it is pointed out that these core-shell graft copolymer as impact modifying agent, because they comprise crosslinking structure, therefore the molding flowability problem will appear.
On the other hand, be known that by with hard segment and soft segment (rubber constituent) in conjunction with the segmented copolymer that obtains, can be by this multipolymer is combined with thermoplastic resin with the form use of composition.As segmented copolymer, be extensive use of styrene-butadiene copolymer, styrene-isoprene multipolymer and hydrogenant multipolymer thereof (being called styrene-ethylene-butylene copolymer and styrene-ethylene-propylene copolymer).Usually, when using these segmented copolymers, though can obtain shock-resistance, the composition of the mobile excellent balance of rigidity and molding, thermoplastic resin are confined to low polar resin, as polystyrene resin, and polyolefin resin and poly-(phenylene ether) resin.
Recently, the known segmented copolymer that comprises methacrylate polymer and acrylate copolymer can play excellent impact modifying agent, and can obtain shock-resistance thermoplastic resin excellent composition by it is combined with thermoplastic resin.In this case, as carrying out the blended thermoplastic resin, high polar resin gathers (methyl methacrylate) resin as poly-(vinylchlorid) resin, polycarbonate resin, and vibrin, or polyamide resin is effective.Yet, in acrylic block copolymers, still not by introduce the known method that response location is controlled physical property balance and therefore improved this performance with resin or the like.Therefore, above-mentioned method is developed in special hope.
In addition, although recently use as thermoplastic elastomer by the above-mentioned segmented copolymer that obtains that hard segment and soft segment are combined, upper temperature limit in use has strict restriction.
Therefore, require to comprise oil-proofness sometimes, the improvement of control balance of physical properties or the like physicals.
Known segmented copolymer with methacrylate polymer block and acrylate copolymer block plays the thermoplastic elastomer effect, but exists similar problem.Yet, still not by introducing the known method that response location is controlled physical property balance and therefore improved this performance with multipolymer and specific resin compounded or with resin or the like.Therefore, above-mentioned method is developed in special hope.
The content of invention
The object of the present invention is to provide a kind of in physical property balance, shock-resistance balance thermoplastic resin excellent composition especially.Another object of the present invention is to provide a kind of crystalline thermoplastic resin that utilizes, thermoplastic resin excellent composition aspect physical property balance.
The present inventor finds, segmented copolymer with methacrylate polymer block and acrylate copolymer block plays excellent rubber constituent and combines with thermoplastic resin to be formed on physical property balance aspect thermoplastic resin excellent composition, and has therefore finished the present invention.
That is, the present invention has following content:
(1) a kind ofly comprises thermoplastic resin (a) and contain methacrylate polymer block (A) and the thermoplastic resin composition of the thermoplastic resin (b) of acrylate copolymer block (B).
(2) according to the thermoplastic resin composition of above-mentioned (1), wherein, thermoplastic resin (a) is a crystalline thermoplastic resin.
(3) according to the thermoplastic resin composition of above-mentioned (2), wherein, thermoplastic resin (a) is crystallized polyurethane resin or crystalline polyamide resin.
(4) according to the thermoplastic resin composition of above-mentioned (1), wherein, in methacrylate polymer block (A) and acrylate copolymer block (B) polymer blocks one of at least, segmented copolymer (b) comprises reactive functional groups (C).
(5) according to the thermoplastic resin composition of above-mentioned (4), wherein, thermoplastic resin (a) is to be selected from poly-(vinylchlorid) resin, poly-(methyl methacrylate) resin, the acrylonitritrile-styrene resin resin, copolymer of methyl methacrylatestyrene resin, polycarbonate resin, the thermoplastic resin of vibrin and polyamide resin.
(6) according to the thermoplastic resin composition of above-mentioned (4), wherein, reactive functional groups (C) is to be selected from epoxy group(ing) at least, hydrolysable silyl group, hydroxyl, amino, carboxyl, anhydride group, thiazolinyl, reactive chlorine group, or a functional group of  azoles quinoline base.
(7), comprise the thermoplastic resin (a) of 99.5-10% weight and the segmented copolymer (b) of 0.5-90% weight according to the thermoplastic resin composition of above-mentioned (1).
(8), comprise the thermoplastic resin (a) of 90-10% weight and the segmented copolymer (b) of 10-90% weight according to the thermoplastic resin composition of above-mentioned (2).
(9) according to each thermoplastic resin composition of above-mentioned (1)-(8), wherein, produce segmented copolymer (b) by controlled radical polymerization.
Preferred forms of the present invention
Below will explain the present invention in detail.
＜(a) thermoplastic resin 〉
The example that is used for thermoplastic resin of the present invention (a) comprises: poly-(vinylchlorid)-Ji resin, polypropylene-Ji resin, cyclic olefine copolymer resin, poly-(methyl methacrylate)-Ji resin, polyethylene-Ji resin, polystyrene-Ji resin; 70-100% weight, be selected from the aromatics alkenyl compound, vinyl monomer that vinyl cyanide compound and (methyl) acrylate are at least a and 0-30% weight, can with the another kind of vinyl monomer such as the ethene of this vinyl monomer copolymerization, propylene or vinyl acetate, and/or diene monomers such as divinyl or isoprene polymerization and the homopolymer or the multipolymer that obtain; Polyphenylene ether-Ji resin, polycarbonate-Ji resin, polyester-Ji resin, polymeric amide-Ji resin, polyacetal resin, polyphenylens sulfide resin, polysulfone resin, polyimide resin, polyetherimide resin, polyether ketone resin, polyether-ether-ketone resin, and polyamide-imide resin, or the like.These resins can use separately or use with two or more mixture.
The example of poly-(vinylchlorid)-Ji resin comprises: poly-(vinylchlorid) homopolymer and poly-(vinylchlorid) multipolymer with different polymerization degree, as vinyl chloride-vinyl acetate copolymer, the chloroethylene-vinyl acetate-maleic acid anhydride copolymer, vinyl chloride-ethylene copolymer, and VCP; Poly-(vinylchlorid) alloy, alloy as poly-(vinylchlorid) and ethylene-vinyl acetate copolymer, the alloy of poly-(vinylchlorid) and acrylonitrile-butadiene-styrene copolymer, the alloy of poly-(vinylchlorid) and MBS, the alloy of poly-(vinylchlorid) and chlorinatedpolyethylene, the alloy of poly-(vinylchlorid) and acrylic copolymer, the alloy of poly-(vinylchlorid) and urethane, the alloy of poly-(vinylchlorid) and NBR; Poly-(vinylchlorid)/filler composite materials, functionalized poly (vinylchlorid), as back-chlorating poly-(vinylchlorid), poly-(vinylidene chloride) homopolymer, poly-(vinylidene chloride) multipolymer, as vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-acrylonitrile copolymer, and vinylidene chloride-acrylate copolymer, or the like.According to consistency, can suitably use any poly-(vinylchlorid)-Ji resin.
The example of polyethylene-Ji resin comprises: polyvinyl resin, and as new LDPE (film grade), high density polyethylene(HDPE), LLDPE, and ultrahigh molecular weight polyethylene(UHMWPE); Multipolymer with ethene and polar monomer, as ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, the ethylene-methyl methacrylate methyl terpolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, ethylene-vinyl acetate-glycidyl methacrylate copolymer, ethylene-acrylic acid copolymer, the multipolymer of the metal-salt of ethene and acrylic or methacrylic acid, maleic anhydride modified polyethylene, maleic anhydride modified ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate dimethylamino methyl terpolymer, vinyl-vinyl alcohol copolymer, and the ethylene oxide adduct of vinyl-vinyl alcohol copolymer.In these polymkeric substance, consider consistency, the multipolymer of ethene and polar monomer is preferred, and, consider consistency, have glycidyl, carboxyl, or the multipolymer of alcoholic extract hydroxyl group is preferred.
The example of polypropylene-Ji resin comprises: polypropylene, as evenly complete with (homoisotactic) polypropylene, the isotatic polypropylene random copolymers that comprises ethene or 1-butylene, the isotatic polypropylene segmented copolymer that comprises ethylene-propylene, Ziegler-Natta catalyst base isotatic polypropylene, metallocene catalyst base isotatic polypropylene, metallocene catalyst base syndiotactic polypropylene, and atactic polypropylene(APP); Functionalization polypropylene, as the polymer alloy of polypropylene and rubber, polypropylene/filler composite materials, the polypropylene of Chlorinated Polypropylene III and toxilic acid modification.In these polymkeric substance, consider consistency, the polypropylene of Chlorinated Polypropylene III and toxilic acid modification is preferred.
The cyclic olefine copolymer resin is had no particular limits, as long as they comprise cycloolefin, as cyclopentadiene or dicyclopentadiene, and for example can be ARTON (making) by JSR Co.Ltd., ZEONEX (making), or the multipolymer of cycloolefin and ethene or propylene by Nippon Zeon Co.Ltd..In these resins, consider the preferred ARTON of consistency.
Poly-(methyl methacrylate)-Ji resin is had no particular limits, as long as they are to comprise the resin of methyl methacrylate as main component, and can be alpha-methyl styrene wherein, maleic anhydride or the like carries out poly-(methyl methacrylate) of copolymerization.Consider consistency and/or reactivity,, therefore, can suitably use in them any because poly-(methyl methacrylate)-Ji resin has ester group in side chain.
The example of polystyrene-based resin comprises: polystyrene homopolymer, and polystyrene-poly butadiene polymer alloy, High Impact Polystyrene (HIPS) such as polystyrene-acrylic rubber polymer alloy, syndiotactic polystyrene, or the like.
As passing through 70-100% weight, be selected from the aromatics alkenyl compound, vinyl cyanide compound and at least a vinyl monomer and 0-30% weight of (methyl) acrylate, can with the another kind of vinyl monomer such as the ethene of this vinyl monomer copolymerization, propylene or vinyl acetate, and/or diene monomers such as divinyl or isoprene polymerization and the homopolymer or the multipolymer that obtain, for example, that can mention has: acrylonitrile-styrene base co-polymer resin, as the acrylonitritrile-styrene resin resin, the acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile-butadiene-styrene (ABS)-α-Jia Jibenyixigongjuwu resin, the acrylonitrile-butadiene-styrene copolymer resin of maleimide-modification, vinyl cyanide-n butyl acrylate styrene resin, vinyl cyanide-ethylene/propene-styrene copolymer resin, the acrylonitrile-chlorianted polyethylene-styrene terpolymer resin; The copolymer of methyl methacrylatestyrene resin; Or the like.Consider consistency/reactivity, suitably use acrylonitrile-styrene (yl) any of its copolymer resin and its copolymer resin of methyl methacrylate-vinylbenzene.
As polyphenylene ether-Ji resin, that can mention has: the polyphenylene ether homopolymer; Polyphenylene ether-Ji alloy, as the alloy of polyphenylene ether and polystyrene, the alloy of polyphenylene ether and polymeric amide, and the alloy of polyphenylene ether and poly-(butylene terephthalate).
As polycarbonate-Ji resin, that can mention has: polycarbonate, as dihydroxyphenyl propane-type aromatic polycarbonate; Polycarbonate-Ji alloy, alloy as polycarbonate and acrylonitrile-butadiene-styrene copolymer, the alloy of polycarbonate and polybutylene terephthalate, the alloy of the alloy of polycarbonate and polyarylate and polycarbonate and poly-(methyl methacrylate).Because polycarbonate-Ji resin is being excellent aspect the consistency of segmented copolymer (b), and the carbonic acid ester bond in main chain, terminal carboxyl(group) and hydroxyl have reactivity, and therefore, they any all can suitably use.
The example of polyester-Ji resin comprises: aliphatic polyester, and as poly-(oxyacetic acid), poly-(lactic acid), polycaprolactone and poly-(Succinic Acid second diester)); Half-aromatic polyester, as polyethylene terephthalate, poly terephthalic acid Sanya methyl esters, polybutylene terephthalate, poly-naphthalene diacid second diester, poly-terephthalic acid hexanaphthene two methylene esters, ethylene glycol terephthalate/terephthalic acid hexanaphthene two methylene esters, 1 type TLCP and 2 type TLCP.In addition, what also can mention is ester-based elastomeric, and it is to have the segmental segmented copolymer of polyester.Because polyester-Ji resin is being excellent aspect the consistency of segmented copolymer (b), and the ester bond in main chain, terminal carboxyl(group) and hydroxyl have reactivity, and therefore, they any all can suitably use.
The example of polymeric amide-Ji resin comprises: based on the aliphatic polyamide of ring-opening polymerization, as PA6 (polycaproamide) and PA12 (poly-lauramide); Based on the polymeric amide of polycondensation, as PA66 (polyhexamethylene adipamide), PA46 (polytetramethylene adipamide), PA610, PA612, and PA11; Half-aromatic poly, as MXD6, PA6T, PA9T, PA6T/66, PA6T/6, and amorphous PA; Entirely-and aromatic poly, as poly-(right-the phenylene terephthalamide), poly-(-the phenylene terephthalamide) and poly-(-phenylene isophthaloyl amine); Or the like.In addition, what can also mention is the amide group elastomerics, and it is the segmented copolymer with polymeric amide fragment.Because polymeric amide-Ji resin is being excellent aspect the consistency of segmented copolymer (b), and the amido linkage in main chain, terminal carboxyl(group) and hydroxyl have reactivity, and therefore, they any all can suitably use.
The example of polyacetal resin comprises the multipolymer of polyacetal homopolymer and formaldehyde and three  alkane.
Because polyphenylens sulfide resin, polysulfone resin, polyimide resin, polyetherimide resin, polyether ketone resin, polyether-ether-ketone resin, polyamide-imide resin is being excellent aspect the consistency of segmented copolymer (b), and the active group of going up endways in main chain neutralization, therefore, they any all can suitably use.
In the present invention, to thermoplastic resin (a) without limits, and can use various thermoplastic resins widely.In these resins, consider the physicals that easy acquisition is wished, those that have excellent compatibility and/or a sound response with segmented copolymer (b) are preferred.In addition, in the present invention, even can also use not so good and do not have reactive resin with segmented copolymer (b) with the consistency of segmented copolymer (b), but by known method, for example, by using silane coupling agent, organic acid anhydride, or the like processing and this resin is carried out the method for chemical modification, or utilize the method for compatibility enhancer, can obtain to have the more preferably composition of physicals.In addition, even when this resin during not with the position of segmented copolymer (b) reaction, by making the segmented copolymer (b) that is scattered in this resin carry out crosslinked chemical stability and the thermotolerance that also can improve this segmented copolymer (b), and, can further control dispersion diameter by during it is mediated with resin, making it crosslinked.
Under the situation that above-mentioned thermoplastic resin is used in combination with two or more, mixture is had no particular limits.When having excellent compatibility and reactive resin (a1) with segmented copolymer (b), have excellent compatibility with segmented copolymer (b) but do not have reactive resin (a2), the resin (a3) that has not so good consistency He responding property with segmented copolymer (b), with have not so good consistency with segmented copolymer (b) and do not have reactive resin (a4) as example when enumerating described mixture, preferably following mixture: (a1) and (a1), (a1) and (a2), (a1) and (a3), (a1) and (a4), (a2) and (a2), (a2) and (a3), (a2) and (a4), (a3) and (a3), and (a3) and (a4).At reactive functional groups (C) is under the situation of epoxy group(ing), and the object lesson of described mixture comprises: as (a1) and mixture (a1), PC/PBT and PET/PBT; As (a1) and mixture (a2), PC/ABS; And the mixture of (a2) of conduct (a2), PVC/ABS.In addition, the consistency in order to improve between the blended resin in addition also may be with segmented copolymer (b) as compatibility enhancer.
In above-mentioned thermoplastic resin, the preferred use gathered (vinylchlorid) resin, poly-(methyl methacrylate) resin, the acrylonitrile styrene copolymer resin, the copolymer of methyl methacrylatestyrene resin, polycarbonate-Ji resin, polyester-Ji resin and polymeric amide-Ji resin at least a, this be because they with the present invention in the segmented copolymer (b) that uses have good consistency and/or reactive and can easily obtain physicals, the especially shock-resistance of excellence.In addition, but they two or more be used in combination, and mixture is had no particular limits.
In addition, thermoplastic resin (a) crystalline thermoplastic resin preferably.
In above-mentioned thermoplastic resin composition, crystalline thermoplastic resin preferably is selected from the thermoplastic resin of crystallized polyurethane resin and crystalline polyamide resin.These resins can use separately or use with two or more mixture.
The example of crystalline polyester-Ji resin comprises: aliphatic polyester, and as poly-(oxyacetic acid), poly-(lactic acid), polycaprolactone and poly-(Succinic Acid second diester)); Half-aromatic polyester, as polyethylene terephthalate, poly terephthalic acid Sanya methyl esters, polybutylene terephthalate, poly-naphthalene diacid second diester, poly-naphthalene diacid fourth diester and poly-terephthalic acid hexanaphthene two methylene esters, ester-based elastomeric; Or the like.In these resins, consider the balance of crystallization velocity and physicals, preferred polybutylene terephthalate.
The example of crystalline polyamide-Ji resin comprises: based on the aliphatic polyamide of ring-opening polymerization, as PA6 (polycaprolactam) and PA12 (nylon 12); Based on the polymeric amide of polycondensation, as PA66 (polyhexamethylene adipamide), PA46 (polytetramethylene adipamide), PA610, PA612, and PA11; Half-aromatic poly, as PA6T/66, acid amides-based elastomeric; Or the like.In these resins, consider the balance and the cost of physicals, preferred PA6.
Under with crystalline thermoplastic resin and segmented copolymer (b) blended situation, its ratio of mixture is had no particular limits, but consider better balance between snappiness and the thermotolerance, preferred 90-10% weight crystal thermoplastic resin and 10-90% weight segmented copolymer (b), more preferably 80-20% weight crystal thermoplastic resin and 20-80% weight segmented copolymer (b), more preferred 70-30% weight crystal thermoplastic resin and 30-70% weight segmented copolymer (b).
Emphasizing under the flexible situation, described ratio is preferably 90-10% weight crystal thermoplastic resin and 10-90% weight segmented copolymer (b), more preferably 70-10% weight crystal thermoplastic resin and 30-90% weight segmented copolymer (b), more preferred 50-10% weight crystal thermoplastic resin and 50-90% weight segmented copolymer (b).
When the combined amount of segmented copolymer (b) during, exist the trend that is difficult to obtain to have the composition of wishing physicals less than 10% weight.When its combined amount surpasses 90% weight, often be difficult to crystalline thermoplastic resin is expressed distinctive intrinsic physicals.
＜segmented copolymer (b) 〉
Structure to above-mentioned segmented copolymer (b) has no particular limits, but preferably linear block copolymers (b1) or side chain (star) segmented copolymer (b2).
Linear block copolymers (b1) can have any structure, but preferably comprises Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, three-segmented copolymer, or its both, and more preferably comprise these segmented copolymers as main component.The structure of the segmented copolymer except that Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock and three-segmented copolymer for example can be many-segmented copolymer.Example as block copolymer structure of the present invention, more preferably: Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, three-segmented copolymer, the mixture of triblock copolymer and Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, the mixture of three-segmented copolymer and many-segmented copolymer, or Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, the mixture of three-segmented copolymer and segmented copolymer.In these segmented copolymers, further preferably, comprise Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock and three-segmented copolymer as main component.
In these cases, when the methacrylate polymer block is represented with A, when the acrylate copolymer block is represented with B, two-segmented copolymer is the A-B type, and three-segmented copolymer is A-B-A type or B-A-B type, and many-segmented copolymer is A-(B-A) n-B type, A-B-(A-B) n-A type, or B-(A-B) n-A-B type, wherein, n is 1 or greater than 1 integer.In these multipolymers, consider force of cohesion, three-block type is preferably the A-B-A type, and many-block type is preferably A-(B-A) n-B type or A-B-(A-B) n-A type.
Side chain (star) segmented copolymer (b2) can have any structure, but considers the physicals of composition, preferably has the segmented copolymer of above-mentioned linear block copolymers as elementary cell.
The structure of above-mentioned segmented copolymer can suitably be used according to intended purpose.In addition, even comprise homopolymerization (acrylate) when these segmented copolymers, homopolymerization (methacrylic ester), or the like the time, what form in process of production is also included within the present invention's scope required for protection.
Can be used for segmented copolymer of the present invention (b) and comprise methacrylate polymer block (a) and acrylate copolymer block (b), still, can comprise reactive functional groups (C) in one of at least at polymer blocks.
Consider the stability of the formed key of reaction, reactive mode, reaction difficulty or ease, the operability of raw material, cost or the like, reactive functional groups (C) preferably is selected from epoxy group(ing), hydrolysable silyl group, hydroxyl, amino, carboxyl, anhydride group, thiazolinyl, reactive chlorine group, or at least a functional group of  azoles quinoline base.Epoxy group(ing) be hyperergy and with various functional group reactionses, and hydrolyzable silyl and airborne reaction of moisture and take place crosslinkedly, these are the unexistent features of other reactive functional groups.In addition, consider the easiness and the cost of introducing, hydroxyl is useful.In addition and since carboxyl have strong polarity and with amino and hydroxyl reaction, so it is useful; Since acid anhydrides have strong reactivity and with various functional group reactionses, so it is useful.According to purposes, can reactive functional groups be introduced in the segmented copolymer with the form of appropriate protection base protection or with functional group's form of reactive functional groups precursor, form reactive functional groups by known chemical reactions then.
Can be used in combination two or more of these reactive functional groups.Be used in combination under the situation of two or more reactive functional groups, situation about can mention has, for example, the reactive functional groups that selection does not react each other, this is because its reactive mode difference; Select to resemble to each other the reactive functional groups of bronsted lowry acids and bases bronsted lowry reaction; Select identical but it is reactive and reaction conditions differs from one another the functional group of its reactive mode; Or the like, and they can suitably use according to predetermined purposes.According to purposes, can form reactive functional groups by known chemical reactions then with the form of appropriate protection base protection or to be that functional group's form of precursor is introduced a reactive functional groups or all reactive functional groups in the acrylic block copolymers.
The preferable range of the quantity of the reactive functional groups that is comprised (C) is according to the reactivity and the reactive mode of reactive functional groups (C), the structure and the component of segmented copolymer (b), constitute the block number of segmented copolymer (b), and wherein comprise the position of reactive functional groups and mode and different.
Under the situation of emphasizing the composition physical property balance, the preferred amount scope of (C) that is comprised is: every mole of segmented copolymer 0.1 or bigger, more preferably 0.2 or bigger, more preferred 0.5 or bigger.Under the situation of the shock-resistance in the lay special stress on physicals, be preferably 1.0 or bigger, more preferably 2.0 or bigger in the content range of every mole of segmented copolymer.The upper limit of contained quantity has no particular limits, but can set according to the characteristic property of resulting composition.In the following description, quantity when being lower than every mole of segmented copolymer 1.0 at comprising of reactive functional groups, should be understood that composition is: every mole of segmented copolymer have 1.0 or more multiple reactionness functional group segmented copolymer and do not have the mixture of the segmented copolymer of reactive functional groups.
The position that wherein comprises reactive functional groups (C) is had no particular limits, but can be included in methacrylate polymer block (A) and acrylate copolymer block (B) among both, or in any, between polymer blocks, and at the end of molecular chain.
Comprise (C) mode be not particularly limited, but can be, and can directly or by suitable organic group be bonded to molecule chain end by monomer derived.Under the situation by monomer derived (C), the quantity of the repeating unit that monomer is formed can be 1 or 2 or more wherein to comprise monomeric each polymer blocks.When quantity is 2 or when bigger, monomeric polymerization methods may be random copolymerization or block copolymerization.For example, under the situation of A-B type Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, multipolymer can be (A/C)-Type B, A-(B/C) type, the C-A-B type, the A-B-C type, or the like any.For example, under the situation of A-B-A type triblock copolymer, multipolymer can be (A/C)-B-A type, (A/C)-B-(A/C) type, A-(B/C)-A type, the C-A-B-A type, the C-A-B-A-C type, or the like any.In these cases, (A/C) mean that functional group (C) is included among the block A.
Under the situation that two or more reactive functionality (C) are used in combination, the position of each group that is comprised and mode can freely be set.In addition, what can also mention is: independent reactive functional groups is included in the situation in the same polymer blocks, and independent group is included in the situation in the different polymer blocks, or the like, and can suitably utilize all situations according to predetermined purposes.
The number-average molecular weight of segmented copolymer (b) has no particular limits, and can determine according to block (A) and the required separately molecular weight of block (B).In major objective is to improve under the situation of shock-resistance, number-average molecular weight scope (b) preferably from 30,000 to 500,000, more preferably from 40,000 to 400,000.In addition, be to improve under the situation of processing characteristics in major objective, described scope preferably from 10,000 to 1,000,000, more preferably from 30,000 to 400,000.In addition, be to obtain Young's modulus under the situation of resin and elastomeric matrix material, described scope preferably from 10,000 to 500,000, more preferably from 30,000 to 400,000, more preferably from 50,000 to 300,000 in purpose.In these cases, determine described molecular weight ranges according to needed physical property balance, this is because little number-average molecular weight tends to make physicals to descend, and big number-average molecular weight tends to make processing characteristics to descend.
To having no particular limits, and be preferably 1.8 or lower, more preferably 1.5 or lower by the weight average molecular weight (Mw) of gel permeation chromatography measurement ratio (Mw/Mn) with number-average molecular weight (Mn).When Mw/Mn surpassed 1.8, the homogeneity of segmented copolymer tended to descend.
The methacrylate polymer block (A) of formation segmented copolymer (b) and the ratio of components of acrylate copolymer block (B) are had no particular limits, and can be according to the desired physicals of intended purpose, desired formability during the composition processing treatment, and block A and the desired separately molecular weight of B block are determined.
The ratio of components of methacrylate polymer block (A) and acrylate copolymer block (B) is preferably 5-90% weight block (A) and 95-10% weight block (B), more preferably 10-80% weight (A) and 90-20% weight (B), more preferably 20-50% (A) and 80-50% weight (B).As (A) during, tend to descend with the consistency of thermoplastic resin and therefore cause the reduction of the defective and the welding property of outward appearance less than 5% weight.When (B) was lower than 10% weight, thermoplastic resin composition's shock-resistance tended to descend.
In addition, be to improve under the situation of processing characteristics in major objective, described ratio is preferably the block (A) of 5-95% weight and the block (B) of 95-5% weight, more preferably 10-90% weight (A) and 90-10% weight (B), more preferably 20-80% weight (A) and 80-20% weight (B).In major objective is to improve under the situation of processing characteristics, and applied compositing range is to improve the situation of shock-resistance usually greater than target, and this is the cause because of the add comparatively small amt of segmented copolymer.When (A) is lower than 5% weight, tends to descend with the consistency of thermoplastic resin and therefore cause macroscopic irregularity and welding property to reduce.When the ratio of (B) was lower than 5% weight, the improvement of thermoplastic resin composition's processing characteristics tended to descend.
In addition, be to obtain its Young's modulus under the situation of the matrix material between resin and the elastomerics in major objective, described ratio is preferably the block (A) of 5-90% weight and the block (B) of 95-10% weight, more preferably 10-80% weight (A) and 90-20% weight (B), more preferably 20-60% weight (A) and 80-40% weight (B).When the ratio of (A) is lower than 5% weight, tends to descend with the consistency of thermoplastic resin and therefore cause macroscopic irregularity and welding property to reduce.When the ratio of (B) was lower than 10% weight, thermoplastic resin composition's physical property balance tended to descend.
Constitute the block (A) of segmented copolymer and the relation between block (B) glass transition temperature and preferably satisfy following formula, wherein, the glass transition temperature of block (A) is represented that by TgA the glass transition temperature of block (B) is represented by TgB.
TgA＞TgB
The above-mentioned glass transition temperature (Tg) of multipolymer can be according to following Fox equation, and monomeric weight ratio is provided with roughly in each polymer moieties by being provided with.
1/Tg＝(W 1/Tg 1)+(W 2/Tg 2)+...+(Wm/Tgm)
W 1+W 2+...+Wm＝1
In the formula, Tg represents the glass transition temperature of polymer moieties, Tg1, and Tg2 ... and Tgm represents the glass transition temperature of each polymerization single polymerization monomer respectively, and W1, W2 ..., Wm represents the weight ratio of each polymerization single polymerization monomer separately.
As the glass transition temperature of each polymerization single polymerization monomer in the above-mentioned Fox equation, for example, can suitably use the value of describing in the polymer handbook (third edition, Wiley-Interscience, 1989).In this respect, can determine above-mentioned glass transition temperature by the tan δ peak of DSC (dsc) or dynamic viscoelastic, but, when the polarity of block (A) and block (B) too near or monomeric quantity is very little the time in block, observed value may depart from the calculated value according to above-mentioned Fox equation sometimes.
In addition, in order to give the thermoplastic resin composition with the transparency, the method that can mention has: the method that the specific refractory power of the specific refractory power of thermoplastic resin and segmented copolymer is complementary, make the dispersion diameter of segmented copolymer (b) reduce to the method that is not more than a certain value, and make this two kinds of method bonded methods.
Under the situation that the specific refractory power of specific refractory power that makes thermoplastic resin and segmented copolymer is complementary, n aAnd n bBetween the scope that differs be preferably 0.1 or littler, more preferably 0.05 or littler, more preferably 0.02 or littler, most preferably 0.01 or littler, wherein, the specific refractory power of thermoplastic resin is by n aExpression, the specific refractory power of segmented copolymer is by n bExpression.In addition, be reduced under the situation that is not more than a certain value at the dispersion diameter that makes segmented copolymer (b), the ultra-thin moulded product sheet that utilization was handled through suitable tinting material, the dispersion diameter scope of (b) is preferably 800 nanometers or littler during with tem observation, 400 nanometers or littler more preferably, more preferably 200 nanometers or littler most preferably are 100 nanometers or littler.In addition, under with two kinds of method bonded situations, with regard to the transparency, can obtain synergistic effect.
As the specific refractory power of above-mentioned resin (a) or segmented copolymer (b), for example, can use the value of describing in the polymer handbook (third edition, Wiley-Interscience, 1989) or utilize the value that D-line (sodium D-line) measures of receiving on the refractometer.
＜methacrylate polymer block (A) 〉
The monomer of formation block (A) comprises the methacrylic ester as main component, and this is because can easily obtain to have the segmented copolymer of wishing physicals, and it is favourable with regard to cost and operability.Speech " main component " means, with 50% weight or more, preferably comprises this composition with 75% weight or more amount.That is, described block (A) comprises 50-100% weight, the methacrylic ester and the 0-50% weight of preferred 75-100% weight, preferred 0-25% weight can with the vinyl monomer of its copolymerization.Obtain by monomer derived and this monomer is included under the situation in the methacrylate polymer block (A) at reactive functional groups (C), this monomer can be any methacrylic ester and can with the vinyl monomer of its copolymerization, but must satisfy the said components requirement.When the ratio of methacrylic ester too hour, methacrylic ester inherent weathering resistance, high glass transition temperature and tend to forfeiture with the consistency of thermoplastic resin.
The required molecular weight of block (A) can be according to the required force of cohesion of block (A), the time that polymerization is required, and the dispersion diameter of the segmented copolymer (b) of relatively hot plastic resin (a) is determined.
Force of cohesion is considered to depend on intermolecular interaction degree (in other words, polarity) and entanglement degree.Therefore, the point that tangles when molecular weight increases increases thereupon, and has therefore strengthened force of cohesion; That is, requiring under the situation of force of cohesion, preferably, M AGreater than MC A, wherein, the required molecular weight of block (A) is by M AExpression, and the molecular weight between the polymkeric substance of formation block (A) the entanglement point is by MC AExpression.
In addition, requiring under the situation of bigger force of cohesion preferred M A* 2*MC AOn the contrary, under the situation of certain force of cohesion of hope and creep property, preferably, MC A＜M A＜2 * MC ADocuments (Polym.Eng.and Sci., Vol.30, pp.753 (1990)) by people such as reference Wu etc. can be known the molecular weight that tangles between the point.For example, when supposing that all blocks (A) when being made of methyl methacrylate, are requiring under the situation of force of cohesion, the number-average molecular weight scope of block (A) is preferably 9200 or bigger.Yet, under the situation of big number-average molecular weight,, therefore, can determine molecular weight according to required throughput, and be preferably 200,000 or lower, more preferably 100,000 or lower because the required time of polymerization tends to increase.
Although the details of dispersion diameter will described subsequently, but for the dispersion diameter that obtains to wish, can design the required molecular weight of block (A), so that (in other words in the consistency of further considering block (A) and resin, polar relationship) and when the content of reactive functional groups (C) and position, when processing treatment, obtains the suitable viscosity of segmented copolymer (b).
The example that constitutes the methacrylic ester of block (A) comprises: the aliphatic hydrocarbon of methacrylic acid (for example., alkyl) ester, as methyl methacrylate, Jia Jibingxisuanyizhi, methacrylic acid just-propyl diester, the methacrylic acid isopropyl esters, methacrylic acid just-butyl ester, Propenoic acid, 2-methyl, isobutyl ester, the methacrylic acid tertiary butyl ester, methacrylic acid n-pentyl ester, methacrylic acid n-hexyl ester, methacrylic n-heptyl acid esters, methacrylic acid n-octyl ester, methacrylic acid 2-(ethyl hexyl) ester, methacrylic acid nonyl ester, the methacrylic acid decyl ester, lauryl methacrylate and methacrylic acid stearyl ester; The alicyclic hydrocarbon ester of methacrylic acid is as cyclohexyl methacrylate and IBOMA; The aralkyl ester of methacrylic acid is as the methacrylic acid benzylester; The aromatic hydrocarbons ester of methacrylic acid is as methacrylic acid phenylester and methyl methacrylate benzoyl ester; Methacrylic acid and the ester with alcohol ether oxygen, that contain functional group are as methacrylic acid 2-methoxy ethyl ester and methacrylic acid 3-methoxyl group butyl ester; The fluoroalkyl of methacrylic acid, as methacrylic acid trifluoromethyl methyl esters, methacrylic acid 2-trifluoromethyl ethyl ester, methacrylic acid 2-perfluor diethyl acetamidomalonate, methacrylic acid 2-perfluor ethyl-2-perfluoro butyl ethyl ester, methacrylic acid 2-perfluor ethyl ester, methacrylic acid perfluor methyl esters, methacrylic acid two perfluoro-methyl methyl esters, methacrylic acid 2-perfluoro-methyl-2-perfluor ethyl methyl esters, methacrylic acid 2-perfluoro hexyl ethyl ester, methacrylic acid 2-perfluor decyl ethyl ester, with methacrylic acid 2-perfluor hexadecyl ethyl ester, or the like.
These resins can use separately or use with two or more mixture.In these resins, consider and the consistency of institute's blended thermoplastic resin that cost, and operability, methyl methacrylate are preferred.Subsequently the conversion reaction of mentioning is introduced under the situation of carboxyl or acid anhydrides in the plan utilization, the methacrylic acid tertiary butyl ester is preferred.In addition, by with IBOMA, the copolymerization of cyclohexyl methacrylate or the like, glass transition temperature can raise.
Can comprise with the example of the vinyl monomer of the methacrylic ester copolymerization that constitutes block (A): acrylate, methacrylic ester, the aromatics alkenyl compound, vinyl cyanide compound, conjugated diene compound, halogen-containing unsaturated compound, the unsaturated dicarboxylic acid compound, the vinyl ester compound, maleimide compound, or the like.
The example of acrylate comprises: acrylic acid aliphatic hydrocrbon (for example alkyl) ester, and as methyl acrylate, ethyl propenoate, vinylformic acid just-propyl diester, the vinylformic acid isopropyl esters, vinylformic acid just-butyl ester, the acryllic acid isobutyl ester, vinylformic acid tertiary butyl ester, vinylformic acid n-pentyl ester, vinylformic acid n-hexyl ester, vinylformic acid n-heptyl ester, vinylformic acid n-octyl ester, 2-EHA, vinylformic acid nonyl ester, vinylformic acid decyl ester, vinylformic acid dodecane ester and stearyl acrylate acyl ester; Acrylic acid alicyclic hydrocarbon ester is as vinylformic acid cyclohexyl ester and isobornyl acrylate; Acrylic acid aromatic hydrocarbons ester is as phenyl acrylate and vinylformic acid toluyl ester; Acrylic acid aralkyl ester is as benzyl acrylate; Vinylformic acid and the ester with alcohol that contains functional group of ether oxygen are as vinylformic acid 2-methoxyl group ethyl ester and vinylformic acid 3-methoxyl group butyl ester; Acrylic acid fluoroalkyl, as vinylformic acid trifluoromethyl methyl esters, vinylformic acid 2-trifluoromethyl ethyl ester, vinylformic acid 2-perfluor diethyl acetamidomalonate, vinylformic acid 2-perfluor ethyl-2-perfluoro butyl ethyl ester, vinylformic acid 2-perfluor ethyl ester, vinylformic acid perfluor methyl esters, vinylformic acid two perfluoro-methyl methyl esters, vinylformic acid 2-perfluoro-methyl-2-perfluor ethyl methyl esters, vinylformic acid 2-perfluoro hexyl ethyl ester, vinylformic acid 2-perfluor decyl ethyl ester, with vinylformic acid 2-perfluor hexadecyl ethyl ester, or the like.
The example of aromatics alkenyl compound comprises vinylbenzene, alpha-methyl styrene, and p-methylstyrene, p-methoxystyrene, or the like.
The example of vinyl cyanide compound comprises vinyl cyanide, methacrylonitrile, or the like.
The example of conjugated diene compound comprises divinyl, isoprene, or the like.
The example of halogen-containing unsaturated compound comprises vinylchlorid, vinylidene chloride, and perfluoro-ethylene, perfluoro propylene, vinylidene fluoride, or the like.
The example of unsaturated dicarboxylic acid compound comprises maleic anhydride, toxilic acid, and the mono alkyl ester of toxilic acid and dialkyl, fumaric acid, the mono alkyl ester of fumaric acid and dialkyl, or the like.
The example of vinyl ester compound comprises vinyl acetate, propionate, and new vinyl acetate acid, vinyl benzoate, vinyl cinnamate, or the like.
The example of maleimide compound comprises maleimide; the methyl maleimide, ethyl maleimide, propyl group maleimide; butyl maleimide; the hexyl maleimide, octyl group maleimide, dodecyl maleimide; the stearyl-maleimide; phenyl maleimide, the cyclohexyl maleimide, or the like.
These resins can use separately or use with two or more mixture.According to the consistency of itself and institute's blended thermoplastic resin, can therefrom select preferred vinyl monomer.In order to give its polymers of block, optionally select preferred resin with some performance.For example, in order to increase the thermotolerance of segmented copolymer, can carry out copolymerization with the monomer that finally makes Tg greater than the Tg of methacrylate polymers.In addition, though by the similar thing of depolymerization Polymerization of Methyl quantitatively of thermolysis, but in order to suppress depolymerization, can make acrylate such as methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid 2-methoxyl group ethyl ester or its mixture, or methacrylic acid, methacrylic anhydride or vinylbenzene carry out copolymerization.In addition, in order to improve oil-proofness, can make vinyl cyanide carry out copolymerization.In addition, in order to improve force of cohesion, can make at the monomer that has different molecular weight between point or the polarity that tangles and carry out copolymerization.
The glass transition temperature of block (A) is preferably 25 ℃ or higher, and more preferably 40 ℃ or higher, more preferably 50 ℃ or higher.When glass transition temperature is lower than 25 ℃, the shock-resistance of thermoplastic resin and thermostability are not enough sometimes as HDT.
The glass transition temperature (Tg) of above-mentioned polymer blocks (A) can be provided with by monomeric weight ratio in each polymer moieties is set according to above-mentioned Fox equation.Utilize the value of describing in the polymer handbook (third edition, Wiley-Interscience, 1989), calculate the glass transition temperature of glass transition temperature as each polymerization single polymerization monomer according to the Fox equation.
＜acrylate copolymer block (B) 〉
The monomer of formation block (B) comprises the acrylate as main component, and this is because can easily obtain to have the composition of wishing physicals, and it is favourable with regard to cost and operability.That is, described block (B) comprises 50-100% weight, the acrylate and the 0-50% weight of preferred 75-100% weight, preferred 0-25% weight can with the vinyl monomer of its copolymerization.Obtain by monomer derived and this monomer is included under the situation in the acrylate copolymer block (B) at reactive functional groups (C), this monomer can be any acrylate and can with the vinyl monomer of its copolymerization, but must satisfy the said components requirement.
When the ratio of acrylate too hour, utilize acrylate institute inherent physicals, especially shock-resistance or snappiness to tend to forfeiture.
The required molecular weight of block (B) can be required according to block (B) Young's modulus and caoutchouc elasticity, time that polymerization is required and determine with respect to the dispersion diameter of thermoplastic resin (a) segmented copolymer (b).
Reactivity of Young's modulus and molecular chain (in other words, glass transition temperature) and molecular weight thereof are closely related, unless therefore molecular weight is not less than certain value, otherwise can not show the inherent Young's modulus.Consider caoutchouc elasticity, wish that same situation will be applicable to caoutchouc elasticity beyond the bigger molecular weight.That is, the required molecular weight ranges of block (B) is preferably M B＞3000, more preferably M B＞5000, more preferred M B＞10000, preferred especially M B＞20000, M most preferably B＞40000, wherein, the required molecular weight of block (B) is by M BExpression.Yet, under the situation of big number-average molecular weight,, therefore, can determine molecular weight according to required throughput, and be preferably 500,000 or lower, more preferably 300,000 or lower because the required time of polymerization tends to increase.
Although the details of dispersion diameter will described subsequently, but for the dispersion diameter that obtains to wish, can design the required molecular weight of block (A), so that (in other words in the consistency of further considering block (B) and resin, polar relationship) and when the content of reactive functional groups (C) and position, when processing treatment, obtains the suitable viscosity of segmented copolymer (b).
The example that constitutes the acrylate of block (B) comprises: acrylic acid aliphatic hydrocrbon (for example alkyl) ester, and as methyl acrylate, ethyl propenoate, vinylformic acid just-propyl diester, the vinylformic acid isopropyl esters, vinylformic acid just-butyl ester, the acryllic acid isobutyl ester, vinylformic acid tertiary butyl ester, vinylformic acid n-pentyl ester, vinylformic acid n-hexyl ester, vinylformic acid n-heptyl ester, vinylformic acid n-octyl ester, 2-EHA, vinylformic acid nonyl ester, vinylformic acid decyl ester, vinylformic acid dodecane ester and stearyl acrylate acyl ester; Acrylic acid alicyclic hydrocarbon ester is as vinylformic acid cyclohexyl ester and isobornyl acrylate; Acrylic acid aromatic hydrocarbons ester is as phenyl acrylate and vinylformic acid toluyl ester; Acrylic acid aralkyl ester is as benzyl acrylate; Vinylformic acid and the ester with alcohol that contains functional group of ether oxygen are as vinylformic acid 2-methoxyl group ethyl ester and vinylformic acid 3-methoxyl group butyl ester; Acrylic acid fluoroalkyl, as vinylformic acid trifluoromethyl methyl esters, vinylformic acid 2-trifluoromethyl ethyl ester, vinylformic acid 2-perfluor diethyl acetamidomalonate, vinylformic acid 2-perfluor ethyl-2-perfluoro butyl ethyl ester, vinylformic acid 2-perfluor ethyl ester, vinylformic acid perfluor methyl esters, vinylformic acid two perfluoro-methyl methyl esters, vinylformic acid 2-perfluoro-methyl-2-perfluor ethyl methyl esters, vinylformic acid 2-perfluoro hexyl ethyl ester, vinylformic acid 2-perfluor decyl ethyl ester, with vinylformic acid 2-perfluor hexadecyl ethyl ester, or the like.These resins can use separately or use with two or more mixture.
In these resins, consider the shock-resistance of thermoplastic resin, cost, and operability, vinylformic acid just-butyl ester is preferred.Require at composition under the situation of oil-proofness, ethyl propenoate is preferred.In addition, requiring under the situation of low-temperature performance, 2-EHA is preferred.In addition, when requiring oil-proofness and low-temperature performance, ethyl propenoate, vinylformic acid just-mixture of butyl ester and vinylformic acid 2-methoxyl group ethyl ester is preferred.
Can comprise with the example of the vinyl monomer of the methacrylic ester copolymerization that constitutes block (B): methacrylic ester, the aromatics alkenyl compound, vinyl cyanide compound, conjugated diene compound, halogen-containing unsaturated compound, unsaturated dicarboxylic acid compound, vinyl ester compound, maleimide compound, or the like.
The example of methacrylic ester comprises: the aliphatic hydrocarbon of methacrylic acid (for example, alkyl) ester, as methyl methacrylate, Jia Jibingxisuanyizhi, methacrylic acid just-propyl diester, the methacrylic acid isopropyl esters, methacrylic acid just-butyl ester, Propenoic acid, 2-methyl, isobutyl ester, the methacrylic acid tertiary butyl ester, methacrylic acid n-pentyl ester, methacrylic acid n-hexyl ester, methacrylic n-heptyl acid esters, methacrylic acid n-octyl ester, methacrylic acid 2-(ethyl hexyl) ester, methacrylic acid nonyl ester, the methacrylic acid decyl ester, lauryl methacrylate and methacrylic acid stearyl ester; The alicyclic hydrocarbon ester of methacrylic acid is as cyclohexyl methacrylate and IBOMA; The aralkyl ester of methacrylic acid is as the methacrylic acid benzylester; The aromatic hydrocarbons ester of methacrylic acid is as methacrylic acid phenylester and methyl methacrylate benzoyl ester; Methacrylic acid with have ether oxygen, contain the ester of the alcohol of functional group, as methacrylic acid 2-methoxy ethyl ester and methacrylic acid 3-methoxyl group butyl ester; The fluoroalkyl of methacrylic acid, as methacrylic acid trifluoromethyl methyl esters, methacrylic acid 2-trifluoromethyl ethyl ester, methacrylic acid 2-perfluor diethyl acetamidomalonate, methacrylic acid 2-perfluor ethyl-2-perfluoro butyl ethyl ester, methacrylic acid 2-perfluor ethyl ester, methacrylic acid perfluor methyl esters, methacrylic acid two perfluoro-methyl methyl esters, methacrylic acid 2-perfluoro-methyl-2-perfluor ethyl methyl esters, methacrylic acid 2-perfluoro hexyl ethyl ester, methacrylic acid 2-perfluor decyl ethyl ester, with methacrylic acid 2-perfluor hexadecyl ethyl ester, or the like.
The example of aromatics alkenyl compound comprises vinylbenzene, alpha-methyl styrene, and p-methylstyrene, p-methoxystyrene, or the like.The example of vinyl cyanide compound comprises vinyl cyanide, methacrylonitrile, or the like.
The example of conjugated diene compound comprises divinyl, isoprene, or the like.
The example of halogen-containing unsaturated compound comprises vinylchlorid, vinylidene chloride, and perfluoro-ethylene, perfluoro propylene, vinylidene fluoride, or the like.
The example of unsaturated dicarboxylic acid compound comprises maleic anhydride, toxilic acid, and the mono alkyl ester of toxilic acid and dialkyl, fumaric acid, the mono alkyl ester of fumaric acid and dialkyl, or the like.
The example of vinyl ester compound comprises vinyl acetate, propionate, and new vinyl acetate acid, vinyl benzoate, vinyl cinnamate, or the like.
The example of maleimide compound comprises maleimide; the methyl maleimide, ethyl maleimide, propyl group maleimide; butyl maleimide; the hexyl maleimide, octyl group maleimide, dodecyl maleimide; the stearyl-maleimide; phenyl maleimide, the cyclohexyl maleimide, or the like.
These resins can use separately or use with two or more mixture.Preferred vinyl monomer can be according to the required glass transition temperature of block (B), Young's modulus, and polarity, and the required physicals of composition and therefrom selecting.For example, in order to increase the oil-proofness of composition, can make vinyl cyanide carry out copolymerization.
The glass transition temperature of block (B) is preferably 25 ℃ or lower, and more preferably 0 ℃ or lower, more preferably-20 ℃ or lower.When glass transition temperature was higher than 25 ℃, the shock-resistance of thermoplastic resin was not enough sometimes.
The glass transition temperature (Tg) of above-mentioned polymer blocks (B) can be provided with by monomeric weight ratio in each polymer moieties is set according to above-mentioned Fox equation.Utilize the value of describing in the polymer handbook (third edition, Wiley-Interscience, 1989), calculate the glass transition temperature of glass transition temperature as each polymerization single polymerization monomer according to the Fox equation.
＜reactive functional group (C) 〉
Reactive functional groups C) preferably is selected from epoxy group(ing), hydrolysable silyl group, hydroxyl, amino, carboxyl, anhydride group, thiazolinyl, reactive chlorine group, with at least one functional group of  azoles quinoline base, more preferably epoxy group(ing) or hydrolyzable silyl, more preferably epoxy group(ing).These functional groups can select optionally.
Hydrolyzable silyl, hydroxyl, amino, carboxyl, anhydride group, thiazolinyl and reactive chlorine group will be described preferably below as the epoxy group(ing) in the functional group of reactive functional groups (C).
(epoxy group(ing))
Epoxy group(ing) is easy to and carboxylic acid or hydroxyl or amino reaction, therefore, epoxy group(ing) can with the polymer reaction that contains above-mentioned polar group.The resin that reacts is had no particular limits, and its example comprises: polyester-Ji resin, polymeric amide-Ji resin, and polycarbonate-Ji resin.In addition, epoxy group(ing) can also suitably be used for high polar resin, as resin or acrylonitrile-butadiene-styrene copolymer (ABS) resin based on vinylchlorid.
Have no particular limits for epoxy group(ing), as long as it is the organic group that contains epoxy group(ing), its example comprises: the aliphatic hydrocrbon (for example, alkyl) that comprises oxirane ring, as 1,2-epoxy ethyl, 2,3-epoxypropyl (being glycidyl) and 2,3-epoxy-2-methyl-propyl; The alicyclic hydrocarbon that contains oxirane ring, as 3, the 4-epoxycyclohexyl; Or the like.These groups can be according to desired response, speed of reaction, and operability, cost or the like is selected, and has no particular limits.In these groups, consider operability, glycidyl is most preferred.
Monomeric example with epoxy group(ing) comprises: methacrylic acid with comprise ester oxirane ring, that contain organic group alcohol, as methyl propenoic acid glycidyl base ester, methacrylic acid 2,3-epoxy-2-methyl-propyl ester, and methacrylic acid (3, the 4-epoxycyclohexyl) methyl esters; Vinylformic acid with comprise ester epoxy group(ing), that contain organic group alcohol, as glycidyl acrylate, vinylformic acid 2,3-epoxy-2-methyl-propyl ester, and vinylformic acid (3, the 4-epoxycyclohexyl) methyl esters; The unsaturated compound that contains epoxy group(ing) is as 4-vinyl-1-tetrahydrobenzene 1,2-epoxide; Or the like.These groups can be according to desired response, speed of reaction, and operability, cost or the like is selected, and has no particular limits.In these monomers, consider operability, glycidyl methacrylate and glycidyl acrylate are most preferred.
(hydrolyzable silyl)
As hydrolyzable silyl, can represent by general formula (1):
-[Si(R 1) 2-b(Y) bO] m-Si(R 2) 3-a(Y) a (1)
Wherein, R 1And R 2The alkyl of representing the 1-20 carbon atom separately, the aryl of 6-20 carbon atom, the aralkyl of 7-20 carbon atom, or by (R ') 3Three organic siloxane groups that SiO-represents, R ' is the monovalence alkyl with 1-20 carbon atom in the formula, and three R ' can be identical or different; When there being two or more R 1Or R 2The time, they can be identical or different; Y represents hydroxyl or hydrolysable group, and when having two or more Y, they can be identical or different; A represents 0,1,2, or 3; B represents 0,1, or 2; M represents the integer of 0-19; And a+m * b 〉=1.
The example of hydrolysable group comprises: group commonly used, and as hydrogen atom, alkoxyl group, acyloxy, ketoxime base (ketoximate group), amino, amide group, aminooxy, thiohydroxy, and alkenyloxy.In these groups, consider gentle hydrolyzable and workability, preferably, and alkoxyl group, amide group, and aminooxy particularly preferably are alkoxyl group.
Hydrolysable group and hydroxyl can 1-3 range key be bonded on the siloxanes atom, and (a+ ∑ b) is preferably in the scope of 1-5.Under the situation of bonding in reactive silyl, they can be identical or different at two or more hydrolysable group and hydroxyl.The quantity that forms the siloxanes atom of reactive silyl is one or more.Under the situation that the siloxanes atom connects by siloxane bond, described quantity is preferably 20 or still less.Particularly, because reactive silyl obtains easily, therefore the reactive silyl by general formula (2) expression is preferred.
-Si(R 2) 3-a(Y) a (2)
In the formula, R 2, Y and a are same as described above.
The example of hydrolysable silyl group comprises: trialkoxysilyl, and as trimethoxysilyl, triethoxysilyl, tripropoxy-sil(ic)ane base, three isopropoxy silyls and three butoxy silyls; Dialkoxy alkyl silyl, as the dimethoxy-methyl silyl, the diethoxymethyl silyl, dipropoxy methyl-silicane base, dibutoxy methyl-silicane base, dimethoxy-ethyl silyl, diethoxy ethyl silicane base, dipropoxy ethyl silicane base and dibutoxy ethyl silicane base; Alkoxyl group dialkyl group silyl, as the methoxyl group dimetylsilyl, the oxyethyl group dimetylsilyl, the propoxy-dimetylsilyl, the butoxy dimetylsilyl, methoxyl group diethylsilane base, oxyethyl group diethylsilane base, propoxy-diethylsilane base and butoxy diethylsilane base; Or the like.
These groups can be according to desired response, speed of reaction, and operability, cost or the like is selected, and has no particular limits.To illustrate reactive design that coupling is wished below.Requiring under the situation of high reaction rate, the alkoxyl group that is bonded on the siloxanes atom is preferably methoxy or ethoxy, more preferably methoxyl group.Under the situation that requires low reaction speed, the alkoxyl group that is bonded on the siloxanes atom preferably has two or more carbon atoms, more preferably has three or more carbon atoms.In addition, the quantity of alkoxyl group also has no particular limits on the silyl for being bonded to.Emphasizing high reaction rate, connective stability, or under the situation of cross-linking density, be suitable for selecting trialkoxysilyl; Under the situation that requires low reaction speed or not too big cross-linking density, be suitable for selecting dialkoxy alkyl silyl; And except that chain lengthening, do not take place under the crosslinked situation in hope, be suitable for selecting alkoxyl group dialkyl group silyl.
Monomeric example with hydrolysable silyl group comprises: methacrylic acid and ester with alcohol of hydrolysable silyl group, and siliceous unsaturated compound, or the like.
Methacrylic acid comprises γ-(methacryloxypropyl) Trimethoxy silane with the example of the ester of the alcohol with hydrolysable silyl group, γ-(methacryloxypropyl) triethoxyl silane, γ-(methacryloxypropyl) tripropoxy silane, γ-(methacryloxypropyl) three isopropoxy silane, γ-(methacryloxypropyl) three butoxy silanes, γ-(methacryloxypropyl) dimethoxy-methyl silane, γ-(methacryloxypropyl) diethoxymethyl silane, γ-(methacryloxypropyl) dipropoxy methyl-monosilane, γ-(methacryloxypropyl) diisopropoxy methyl-monosilane, γ-(methacryloxypropyl) dibutoxy methyl-monosilane, or the like.Kind to the alkyl that connects methacryloxy and silyl has no particular limits, but considers operability, and what enumerate at this is propyl group.
The example that contains the unsaturated compound of siloxanes comprises: vinyltrimethoxy silane, vinyltriethoxysilane, vinyl tripropoxy silane, vinyl silane triisopropoxide, vinyl three butoxy silanes, vinyl-dimethyl oxygen ylmethyl silane, vinyl diethoxymethyl silane, vinyl dipropoxy methyl-monosilane, vinyl diisopropoxy methyl-monosilane, vinyl dibutoxy methyl-monosilane, vinyl-dimethyl oxygen base ethylsilane, vinyl diethoxy ethylsilane, vinyl dipropoxy ethylsilane, vinyl diisopropoxy ethylsilane, vinyl dibutoxy ethylsilane, vinyl methoxyl group dimethylsilane, vinyl oxyethyl group dimethylsilane, vinyl propoxy-dimethylsilane, vinyl isopropoxy dimethylsilane, vinyl butoxy dimethylsilane, or the like.
(amino)
To amino without limits, and can be amino by general formula (3) expression:
-NR 3 2 (3)
Wherein, R 3Be hydrogen or organic group with 1-20 carbon atom, and two R 3Each other can be identical or different, and to be connected to form ring texture at the other end each other; Or by the ammonium salt of general formula (4) expression:
(4)：
-(NR 3 3) +z -(4)
Wherein, R 3Same as described above, and three R 3Each other can be identical or different, and can be interconnected to form ring texture at the other end, and Z-is a counter anion.
In above-mentioned formula, R3 is hydrogen or the organic group with 1-20 carbon atom, and can be hydrogen, has the alkyl of 1-20 carbon atom, has the aryl of 6-20 carbon atom, has the aralkyl of 7-20 carbon atom, or the like.
Having amino monomeric example comprises: methacrylic acid 2-amino ethyl ester, and vinylformic acid 2-amino ethyl ester, or the like.
(thiazolinyl)
Except representing, thiazolinyl is had no particular limits by general formula (5):
H2C＝C(R 4)- (5)
Wherein, R 4For hydrogen atom or have the alkyl of 1-20 carbon atom, be preferably hydrogen atom.
Example with alkyl of 1-20 carbon atom particularly comprises as follows:
-(CH 2) n-CH 3
-CH(CH 3)-(CH 2) n-CH 3
-CH(CH 2CH 3)-(CH 2) n-CH 3，-CH(CH 2CH 3) 2
-C(CH 3) 2-(CH 2) n-CH 3
-C(CH 3)(CH 2CH 3)-(CH 2) n-CH 3
-C 6H 5，-C 6H 4(CH 3)
-C 6H 3(CH 3) 2，-(CH 2) n-C 6H 5，-(CH 2) n-C 6H 4(CH 3)
-(CH 2) n-C 6H 3(CH 3) 2
N is 0 or bigger integer.The sum of carbon atom is not more than 20 in each group.
The mode of connection of thiazolinyl and main polymer chain has no particular limits, but preferably, and they are by C-C, ester bond, ehter bond, carbonic acid ester bond, amido linkage, the carbamate key, or the like connect.
As the monomer with thiazolinyl, what can mention for example is allyl methacrylate(AMA) or the like.
(reactive chlorine group)
The reactive chlorine group is had no particular limits and is represented by general formula (6):
ClCR 5R 6-CR 7CR 8-W-(6)
Wherein, R 5, R 6, R 7, and R 8Be respectively hydrogen atom or have the alkyl of 1-20 carbon atom, be preferably hydrogen atom, and W is a divalent linker.
In above-mentioned formula (6), R 5, R 6, R 7, and R 8Example comprise organic group with 1-20 carbon atom, as have the alkyl of 1-20 carbon atom, have the aryl of 6-20 carbon atom and have the aralkyl of 7-20 carbon atom.
W is a divalent linker.As divalent linker, that can mention has a Sauerstoffatom, sulphur atom, or the like.In these groups, Sauerstoffatom is most preferred.Particularly, because the reactive chlorine group obtains easily, therefore be preferred, and represent this reactive chlorine group by general formula (7):
ClCH 2-CH 2-O- (7)
As the monomer with reactive chlorine group, what can mention for example is 2-chloroethyl vinyl ether.
( azoles quinoline group)
 azoles quinoline group and epoxy group(ing), amino, carboxyl, therefore acid anhydrides or the like reaction can react with the polymkeric substance that comprises above-mentioned polar group.The resin that reacts is had no particular limits, as long as it is the polymkeric substance that comprises above-mentioned polar group, but preferably: polyester-Ji resin, polymeric amide-Ji resin, polycarbonate-Ji resin or the like.
To  azoles quinoline group without any restriction, but preferably by the group of general formula (8) expression:
Figure A20071008779100251
In formula (8), R 1, R 2, R 3, and R 4Be hydrogen atom independently of one another, halogen atom has the alkyl of 1-20 carbon atom, has the aralkyl of 7-20 carbon atom, and cycloalkyl has the aryl of 6-20 carbon atom and the aryl that replaces.
Monomeric example with  azoles quinoline group comprises: 2-vinyl-2- azoles quinoline, 2-vinyl-4-methyl-2- azoles quinoline, 2-vinyl-5-methyl-2- azoles quinoline, 2-pseudoallyl-2- azoles quinoline, 2-pseudoallyl-4-methyl-2- azoles quinoline, 2-pseudoallyl-5-methyl-2- azoles quinoline, 2-pseudoallyl-5-ethyl-2- azoles quinoline, or the like.
(hydroxyl)
Without any restriction, but alcoholic extract hydroxyl group is preferred for hydroxyl.
Monomeric example with hydroxyl comprises: 2-hydroxyethyl methacrylate, and methacrylic acid 2-hydroxy propyl ester, the ethylene oxide adduct of methacrylic acid, vinylformic acid 2-hydroxy methacrylate, vinylformic acid 2-hydroxy propyl ester, acrylic acid ethylene oxide adduct, or the like.
(anhydride group)
Without any restriction, but carboxylic acid anhydride is preferred for anhydride group.In these acid anhydrides, any position in the polymkeric substance is fundamental point, and the acid anhydrides that can mention has: 1, and 2-dicarboxylic anhydride (5-unit ring), 1,3-dicarboxylic anhydride (6-unit ring), 1,4-dicarboxylic anhydride (7-unit ring), or the like.
Monomeric example with anhydride group comprises: maleic anhydride, and acrylic anhydride, methacrylic anhydride, or the like.
The introducing method of＜reactive functional groups (C) 〉
Under reactive functional groups (C) was included in situation in the segmented copolymer, the introducing method of reactive functional groups (C) will be described below.Described method is divided into following method roughly: by polymerization the monomer with reactive functional groups (C) is incorporated into the method on the polymer blocks and by functional end-group is transformed reactive functional groups (C) is incorporated into method on the molecule chain end.To be described each method below.
In the monomer that will have reactive functional groups (C) is incorporated into method on the polymer blocks, functional group (C) will be included in methacrylate polymer block (A) and the acrylate copolymer block (B), or be included in its any in.
By this method, introduce epoxy group(ing), hydrolysable silyl group group, hydroxyl, amino, carboxyl, reactive chlorine group and  azoles quinoline group.
In this case, the monomeric example with reactive functional groups (C) comprises: methacrylic acid or methacrylic ester, vinylformic acid or acrylate, the unsaturated compound that contains siloxanes, the unsaturated compound that contains epoxy group(ing) contains the unsaturated compound of reactive chlorine group, or the like.Object lesson is top mentioned, but to the monomer that comprises reactive functional groups (C) without any restriction.
In the method that by functional end-group is transformed reactive functional groups (C) is incorporated on the molecule chain end, reactive functional groups (C) directly or be connected to the end of molecular chain by suitable organic group.
As the synthetic method that has the segmented copolymer of hydrolysable group in the end, that can mention for example has: in the presence of hydrosilylation catalysts, the hydrosilanes compound that will have a hydrolysable silyl group is added to the method that has in the end on the segmented copolymer of thiazolinyl; Make the segmented copolymer that has hydroxyl in the end with have reactive silyl and can with the method for the compound reaction of the group of hydroxyl reaction such as the isocyanate group in a part; Or the like.
As synthesizing the method that has the segmented copolymer of thiazolinyl in the end, that can mention for example has: make segmented copolymer that has hyperergy carbon-halogen bond in the end and the oxygen anion with thiazolinyl or carboxylate anion reaction to replace the method for halogen.
As synthesizing the method that has the segmented copolymer of hydroxyl in the end, that can mention for example has: make segmented copolymer that has hyperergy carbon-halogen bond in the end and the oxygen anion with hydroxyl or carboxylate anion reaction to replace the method for halogen.The segmented copolymer that has hyperergy carbon-halogen bond referred in this in the end can obtain by the active radical polymerization that will mention subsequently.By these methods, can introduce hydrolyzable silyl, thiazolinyl, and hydroxyl.
In addition, can introduce monomeric ester moiety in the polymer blocks by polymerization and stand functional group's conversion reaction and introduce carboxyl and anhydride group by making.
Synthetic method as segmented copolymer with carboxyl, such method is for example arranged: synthesize and contain monomeric segmented copolymer, it is the functional group of carbonyl precursor that described monomer has, it for example is the methacrylic acid tertiary butyl ester, the vinylformic acid tertiary butyl ester, methacrylic acid trimethyl silyl ester, or vinylformic acid trimethyl silyl ester; Form carboxylic acid by known chemical reactions such as hydrolysis or acidolysis then, for example be described in JP-A-10-298248, JP-A 2001-234146, or the like in any method.
As the synthetic method of segmented copolymer with anhydride group, the above-mentioned segmented copolymer with carboxyl is heated, to dewater or dealcoholysis (dealcoholation), can make the ester moiety of adjacent monomer change into carboxylic acid anhydride thus.
In addition, also can contain monomeric segmented copolymer by synthesizing, heating then to carry out dealcoholysis makes the ester moiety of adjacent monomer change into carboxylic acid anhydride, described monomer has the functional group for carboxyl precursor, monomer for example is the methacrylic acid tertiary butyl ester, the vinylformic acid tertiary butyl ester, methacrylic acid trimethyl silyl ester, or vinylformic acid trimethyl silyl ester.
In addition; when producing segmented copolymer by the active radical polymerization that will mention subsequently; except that polymerization starter as initiator, have the Organohalogen compounds or the halogenation sulfonyl compound of functional group by utilization, can be easily with thiazolinyl; hydroxyl; epoxy group(ing), amino, amide group; hydrolysable silyl group, or the like cause on the polymkeric substance.
In addition, by the segmented copolymer with hyperergy carbon-halogen bond is heat-treated so that carry out dehydrohalogenation reaction, can be endways or the inner alkene that forms, described key is to obtain by the active radical polymerization that will mention subsequently.
The preparation method of＜segmented copolymer (b) 〉
Preparation method to above-mentioned segmented copolymer has no particular limits, but the preferred controlled fusion that utilizes polymerization initiator that uses.The example of controlled fusion comprises: active anionic polymerization, utilize the radical polymerization of chain-transfer agent and the active radical polymerization of exploitation recently.In these polymerization processs, consider control to block copolymer amount and structure, active radical polymerization is preferred.
Active radical polymerization refers to such radical polymerization, and it still keeps active when polymerization finishes.Narrow sense ground, living polymerization refers to end and always keeps active polymerization, yet also comprises false living polymerization usually, and it has the end of activation or inactivate when equilibrium state.Definition at this also is the latter.Recently, different groups are studied active radical polymerization just energetically.
Its example comprises: utilize the polymerization of chain-transfer agent such as polysulfide; Utilize the polymerization of radical-trapping agent such as cobalt metalloporphyrin complex (J.Am.Chem.Soc., Vol.116,7943 (1994)) or nitroxide compound (Macromolecules, Vol.27,7228 (1994)); Atom transfer radical polymerization (ATRP), it utilizes Organohalogen compounds or the like as initiator, and transition metal complex is as catalyzer.For utilizing these methods without any special restriction, but consider easy control, atom transfer radical polymerization is preferred.
In atom transfer radical polymerization; by Organohalogen compounds or halogenated sulfonyl compound as initiator; with as catalyzer, its central metal for being selected from the periodic table of elements the 8th; the 9th; the metal complexes of the element of the tenth or the tenth gang and initiated polymerization (for example, people such as Matyjaszewski, J.Am.Chem.Soc.; Vol.117; 5614 (1995), Macromolecules Vol.28,7901 (1995); Science; Vol.272,866 (1995), or people such as Sawamoto; Macromolecules Vol.28,1721 (1995)).
According to these polymerization processs, although with very high rate of polymerization carry out polymerization and be wherein termination reaction as the incident radical polymerization of the coupling between radical, but it is to carry out so that polymkeric substance to be provided in active mode, therefore, polymkeric substance has narrow molecular weight distribution (Mw/Mn=1.1-1.5), and, can at random control molecular weight by changing the charge ratio of monomer and initiator.
In atom transfer radical polymerization method, the Organohalogen compounds or the halogenated sulfonyl compound that use as initiator comprise: simple function, two senses or polyfunctional compound.These can be selected according to purposes.Under the situation of producing Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, consider the operability of initiator, monofunctional compound is preferred.Under the situation of producing A-B-A type triblock copolymer or B-A-B type triblock copolymer, consider reactions steps quantity and save time that difunctional's compound is preferred.Under the situation of production branched block copolymer, consider reactions steps quantity and save time, the polyfunctional compound is preferred.
In addition, also can use aforesaid polymerization initiator.In Organohalogen compounds and halogenated sulfonyl compound, polymerization initiator refers to: comprise the compound of polymkeric substance, described polymkeric substance is connected with halogen atom on molecule chain end.Because above-mentioned polymerization initiator can the controlled fusion method by except that active radical polymerization prepare, and therefore, have such feature, can obtain by different polymerization processs acquisitions, be the segmented copolymer of polymeric blends.
The example of monofunctional compound comprises the compound of following expression:
C 6H 5-CH 2X，
C 6H 5-C(H)(X)-CH 3，
C 6H 5-C(X)(CH 3) 2，
R 1-C(H)(X)-COOR 2，
R 1-C(CH 3)(X)-COOR 2，
R 1-C(H)(X)-CO-R 2，
R 1-C(CH 3)(X)-CO-R 2，
R 1-C 6H 5-SO 2X, or the like.
In described formula, C 6H 5The expression phenyl, C 6H 4Expression phenylene (any of ortho position-replacement, position-replacement and contraposition-replacement); R 1The expression hydrogen atom has the alkyl of 1 to 20 carbon atom, has the aryl of 6 to 20 carbon atoms, or has the aralkyl of 7 to 20 carbon atoms; X represents chlorine, bromine, or iodine; And R 2Expression has any monovalent organic radical of 1 to 20 carbon atom.
For R 1, the object lesson that comprise alicyclic hydrocarbon group, has an alkyl of 1 to 20 carbon atom comprises: methyl, and ethyl, propyl group, sec.-propyl, just-and butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, the 2-ethylhexyl, nonyl, decyl, dodecyl, isobornyl, or the like.Object lesson with aromatic yl group of 6 to 20 carbon atoms comprises phenyl, tolyl, and naphthyl, or the like.Object lesson with aralkyl of 7 to 20 carbon atoms comprises phenmethyl, styroyl, or the like.
The object lesson of monofunctional compound comprises the tolylsulfonyl bromine, the 2 bromopropionic acid methyl esters, and the 2 bromopropionic acid ethyl ester, the 2 bromopropionic acid butyl ester, 2-isobutyl bromide methyl esters, the 2-isobutyl ethyl bromide, 2-isobutyl bromide butyl ester, or the like.In these materials, because they and acrylate monomer are structurally similar, therefore, consider that polymeric controls easily, 2 bromopropionic acid ethyl ester and 2 bromopropionic acid butyl ester are preferred.
The example of difunctional's compound comprises the compound of following expression:
X-CH 2-C 6H 4-CH 2-X，
X-CH(CH 3)-C 6H 4-CH(CH 3)-X，
X-C(CH 3) 2-C 6H 4-C(CH 3) 2-X，
X-CH(COOR 3)-(CH 2) n-CH(COOR 3)-X，
X-C(CH 3)(COOR 3)-(CH 2) n-C(CH 3)(COOR 3)-X，
X-CH(COR 3)-(CH 2) n-CH(COR 3)-X，
X-C(CH 3)(COR 3)-(CH 2) n-C(CH 3)(COR 3)-X，
X-CH 2-CO-CH 2-X，
X-CH(CH 3)-CO-CH(CH 3)-X，
X-C(CH 3) 2-CO-C(CH 3) 2-X，
X-CH(C 6H 5)-CO-CH(C 6H 5)-X，
X-CH 2-COO-(CH 2) n-OCO-CH 2-X，
X-CH(CH 3)-COO-(CH 2) n-OCO-CH(CH 3)-X，
X-C(CH 3) 2-COO-(CH 2) n-OCO-C(CH 3) 2-X，
X-CH 2-CO-CO-CH 2-X，
X-CH(CH 3)-CO-CO-CH(CH 3)-X，
X-C(CH 3) 2-CO-CO-C(CH 3) 2-X，
X-CH 2-COO-C 6H 4-OCO-CH 2-X，
X-CH(CH 3)-COO-C 6H 4-OCO-CH(CH 3)-x，
X-C(CH 3) 2-COO-C 6H 4-OCO-C(CH 3) 2-x，
X-SO 2-C 6H 4-SO 2-X, or the like.
In described formula, R 3The alkyl of expression 1 to 20 carbon atom has the aryl of 6 to 20 atoms, or has the aralkyl of 7 to 20 carbon atoms, and n represents the integer of 0-20; And C 6H 5, C 6H 4Same as described above with X.
Be used for R 3The alkyl with 1 to 20 carbon atom, have the aryl of 6 to 20 carbon atoms, or have 7 to 20 carbon atoms aralkyl object lesson be used for R 1The alkyl with 1 to 20 carbon atom have the aryl of 6 to 20 carbon atoms, or it is identical to have an object lesson of aralkyl of 7 to 20 carbon atoms, therefore omits its explanation at this.
The object lesson of difunctional's compound comprises: two (brooethyl) benzene, two (1-bromotrifluoromethane) benzene, two (1-bromine sec.-propyl) benzene, 2,3-dibromo-succinic acid dimethyl ester, 2,3-dibromo-succinic acid diethyl ester, 2,3-dibromo-succinic acid dibutylester, 2,4-dibromo Methyl glutarate, 2,4-dibromo ethyl glutarate, 2,4-dibromo pentanedioic acid dibutylester, 2,5-dibromo dimethyl adipate, 2,5-dibromo diethylene adipate, 2,5-dibromo Polycizer W 260,2,6-dibromo NSC 52563,2,6-dibromo pimelic acid diethyl ester, 2,6-dibromo pimelic acid dibutylester, 2,7-dibromo suberic acid dimethyl ester, 2,7-dibromo suberic acid diethyl ester, 2,7-dibromo suberic acid dibutylester, or the like.In these materials, consider the operability of raw material, two (brooethyl) benzene, 2,5-dibromo diethylene adipate and 2,6-dibromo pimelic acid diethyl ester is preferred.
Polyfunctional compound's example comprises the compound of following expression:
C 6H 3-(CH 2-X) 3，
C 6H 3-(CH(CH 3)-X) 3，
C 6H 3-(C(CH 3) 2-X) 3，
C 6H 3-(OCO-CH 2-X) 3，
C 6H 3-(OCO-CH(CH 3)-X) 3，
C 6H 3-(OCO-C(CH 3) 2-X) 3，
C 6H 3-(SO 2-X) 3, or the like.
In described formula, C 6H 3Expression wherein three connection positions can be the phenenyl of 1-position to 6-position arbitrary combination, and X is same as described above.
Polyfunctional compound's object lesson comprises: three (brooethyl) benzene, and three (1-bromotrifluoromethane) benzene, three (1-bromine sec.-propyl) benzene, or the like.In these materials, consider the operability of raw material, three (brooethyl) benzene is preferred.
In addition; such polymkeric substance can also be provided; have the Organohalogen compounds or the halogenated sulfonyl compound of the functional group except that the group of initiated polymerization by utilization, easily introduced functional group except that the group of initiated polymerization to this polymkeric substance endways or in molecule.The example of the described functional group except that the group of initiated polymerization comprises: thiazolinyl, and hydroxyl, epoxy group(ing), amino, amide group, silyl, or the like.
In the halogenated organic compound or halogenated sulfonyl compound that can use as above-mentioned initiator, the carbon atom that connects halogen group is connected to carbonyl, phenyl, or the like on, therefore, activated carbon-halogen bond, thus initiated polymerization.According to the molecular weight of required segmented copolymer,, can determine its consumption according to initiator and monomeric ratio.That is to say that the molecular weight of segmented copolymer can be controlled according to every mole of used monomeric mole number of initiator.
Have no particular limits for transition-metal catalyst, but preferably include: the title complex of monovalence or zerovalent copper, ruthenious title complex and ferrous title complex, and the title complex of nickelous as above-mentioned atom transfer radical polymerization catalyzer.
In these materials, consider cost and the control to reacting, the title complex of copper is preferred.The example of monovalence copper compound comprises cupric chloride (I), cupric bromide (I), and cupric iodide (I), cupric cyanide (I), cupric oxide (I), cupric perchlorate (I), or the like.In these materials, consider that cupric chloride (I) and cupric bromide (I) are preferred to polymeric control.When using the monovalence copper compound,, can add based on 2 as the ligand that is used to improve catalytic activity, 2 '-Bipyridine compound, as 2,2 '-dipyridyl and derivative thereof, for example 4,4 '-dinonyl (dinolyl)-2,2 '-dipyridyl, 4,4 '-two (5-nonyls)-2,2 '-dipyridyl, or the like; Based on 1, the 10-phenanthroline compounds, as 1,10-phenanthroline and derivative thereof, for example, and 4,7-dinonyl-1,10-phenanthroline or the like; And polyamines, as tetramethyl-ethylidene triamine (TMEDA), five methyl diethylentriamine, or hexamethyl (2-amino-ethyl) amine.
In addition, as catalyzer, divalence ruthenium chloride (RuCl 2(PPh 3) 3) three (triphenylphosphine) title complex also be preferred.When ruthenium compound was used as catalyzer, aluminum alkoxide can be used as activator and adds.Ferrous two (triphenylphosphine) title complex (FeCl 2(PPh 3) 2), two (triphenylphosphine) title complex (NiCl of nickelous 2(PPh 3) 2) and two (tributylphosphine) title complex (NiBr of nickelous 2(PBu 3) 2) also be preferred as catalyzer.
For used catalyzer, ligand and activator have no particular limits, but can be according to initiator, and the relation between monomer and solvent and the required speed of reaction is carried out suitable determining.For example; in the polymerization of Acrylic Acid Monomer such as acrylate; owing to consider polymeric controlled; the growing end of polymer chain preferably has carbon-bromine key, it is therefore preferable that used initiator is organic bromide or alkylsulfonyl bromine; and solvent is an acetonitrile; and preferably, ligand such as five methyl diethylentriamine use with copper bearing metal-complexing catalyzer, described copper as central metal be included in cupric bromide, preferably in the cupric bromide (I).In addition, in the polymerization of methacrylic acid monomer such as methacrylic ester, owing to consider polymeric controlled, the growing end of polymer chain preferably has carbon-chlorine key, therefore preferably, used initiator is organic chloride or SULPHURYL CHLORIDE, and solvent is an acetonitrile, perhaps be mixed solvent as required with toluene etc., and preferably, ligand such as five methyl diethylentriamine use with copper bearing metal-complexing catalyzer, described copper as central metal be included in cupric chloride, preferably in the cupric chloride (I).
Catalyzer and ligand consumption can be according to initiators, and the relation between the consumption of monomer and solvent and the required speed of reaction is carried out suitable determining.For example, have under the situation of high-molecular weight polymer in acquisition, initiator/monomeric ratio should be lower than acquisition and have the situation of low-molecular weight polymer, and in this case, speed of reaction can be increased by the consumption that increases catalyzer and ligand.In addition, have under the situation of polymkeric substance that glass transition temperature is higher than room temperature in formation, when the interpolation appropriate organic solvent also increases stirring efficiency thus to reduce system viscosity, speed of reaction tends to descend, but in this case, speed of reaction can increase by the consumption that increases catalyzer and ligand.
Above-mentioned atom transfer radical polymerization can be without any solvent (mass polymerization) or carry out in different solvents.In addition, in mass polymerization or the polymerization in different solvents, polymerization can Halfway Stopping.
As above-mentioned solvent, for example, can use hydrocarbon flux, ether solvents, halogenated hydrocarbon solvent, ketone solvent, alcoholic solvent, the nitrile solvent, ester solvent, carbonate solvent, or the like.
Hydrocarbon flux comprises benzene, toluene, or the like.Ether solvents comprises diethyl ether, tetrahydrofuran (THF), or the like.Halogenated hydrocarbon solvent comprises methylene dichloride, trichloromethane, or the like.Ketone solvent comprises acetone, methyl ethyl ketone, and methyl iso-butyl ketone (MIBK), or the like.Alcoholic solvent comprises methyl alcohol, ethanol, and propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, or the like.The nitrile solvent comprises acetonitrile, propionitrile, and benzonitrile, or the like.Ester solvent comprises ethyl acetate, N-BUTYL ACETATE, or the like.Carbonate solvent comprises ethylene carbonate, Texacar PC or the like.
These resins can use separately or use with two or more mixture.
Utilizing under the situation of solvent, its consumption can suitably be determined according to the viscosity of whole system and the relation between the required stirring efficiency (being speed of reaction).In addition, stop under the polymeric situation in mass polymerization or the polymeric process in different solvents, monomer conversion can carry out suitably determining according to the viscosity and the required stirring efficiency (speed of reaction) of whole system when reaction stops.
Above-mentioned polymerization can be carried out in preferred 50-150 ℃ the temperature range in room temperature to 200 ℃.
In order to produce segmented copolymer, such certain methods is arranged: sequentially add monomer methods by above-mentioned polymerization; Next block and previous synthetic are carried out the polymeric method as the polymkeric substance of polymerization initiator; Make the method for independent polymeric polymkeric substance combination by reaction, or the like.Can use any in these methods according to purpose.Consider the facility of production process, it is preferred that order is added monomer methods, and under the situation of the monomer copolymerizable of avoiding making next block and previous block to stay, it is preferred making next block and previous synthetic carry out the polymeric method as the polymkeric substance of polymerization initiator.
Below monomeric situation is added in explanation in detail in proper order and make next block and the situation of previous synthetic as the polymer polymerizing of polymerization initiator, but these explanations and do not mean that qualification to segmented copolymer production method of the present invention.
Add under the monomeric situation in order, when wishing that its polymerisation conversion of monomer that formerly adds reaches 80-95%, add the next one and treat polymerization single polymerization monomer.When polymerization proceeds to transformation efficiency always and surpasses 95%, when for example reaching 96-100%, will the inhibition at random of polymer chain growth response appear.In addition,, therefore tend to take place side reaction because polymer radical is easy to react each other, as disproportionation, coupling, and chain transfer.When being lower than 80% at transformation efficiency, for example 79% or add when lower when treating the next monomer of polymeric, always will occur sometimes, the monomer that promptly is used for first pre-polymerization and is added may be treated polymeric monomer generation copolymerization with the next one.
In this case, following method is arranged in proper order: (x1) at first add Acrylic Acid Monomer and polymerization, add methacrylic acid monomer and polymerization then as interpolation; (y1) at first add methacrylic acid monomer and polymerization, add Acrylic Acid Monomer and polymerization then.Consider that preferred method (x1) promptly at first adds Acrylic Acid Monomer and polymerization, adds methacrylic acid monomer and polymerization then to polymeric control.This is because preferably the end from the acrylate copolymer block increases the methacrylate polymer block.
As making next block and the method for previous synthetic as the polymer polymerizing of polymerization initiator, that can mention for example has such method: in case in active condition, the desired time point reduces to stop polymerization temperature in the first block polymerization process, and under reduced pressure remove after the monomer of first block, add the monomer that is used for second block.Make the 3rd and the situation of block polymerization of order under, the available mode identical with second block carried out polymerization.In the method, second and the polymerization process of block of order in, can avoid the previous monomeric copolymerization that stays.
In this case, the order as block polymerization has following method: (x2) at first make the vinylformic acid block polymerization, make the methacrylic acid block polymerization then; (y2) at first make the methacrylic acid block polymerization, make the vinylformic acid block polymerization then.Consider that preferred method (x2) promptly at first makes the vinylformic acid block polymerization, makes the methacrylic acid block polymerization then to polymeric control.This is because preferably the end from the acrylate copolymer block increases the methacrylate polymer block.
Acrylic Acid Monomer, the method for methacrylic acid monomer or the like transformation efficiency measured will be described below.In order to determine transformation efficiency, can use gas-chromatography (GC) method, weighting method or the like.The GC method is a kind of like this method: the reaction solution to polymerization system is sampled in reaction process at first before beginning to react and as required, serves as that monomeric consumption is determined on the basis with monomer and the ratio that before had been added into internal standard material in the polymerization system then.The advantage of this method is: even when in system, existing multiple monomer, also may determine independent transformation efficiency independently.Weighting method is a kind of like this method: the reaction solution to polymerization system is sampled, and with before dry and dried weight serve as the concentration that solid matter is determined on the basis, thereby determine whole monomeric transformation efficiency.The advantage of this method is to determine transformation efficiency easily.In these methods, when existing multiple monomer in the system, when for example comprising Acrylic Acid Monomer as the copolymerization component of methacrylic acid monomer, the GC method is preferred.
The mixing of＜thermoplastic resin (a) and segmented copolymer (b) 〉
The combined amount of thermoplastic resin (a) and segmented copolymer (b) has no particular limits, but, be to improve under the situation of shock-resistance in main purpose, the component ratio ranges is preferably the thermoplastic resin (a) of 99.5-30% weight and the segmented copolymer (b) of 0.5-70% weight.More preferably, described scope is the thermoplastic resin (a) of 99.5-50% weight and the segmented copolymer (b) of 0.5-50% weight, the most preferably segmented copolymer (b) of thermoplastic resin of 99.5-70% weight (a) and 0.5-30% weight.When the combined amount of segmented copolymer (b) during less than 0.5% weight, the improvement effect of shock-resistance tends to reduce, and when combined amount during above 70% weight, often is difficult to show the feature of thermoplastic resin.
In addition, improving under the situation that processing characteristics is a main purpose, described scope is preferably the thermoplastic resin (a) of 99.9-70% weight and the segmented copolymer (b) of 0.1-30% weight.More preferably, described scope is the thermoplastic resin (a) of 99.5-50% weight and the segmented copolymer (b) of 0.5-50% weight, the most preferably segmented copolymer (b) of thermoplastic resin of 99.5-70% weight (a) and 0.5-30% weight.Be to improve under the situation of processing characteristics in purpose, the addition of segmented copolymer (b) usually is to improve the situation of shock-resistance less than purpose, so that do not make resin inherent characteristic variation.When the combined amount of segmented copolymer (b) during less than 0.1% weight, the improvement effect of processing characteristics tends to reduce, and when combined amount during above 30% weight, often is difficult to show thermoplastic resin (a) institute inherent characteristic.
In addition, obtaining its Young's modulus under the situation of the matrix material between resin and the elastomerics, described scope is preferably the thermoplastic resin (a) of 90-10% weight and the segmented copolymer (b) of 10-90% weight.More preferably, described scope is the thermoplastic resin (a) of 80-15% weight and the segmented copolymer (b) of 20-85% weight, the most preferably segmented copolymer (b) of thermoplastic resin of 30-80% weight (a) and 70-20% weight.When the combined amount of segmented copolymer (b) during less than 10% weight, often be difficult to obtain to have the composition of wishing physicals, this is because the Young's modulus and the thermoplastic resin (a) of composition are basic identical, and when combined amount surpasses 90% weight, often be difficult to show thermoplastic resin (a) institute inherent physicals.
Segmented copolymer (b) to the dispersion diameter of thermoplastic resin (a) usually according to the polar relationship between thermoplastic resin (a) and the segmented copolymer (b), thermoplastic resin (a) and the viscosity relationship of segmented copolymer (b) when processing treatment, and it is reactive, mole number, the position that reactive functional groups (C) exists is determined.
The method that reduces dispersion diameter is had no particular limits, and its example comprises: the method that increases functional group (C) consumption; The functional group that will have a hyperergy functional group (C) introduces the method in the resin (a); The method that polarity difference between resin (a) and the segmented copolymer (b) is reduced; With the method for viscosity that reduces segmented copolymer (b) when the processing temperature.On the contrary, the method that increases dispersion diameter is also had no particular limits, and its example comprises: the method that reduces functional group (C) amount; Suppress functional group (C) to the reactive method of resin (a); Increase the method for polarity difference between resin (a) and the segmented copolymer (b); The method that segmented copolymer (b) viscosity increases when making processing temperature.
＜catalysts 〉
In composition of the present invention, depend on the kind and the purposes of reactive functional groups (C), need to be used to quicken the reaction between functional group (C) and the resin (a) or the catalyzer of the crosslinking reaction between the functional group (C) sometimes.
At reactive functional groups (C) is under the situation of epoxy group(ing), catalyst for reaction has no particular limits between functional group (C) and the resin (a) to quickening, but normally being selected from, it quickens the carboxylic acid group, a kind of compound of hydroxyl and ester group and epoxy reaction or the mixture of two or more compounds.The example of above-claimed cpd comprises: based on the compound of amine, as tertiary amine and quaternary ammonium salt; Based on the compound of phosphorus, as  salt and phosphine; And imidazoles.In these compounds, consider thermostability, be particularly preferred based on the compound of phosphorus.Specifically, the compound that can mention has:  salt, as four (just-and butyl) bromination , four (just-and butyl) chlorination , three (just-and butyl) methyl iodate , three (just-butyl) benzyl chlorination  and three (just-and butyl) allyl group bromination ; Phosphine is as triphenylphosphine; Or the like.
With respect to 100 weight parts resin combination of the present invention, catalyst consumption is from the 0.001-2 weight part, preferably from the 0.005-1 weight part.When described consumption during, the acceleration effect that can not obtain to react, and, mechanical property will be descended when described consumption during greater than above-mentioned scope less than above-mentioned scope.
In addition, as being used for crosslinked solidifying agent of functional group (C) and the curing catalysts that is used for accelerated reaction, can use to be generally used for curing agent for epoxy resin and curing catalysts.Its example comprises: polyamines, and modified polyamine, acid anhydrides, polyphenol, polythiol, isocyanic ester, organic acid, tertiary amine, imidazoles, Lewis acid, bronsted acid salt, or the like.Polyamines, modified polyamine, acid anhydrides, polyphenol, polythiol, isocyanic ester and organic acid they itself take place crosslinked with epoxy reaction.Tertiary amine, imidazoles, Lewis acid, and bronsted acid salt is polymeric catalyzer between the epoxy group(ing).
At reactive functional groups (C) is under the situation of hydrolysable silyl group, the catalyzer of silanol condensation can be used as the catalyzer of accelerated reaction.The example of the catalyzer of silanol condensation comprises: stannic compound, Bivalent Tin compound, titanic acid ester, organo-aluminium compound, inner complex, lead octoate 36 is based on the compound of amine, salt based on the compound of amine and carboxylic acid or the like, the reaction product and the mixture of amine-type compound and organo-tin compound, low-molecular-weight polyamide resin, the reaction product of excessive polyamine and epoxy compounds, silane-coupling agent, or the like.In addition, also can use other known silanol-condensation catalyst, as an acidic catalyst or basic catalyst.
At reactive functional groups (C) is under the situation of hydroxyl, and the catalyzer that can mention has: known esterifying catalyst or transesterification catalyst, and for example tetravalence or Bivalent Tin compound, titanic acid ester, or the like.
＜dopant 〉
In composition of the present invention, depend on final purposes, can add various dopants, so that improve physicals.For example, by mixed fillers, can play enhancement and reduce cost.By plastic binder or unvulcanized rubber, can reduce the consistency and elasticity modulus.In addition, in order to regulate physical property balance, can mix multiple dopant.
Dopant is had no particular limits, still, for example can mixed rubber, thermoplastic elastomer, the compounded rubber particle, pigment, filler, stablizer, softening agent, lubricant, fire retardant, or the like.
Described rubber is for being selected from acrylate copolymer rubber, ethylenic polymer rubber, dienopolymer rubber, natural rubber, silicon rubber and viton at least a.
As acrylate copolymer rubber, can use by making to comprise rubber or the known acrylic rubber that acrylate obtains as the monomer polymerization of main component, and have no particular limits.As acrylic rubber, specifiable have: by the monomer be made up of ethyl propenoate and/or butyl acrylate and a small amount of one or both or multiple other monomer such as 2-chloroethyl vinyl ether, methyl vinyl ketone, vinylformic acid, vinyl cyanide, or divinyl carries out copolymerization and the acrylic rubber that obtains.
As ethylenic polymer rubber, what can enumerate is: isoprene-isobutylene rubber, ethylene-propylene rubber(EPR), ethylene-propylene-elastoprene, isobutene polymer rubber and ethylene-vinyl acetate copolymer rubber.
As dienopolymer rubber, what can enumerate is: synthetic polyisoprene, divinyl rubber, 1,2-polybutadiene rubber, styrene butadiene rubbers, chloroprene rubber, paracril, and acrylonitrile-butadiene rubber.
In these rubber, need under the situation of oil-proofness preferred acrylic rubber, chloroprene rubber, or paracril in said composition.By acrylic rubber is used as rubber, can obtain to have more excellent in resistance butyrous composition.
Rubber can be uncrosslinked or crosslinked rubber.Cross-linked rubber is the rubber of dynamic crosslinking with the thermoplastic compounds melting mixing time, or with previous crosslinked rubber before thermoplastic compounds mixes.
The example of thermoplastic elastomer comprises: be disclosed in the acrylate-methacrylic acid ester block copolymer among the JP-A-2000-154329, be disclosed in the iso-butylene-methacrylic acid ester block copolymer among the JP-A-2000-154330, be disclosed in the siloxanes-methacrylic acid segmented copolymer among the JP-A-2000-154328, styrene-butadiene-styrene block copolymer (SBS), styrene isoprene styrene block copolymer (SIS) (SIS), styrene-ethylene butylene-styrene segmented copolymer (SEBS), styrene-ethylene propylene-styrene segmented copolymer (SIPS), and vinylbenzene-iso-butylene-styrene block copolymer, olefinic thermoplastic elastomer (TPO, TPV), thermoplastic elastomer (TPVC) based on vinylchlorid, thermoplastic elastomer based on acid amides, thermoplastic elastomer based on ester, based on the thermoplastic elastomer of carbamate, or the like.
The example of compounded rubber particle comprises MBS (MBS resin), acrylic acid graft copolymer, vinylformic acid-siloxanes compounded rubber graft copolymer, graft copolymer based on iso-butylene, iso-butylene-vinylformic acid compounded rubber graft copolymer, iso-butylene-siloxanes compounded rubber graft copolymer, or the like.The MBS resin, as Kaneace B series and Kaneace M series (by Kanegafuchi Chemical Industry Co., Ltd. make), acrylic acid graft copolymer, as Kaneace FM series (by Kanegafuchi Chemical Industry Co., Ltd. makes), vinylformic acid-siloxanes compounded rubber graft copolymer, all can obtain by mechanicals as Metablen S-2001 (by Mitsubishi Rayon Co., Ltd. makes).Polyisobutene-vinylformic acid compounded rubber graft copolymer can be according to the method preparation that is disclosed among the JP-A-9-302169.
The example of pigment comprises titanium dioxide, zinc sulphide, and zinc oxide, or the like.
As filler, specifiablely be: silicon-dioxide, talcum, mica, glass fibre, granulated glass sphere, Hollow Glass Sphere, glass flake, neutral clay, carbon fiber, Kevlar, aromatic polyester fiber, vinylon fiber, carbide fibre, silicon carbide fiber, sapphire whisker, potassium titanate fiber, steel fiber, carbon black, lime carbonate, magnesium hydroxide, barium sulfate, asbestos, wollastonite, or the like.These fibers can use separately or use with two or more mixture.
Utilizing under the situation of filler, with respect to 100 weight parts resin combination of the present invention, can be suitably with preferred 1-100 weight part, more preferably the 5-50 weight part uses and without limits.When ratio surpassed above-mentioned scope, the balance of molding flowability or the like will be by variation, and when ratio is lower than above-mentioned scope, adds effect and tend to decline.
Example as the stablizer of antioxidant comprises: based on the compound of phenol with based on the compound of sulfo-ether, and as 2,4-two (n-octyl sulfo-)-6-(4-hydroxyl-3,5-two-tert.-butylbenzene amido)-1,3, the 5-triazine, [3-(3 for tetramethylolmethane four, 5-two-tert-butyl-hydroxy phenyl) propionic ester], 2,2-sulfo--diethylidene two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], octadecyl (octadesyl)-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, 2,2-sulfo-two (4-methyl-6-tert butyl phenol), 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene; Based on the compound of phosphorus, as four (2, the 4-di-tert-butyl-phenyl)-4,4 '-biphenylene phosphinate and three (2, the 4-di-tert-butyl-phenyl) phosphinate; Or the like.
In addition, as first stablizer, what can mention is, based on the compound of bulky amine, as dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxyl-2,2,6,6-tetramethyl piperidine polycondensate, it is poly-that [[6-(1,1,3, the 3-tetramethyl butyl)-imino--1,3,5-triazine-2,4-two bases] [(2,2,6,6-tetramethyl--4-piperidyl) imino-hexa-methylene [2,2,6, the 6-tetramethyl-piperidyl) imino-]], with two (1,2,2,6,6-pentamethyl--4-piperidyl) 2-(3,5-di-t-butyl-4-acrinyl) 2-n-butylmalonic acid ester.
These materials can use separately or use with two or more mixture.When using, to the consumption of stablizer without limits, with respect to 100 weight parts resin combination of the present invention, preferably 0.01-20 weight part.When described consumption during less than above-mentioned scope, stablizer-interpolation effect is insufficient, and when described consumption during greater than above-mentioned scope, mechanical property tends to descend.
The example of softening agent comprises: based on the process oil of paraffin, and based on the process oil of naphthalene, the aromatics process oil, light oil, spindle oil, machine oil, Toenol 1140, sesame oil, Viscotrol C, tsubaki oil, liquid polybutene, liquid polyisoprene, dioctyl phthalate (DOP), dibutyl phthalate, Octyl adipate, Tritolyl Phosphate, or the like.
The example of lubricant comprises polyethylene wax, Poly Propylene Wax or based on the wax of single montanate;
The example of fire retardant comprises: halogenated fire retardant, and as tetrabromo-bisphenol, 2,2-two (4-hydroxyl-3,5-dibromo phenyl) propane, hexabromobenzene, three (2, the 3-dibromopropyl) isocyanuric acid ester, 2,2-two (4-hydroxyl-oxethyl-3, the 5-dibromo phenyl) propane, decabromodiphenyl oxide, bromination polyphosphate, chlorination polyphosphate, and clorafin; Based on the fire retardant of phosphorus, as ammonium phosphate, Tritolyl Phosphate, triethyl phosphate, Trichloroethyl Phosphate, tricresyl phosphate (β-chloroethyl) ester, trichloropropyl phosphate, tricresyl phosphate base phenyl ester, di(2-ethylhexyl)phosphate tolyl diphenyl ester, acid phosphoric acid ester and containing-the nitrogen phosphorus compound; Inorganic combustion inhibitor, as red phosphorus, stannic oxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, zirconium hydroxide, barium metaborate, aluminium hydroxide, and magnesium hydroxide; Polymer flame retardant, as brominated Polystyrene, bromination is gathered-alpha-methyl styrene, brominated polycarbonate, the bromination poly epoxy resin, chlorinatedpolyethylene, chlorination gathers-alpha-methyl styrene, chlorination polycarbonate and chlorination poly epoxy resin.These materials can use separately or use with two or more mixture.
When using, to the consumption of above-mentioned fire retardant without limits, but, can suitably use preferred 1-50 weight part, more preferably the 3-30 weight part with respect to 100 weight parts resin combination of the present invention.When described consumption during less than above-mentioned scope, can not obtain to give fire-retardant effect, and when described consumption during greater than above-mentioned scope, will make that molding is mobile to be reduced and mechanical property decline.
＜thermoplastic resin composition's manufacturing 〉
As thermoplastic resin composition's of the present invention mixing and production method, known method be can use, as known devices such as Banbury mixer utilized, roller crusher or twin-screw extruder carry out mechanically mixing to composition and are shaped to the method for pellet.The pellet of moulding can be in the wide temperature range inner mold, and for molding, can use conventional plastic-injection moulding machine, blow moulding machine, and the extrusion die molding machine, plasticator, or the like.
＜detailed illustration of the present invention 〉
The physicals that to wish according to the present invention lists some designs below, but scope of the present invention is not limited thereto.
To enumerate below and can be used for segmented copolymer of the present invention.EA, BA, MEA, MMA, TSMA, DSMA, GMA, IBMA, 2EHA, CHMA, MA, MAH, HEA and HEMA refer to ethyl propenoate, butyl acrylate respectively at this, vinylformic acid 2-methoxyl group ethyl ester, methyl methacrylate, γ-(methacryloxypropyl) Trimethoxy silane, γ-(methacryloxypropyl) dimethoxy silane, glycidyl methacrylate, IBOMA, 2-EHA, cyclohexyl methacrylate, methacrylic acid, methacrylic anhydride, hydroxyethyl acrylate, and hydroxyethyl methylacrylate.In addition, A-b-B refers to the segmented copolymer of being made up of as main component as main component and the block that comprises the B component the block that comprises the A component.In addition,, (A/B) refer to, A and B are random copolymerizations.
Methacrylic anhydride comprises two polymerizable double bonds, but embodiment shows in the same polymer main chain those materials of polymeric abreast.
Example with diblock polymer of epoxy group(ing) comprises: (MMA/GMA)-and b-BA, (MMA/GMA)-b-EA, (MMA/GMA)-b-(BA/EA/MEA), (MMA/GMA)-b-2EHA, (IBMA/GMA)-BA, (IBMA/GMA)-b-EA, (IBMA/GMA)-b-(BA/EA/MEA), (IBMA/GMA)-b2EHA, or the like.
Example with diblock polymer of silyl comprises: (MMA/TSMA)-and b-BA, (MMA/TSMA)-b-EA, (MMA/TSMA)-b (BA/EA/MEA), (MMA/TSMA)-b-2EHA, (MMA/DSMA)-b-BA, (MMA/DSMA)-b-EA, (MMA/DSMA)-b-(BA/EA/MEA), (MMA/DSMA)-b2EHA, (IBMA/TSMA)-b-BA, (IBMA/TSMA)-b-EA, (IBMA/TSMA)-b (BA/EA/MEA), (IBMA/TSMA)-b-2EHA, (IBMA/DSMA)-b-BA, (IBMA/DSMA)-b-EA, (IBMA/DSMA)-b-(BA/EA/MEA), (IBMA/DSMA)-b-2EHA, or the like.
Example with triblock polymer of epoxy group(ing) comprises: (MMA/GMA)-and b-BA-b-(MMA/GMA), (MMA/GMA)-b-EA-b-(MMA/GMA), (MMA/GMA)-b-(BA/EA/MEA)-b-(MMA/GMA), (MMA/GMA)-b-2EHA-b-(MMA/GMA), (CHMA/GMA)-b-BA-b (CHMA/GMA), (CHMA/GMA)-b-EA-b-(CHMA/GMA), (CHMA/GMA)-b (BA/EA/MEA)-b-(CHMA/GMA), (CHMA/GMA)-b-2EHA-b-(CHMA/GMA), (IBMA/GMA)-b-BA-b-(IBMA/GMA), (IBMA/GMA)-b-EA-b-(IBMA/GMA), (IBMA/GMA)-b-(BA/EA/MEA)-b-(IBMA/GMA), (IBMA/GMA)-b-2EHA-b-(IBMA/GMA), or the like.
Example with triblock polymer of silyl comprises: (MMA/TSMA)-and b-BA-b-(MMA/TSMA), (MMA/TSMA)-bEA-b-(MMA/TSMA), (MMA/TSMA)-b-(BA/EA/MEA)-b-(MMA/TSMA), (MMA/TSMA)-b-2EHA-b-(MMA/TSMA), (MMA/DSMA)-b-BA-b (MMA/DSMA), (MMA/DSMA)-b-EA-b-(MMA/DSMA), (MMA/DSMA)-b-(BA/EA/MEA)-b-(MMA/DSMA), (MMA/DSMA)-b-2EHA-b-(MMA/DSMA), (CHMA/TSMA)-b-BA-b-(CHMA/TSMA), (CHMA/TSMA)-b-EA-b (CHMA/TSMA), (CHMA/TSMA)-b-(BA/EA/MEA)-b-(CHA/TSMA), (CHMA/TSMA)-b-2EHA-b-(CHMA/TSMA), (CHMA/DSMA)-b-BA-b-(CHMA/DSMA), (CHMA/DSMA)-b-EA-b-(CHMA/DSMA), (CHMA/DSMA)-b-(BA/EA/MEA)-b-(CHMA/DSMA), (CHMA/DSMA)-b-2EHA-b-(CHMA/DSMA), (IBMA/TSMA)-b-BA-b-(IBMA/TSMA), (IBMA/TSMA)-b-EA-b-(IBMA/TSMA), (IBMA/TSMA)-b-(BA/EA/MEA)-b (IBMA/TSMA), (IBMA/TSMA)-b-2EHA-b-(IBMA/TSMA), (IBMA/DSMA)-b-BA-b-(IBMA/DSMA), (IBMA/DSMA)-b-EA-b (IBMA/DSMA), (IBMA/DSMA)-b-(BA/EA/MEA)-b-(IBMA/DSMA), (IBMA/DSMA)-b-2EHA-b-(IBMA/DSMA), or the like.
Example with diblock polymer of methacrylic acid comprises: (MMA/MA)-and b-BA, (MMA/MA)-b-EA, (MMA/MA)-b-(BA/EA/MEA), (MMA/MA)-b-2EHA, (IBMA/MA)-BA, (IBMA/MA)-bEA, (IBMA/MA)-b-(BA/EA/MEA), (IBMA/MA)-b-2EHA, or the like.
Example with triblock polymer of methacrylic acid comprises: (MMA/MA)-and b-BA-b-(MMA/MA), (MMA/MA)-b-EA-b-(MMA/MA), (MMA/MA)-b-(BA/EA/MEA)-b (MMA/MA), (MMA/MA)-b-2EHA-b-(MMA/MA), (CHMA/MA)-b-BA-b-(CHMA/MA), (CHMA/MA)-b-EA-b-(CHMA/MA), (CHMA/MA)-b-(BA/EA/MEA)-b-(CHMA/MA), (CHMA/MA)-b-2EHA-b-(CHMA/MA), (IBMA/MA)-b-BA-b-(IBMA/MA), (IBMA/MA)-b-EA-b-(IBMA/MA), (IBMA/MA)-b-(BA/EA/MEA)-b-(IBMA/MA), (IBMA/MA)-b-2EHA-b-(IBMA/MA), or the like.
Example with diblock polymer of anhydride group comprises: (MMA/MAH)-and b-BA, (MMA/MAH)-b-EA, (MMA/MAH)-b-(BA/EA/MEA), (MMA/MAH)-b-2EHA, (IBMA/MAH)-BA, (IBMA/MAH)-b-EA, (IBMA/MAH)-b-(BA/EA/MEA), (IBMA/MAH)-b2EHA, or the like.
Example with triblock polymer of anhydride group comprises: (MMA/MAH)-and b-BA-b-(MMA/MAH), (MMA/MAH)-b-EA-b-(MMA/MAH), (MMA/MAH)-b-(BA/EA/MEA)-b (MMA/MAH), (MMA/MAH)-b-2EHA-b-(MMA/MAH), (CHMA/MAH)-b-BA-b-(CHMA/MAH), (CHMA/MAH)-b-EA-b-(CHMA/MAH), (CHMA/MAH)-b (BA/EA/MEA)-b-(CHMA/MAH), (CHMA/MAH)-b-2EHA-b-(CHMM/MAH), (IBMA/MAH)-b-BA-b-(IBMA/MAH), (IBMA/MAH)-b-EA-b-(IBMA/MAH), (IBMA/MAH)-b-(BA/EA/MEA)-b-(IBMA/MAH), (IBMA/MAH)-b-2EHA-b-(IBMA/MAH), or the like.
Example with diblock polymer of hydroxyl comprises: (MMA/HEMA)-and b-BA, (MMA/HEMA)-b-EA, (MMA/HEMA)-b-(BA/EA/MEA), (MMA/HEMA)-b-2EHA, (IBMA/HEMA)-BA, (IBMA/HEMA)-b-EA, (IBMA/HEMA)-b-(BA/EA/MEA), (IBMA/HEMA)-b-2EHA, MMA-b-(BA/HEA), MMA-b-(EA/HEA), MMA-b-(BA/EA/MEA/HEA), MMA-b-(2EHA/HEA), IBMA-b-(BA/HEA), IBMA-b-(EA/HEA), IBMA-b-(BA/EA/MEA/HEA), IBMA-b-(2EHA/HEA), or the like.
Example with triblock polymer of hydroxyl comprises: (MMA/HEMA)-and b-BA-b-(MMA/HEMA), (MMA/HEMA)-bEA-b-(MMA/HEMA), (MMA/HEMA)-b-(BA/EA/MEA)-b-(MMA/HEMA), (MMA/HEMA)-b-2EHA-b-(MMA/HEMA), (CHMA/HEMA)-b-BA-b (CHMA/HEMA), (IBMA/HEMA)-b-BA-b-(IBMA/HEMA), (IBMA/HEMA)-b-EA-b-(IBMA/HEMA), (IBMA/HEMA)-b-(BA/EA/MEA)-b (IBMA/HEMA), (IBMA/HEMA)-b-2EHA-b-(IBMA/HEMA), MMA-b (BA/HEA)-b-MMA, MMA-b-(EA/HEA)-b-MMA, MMA-b-(BA/EA/MEA/HEA)-b-MMA, MMA-b-(2EHA/HEA)-b-MMA, IBMA-b-(BA/HEA)-b-IBMA, IBMA-b-(EA/HEA)-b-IBMA, IBMA-b (BA/EA/MEA/HEA)-b-IBMA, IBMA-b-(2EHA/HEA)-b-IBMA, or the like.
The present invention will further specify with reference to following embodiment.
(1) purpose is to improve the situation of poly-(vinylchlorid) resin shock-resistance
With respect to poly-(vinylchlorid) resin of 100 weight parts, preferably, add the 5-15 weight part, contain the acrylic block copolymers of epoxy group(ing).The acrylic block copolymers that contains epoxy group(ing) is (MMA/GMA)-b-BA-b-(MMA/GMA) and its molecular weight preferably 50,000 to 150,000 preferably.The component of BA and MMA is preferably 80/20 to 70/30 (% weight), and with respect to whole composition, as the weight ratio of GMA, epoxy group content is preferably 0.1-5%.
(2) purpose is to improve the situation of poly-(vinylchlorid) resin treatment performance
With respect to poly-(vinylchlorid) resin of 100 weight parts, preferably, add 0.5 to 1.5 weight part, contain the acrylic block copolymers of epoxy group(ing).The acrylic block copolymers that contains epoxy group(ing) is (MMA/GMA)-b-BA-b-(MMA/GMA) and its molecular weight preferably 50,000 to 150,000 preferably.The component of BA and MMA is preferably 80/20 to 60/40 (% weight), and with respect to whole composition, as the weight ratio of GMA, epoxy group content is preferably 0.1-5%.
(3) when keeping it transparent, purpose is to improve the situation of poly-(vinylchlorid) resin shock-resistance
With respect to poly-(vinylchlorid) resin of 100 weight parts, preferably, add 5 to 40 weight parts, contain the acrylic block copolymers of epoxy group(ing).The acrylic block copolymers that contains epoxy group(ing) is (MMA/GMA)-b-BA-b-(MMA/GMA) and its molecular weight preferably 50,000 to 150,000 preferably.The component of BA and MMA is preferably 80/20 to 40/60 (% weight), and with respect to whole composition, as the weight ratio of GMA, epoxy group content is preferably 0.1-5%.
(4) purpose is to improve the situation of polycarbonate resin shock-resistance
With respect to 100 weight part polycarbonate resins, preferably, add 5 to 20 weight parts, contain the acrylic block copolymers of epoxy group(ing).The acrylic block copolymers that contains epoxy group(ing) is (MMA/GMA)-b-BA-b-(MMA/GMA) and its molecular weight preferably 50,000 to 150,000 preferably.The component of BA and MMA is preferably 80/20 to 60/40 (% weight), and with respect to whole composition, as the weight ratio of GMA, epoxy group content is preferably 0.1-10%.
(5) purpose is to improve equilibrated situation between polybutylene terephthalate resin flowability and the shock-resistance
With respect to 100 weight part polybutylene terephthalate resins, preferably, add 5 to 20 weight parts, contain the acrylic block copolymers of epoxy group(ing).The acrylic block copolymers that contains epoxy group(ing) is (MMA/GMA)-b-BA-b-(MMA/GMA) and its molecular weight preferably 50,000 to 150,000 preferably.The component of BA and MMA is preferably 80/20 to 60/40 (% weight), and with respect to whole composition, as the weight ratio of GMA, epoxy group content is preferably 0.1-10%.
(6) purpose is to improve the situation of polyethylene terephthalate resin shock-resistance
With respect to 100 weight part polyethylene terephthalate resins, preferably, add 5 to 20 weight parts, contain the acrylic block copolymers of epoxy group(ing).The acrylic block copolymers that contains epoxy group(ing) is (MMA/GMA)-b-BA-b-(MMA/GMA) and its molecular weight preferably 50,000 to 150,000 preferably.The component of BA and MMA is preferably 80/20 to 60/40 (% weight), and with respect to whole composition, as the weight ratio of GMA, epoxy group content is preferably 0.1-10%.
(7) when keeping it transparent, purpose is to improve the situation of PET-G resin (ethylene glycol terephthalate/terephthalic acid cyclohexanedimethanoester ester polymkeric substance) shock-resistance
With respect to 100 weight part PET-G resins, preferably, add 5 to 20 weight parts, contain the acrylic block copolymers of epoxy group(ing).The acrylic block copolymers that contains epoxy group(ing) is (MMA/GMA)-b-BA-b-(MMA/GMA) and its molecular weight preferably 50,000 to 150,000 preferably.The component of BA and MMA is preferably 80/20 to 60/40 (% weight), and with respect to whole composition, as the weight ratio of GMA, epoxy group content is preferably 0.1-20%.
(8) purpose is to improve the situation of polyamide resin shock-resistance
With respect to 100 weight parts of polyamide resins, preferably, add 5 to 20 weight parts, contain the acrylic block copolymers of epoxy group(ing), carboxyl or anhydride group.Comprise epoxy group(ing), the acrylic block copolymers of reactive functional groups is (MMA/GMA)-b-BA-b (MMA/GMA) preferably, (MMA/MAH)-and b-BA-b-(MMA/MAH), (MMA/MA)-b-BA-b (MMA/MA), and its molecular weight preferably 50,000 to 150,000.The component of BA and MMA is preferably 80/20 to 60/40 (% weight), and with respect to whole composition, as the weight ratio of GMA, epoxy group content is preferably 0.1-20%.Consider the content of functional group, the quantity of functional group is preferably every mole 1 or more a plurality of.
(9) purpose is to improve the situation of vibrin melt viscosity
With respect to 100 weight part vibrin, preferably, add 1 to 30 weight part, contain epoxy group(ing), carboxyl or anhydride group acrylic block copolymers as reactive functional groups.The acrylic block copolymers that comprises reactive functional groups is (MMA/GMA)-b-BA-b-(MMA/GMA) preferably, (MMA/MAH)-b-BA-b-(MMA/MAH), (MMA/MA)-b-BA-b-(MMA/MA), and its molecular weight preferably 50,000 to 150,000.Consider the content of functional group, the component of BA and MMA is preferably 90/10 to 10/90 (% weight), and the quantity of functional group is preferably every mole 2 or more a plurality of.This mixture is applicable to by the melt viscosity of improving polyethylene terephthalate the purpose of molding easily.
Embodiment
The present invention will further describe with reference to following embodiment, but the present invention also not only is confined to these embodiment.
In an embodiment, EA, BA, MEA, MMA, TSMA, DSMA, GMA, SMA, IBMA, 2EHA, HEA, TBMA and MA represent respectively: ethyl propenoate, butyl acrylate, vinylformic acid 2-methoxyl group ethyl ester, methyl methacrylate, γ-(methacryloxypropyl) Trimethoxy silane, γ-(methacryloxypropyl) dimethoxy-methyl silane, glycidyl methacrylate, methacrylic acid stearyl ester, IBOMA, 2-EHA, hydroxyethyl acrylate, tert-butyl acrylate, and methacrylic acid.
＜test method 〉
(molecular weight)
With the gpc analysis device (system: by Waters, the GPC system of manufacturing, post: the ShodexK-804 (polystyrene gel) that makes by Showa DenkoK.K.) measure the molecular weight of segmented copolymer.Utilize trichloromethane as moving phase, determine the molecular weight that calculates as polystyrene.
(per-cent of block polymer)
From insoluble part, separate soluble part with ethanol, and take out soluble part with the form of homopolymerization (acrylate).Then, utilize 15/85 (% weight) trichloromethane of ratio from insoluble part, to separate soluble part, and with homopolymerization (methacrylic ester), the form of for example homopolymerization (methyl methacrylate) is removed insoluble part with the mixing solutions of methyl alcohol.Remaining soluble part is considered to segmented copolymer, and its weight percent is determined with the form of the per-cent of block polymer.
(component)
By 1H-NMR confirms the weight percent of poly-(acrylate) and poly-(methacrylic ester) in the segmented copolymer.Under the inapplicable situation of described method, can use the method for determining per-cent based on the weight of loading monomeric weight and monomer consumption on the gas chromatograph.
The manufacturing of＜segmented copolymer 〉
Preparation embodiment 1
(synthesizing of MMA-BA-MMA type segmented copolymer)
In the reactor of 50L, add 112.56g cupric bromide (I), and with the atmosphere in the nitrogen replacement reactor.The solution that mixes 627.44g acetonitrile and 1072.8g butyl acrylate in advance and obtain is added in its inner reactor that keeps under reduced pressure, make temperature rise to 65 ℃ and stirred 30 minutes then.Thereafter, will be by dissolving 56.50g 2, the solution that 5-dibromo diethylene adipate obtains in 6973.2g butyl acrylate and 158.76g N-BUTYL ACETATE, and the 784.30g acetonitrile adds in the reactor, makes temperature rise to 85 ℃ then, and restir 30 minutes in addition.Cause the polymerization that butyl acrylate becomes first block by adding 16 milliliters of five methyl diethylentriamines.
When transformation efficiency reaches 95%, in reactor, add 14228.8g toluene, 77.68g cupric chloride (I) and 5182.5g methyl methacrylate, and cause the polymerization that methyl methacrylate becomes second block by adding 16 milliliters of five methyl diethylentriamines.When transformation efficiency reaches 56%, add 8660g toluene so that dilute reaction solution meanwhile makes reactor cooling to stop polymerization.
According to the gpc analysis to the gained segmented copolymer, number-average molecular weight Mn is 107,000, and molecular weight distribution mw/mn is 1.46.In addition, according to the composition analysis of NMR, MMA/BA is 29/71 (% weight).
By toluene being added in the block copolymer solution that obtains and polymer concentration is diluted to 14.6% weight, and to wherein add 32g right-toluenesulphonic acids.Then, by the atmosphere in the nitrogen replacement reactor, and at room temperature whole inclusion was stirred 3 hours.To reaction solution sampling and confirm this solution be colourless and transparent after, make reaction terminating.Then, give off solution, and remove solid matter by the separating disc type whizzer.
In the block copolymer solution of 50L, add 150 gram KYOWARD 500SH, then,, and at room temperature whole inclusion was stirred 3 hours by the atmosphere in the nitrogen replacement reactor.To after the reaction solution sampling and confirming that this solution is neutrality, make reaction terminating.Then, give off solution, and carry out solid-liquid and separate, to remove sorbent material.
Above-mentioned polymers soln is conducted in the horizontal-type evaporator that vapor opening is housed, and makes solvent and unreacted monomer evaporation, isolating polymer whereby.Utilize heating medium with the temperature regulation to 200 of the chuck of vaporizer and spiral ℃, and vaporizer inside is maintained at about under 0.01MPa or the lower decompression by vacuum pump.By cutting-type nodulizer under water, the resin that obtains is carried out granulation.Forcing machine has single screw rod and screw diameter is 50 millimeters, and in resin-supply rate operation of 160 ℃ and 12 kilograms/hour.The aperture of die head part is 2.4 millimeters and is double-hole, and utilizes the cutters that have four blades.Stearic amide with 0.3% weight, is added in the recirculated cooling water, and with the temperature that is provided with of 260L/ minute flow velocity and 34 ℃, the place handles with recirculated cooling water at heat exchanger outlet.From this device, obtained diameter and be about 3 millimeters spherical pellets (M-1).
Preparation embodiment 2
(MMA-co-GMA)-b-BA-b-(MMA-co-GMA) type segmented copolymer (being also referred to as the MMA-BA-MMA type segmented copolymer that contains epoxy group(ing)) synthetic
After the inside with the aggregation container of 500 milliliters of separable flasks of nitrogen replacement, weighing 1.32 gram (9.2mmol) cupric bromide (cupric bromides (I), identical hereinafter material will be used) add in the described container, and to wherein adding 20 milliliters of acetonitriles (on molecular sieve, carry out drying, carry out bubbling with nitrogen then).Under agitation after 70 ℃ of heating 5 minutes, whole equipment is cooled to room temperature and to wherein adding 0.63g (1.7mmol) initiator, 2,5-dibromo diethylene adipate, and 89.4g (100 milliliters) BA.Under agitation in 80 ℃ to mixture heating up after, by to wherein adding 0.19 milliliter of (0.9mmol) ligand, five methyl diethylentriamine (being abbreviated as triamine hereinafter) forms catalyzer in system, thus initiated polymerization.At set intervals, for example began 30 minutes, polymeric solution is taken a sample about 0.2 milliliter, and determine the transformation efficiency of BA by the gas chromatographic analysis of sample solution from polymerization.When the rate of rise of the transformation efficiency of being measured is lower than when wishing speed, as required, in system, forms catalyzer and regulate rate of polymerization by adding triamine.
Transformation efficiency at BA reaches at 88% o'clock (after 5 hours), add 69.8g (74.6mL) MMA immediately, 5.0g (4.8mL) GMA, 1.82g (18.5mmol) cupric chloride (cupric chloride (I), identical hereinafter will use), 0.19mL (0.9mmol) triamine and 82.9mL toluene (dry on molecular sieve, then and nitrogen carry out bubbling).
Immediately sample is carried out gpc analysis after adding, number-average molecular weight Mn is 55,600, and molecular weight distribution mw/mn is 1.13.
Similarly, the transformation efficiency of MMA is measured.
Transformation efficiency at BA reaches 90%, and the transformation efficiency of MMA is 37%, and the transformation efficiency of GMA is 47% o'clock (after 0.5 hour), adds 500 milliliters of toluene, and make reactor cooling in water-bath, so that termination reaction.
By activated alumina reaction soln is filtered, remove copper complex whereby.Remove from filtrate by reduction vaporization and to desolvate, and the polymkeric substance that obtains was carried out vacuum-drying 24 hours, obtained target segmented copolymer (M-2) thus at 60 ℃.
According to the gpc analysis to the gained segmented copolymer, number-average molecular weight Mn is 863,000, and molecular weight distribution mw/mn is 1.43.In addition, according to the composition analysis of NMR, BA/MMA/GMA is 72/26/2 (% weight).Block per-cent is 74% weight, does not detect homopolymerization-PMMA.
With with preparation embodiment 1 similar mode, synthesize the MMA-BA-MMA type segmented copolymer (M-2 ') that contains epoxy group(ing), its number-average molecular weight Mn is 100,800, molecular weight distribution mw/mn is 1.46, the component of BA/MMA/GMA is 73/26/1 (% weight).
Preparation embodiment 3
MMA-BA-MMA type segmented copolymer (below be abbreviated as M3AM) synthetic
In the reactor of 50L, add 123.10g cupric bromide (I), and with the atmosphere in the nitrogen replacement reactor.The solution that mixes 627.44g acetonitrile and 1072.8g butyl acrylate in advance and obtain is added in its inner reactor that keeps under reduced pressure, make temperature rise to 65 ℃ and stirred 30 minutes then.Thereafter, will be by dissolving 61.79g 2,5-dibromo diethylene adipate is in the 2160.7g butyl acrylate, 3175.3g ethyl propenoate,, 1970.0g vinylformic acid 2-methoxyl group ethyl ester, with the solution that obtains in the 158.76g N-BUTYL ACETATE, and the 784.30g acetonitrile adds in the reactor, makes temperature rise to 85 ℃ then, and restir 30 minutes in addition.
Cause butyl acrylate/ethyl propenoate/vinylformic acid 2-methoxyl group ethyl ester and become the polymerization of first block by adding 18 milliliters of five methyl diethylentriamines.
When transformation efficiency reaches 96%, in reactor, add 14948g toluene,, 84.95g cupric chloride (I), with the 5385.5g methyl methacrylate, and cause the polymerization that methyl methacrylate becomes second block by adding 18 milliliters of five methyl diethylentriamines.When transformation efficiency reaches 58%, add 8660g toluene so that dilute reaction solution meanwhile makes reactor cooling to stop polymerization.According to the gpc analysis to the gained segmented copolymer, number-average molecular weight Mn is 111,800, and molecular weight distribution mw/mn is 1.48.In addition, according to the composition analysis of NMR, MMA/BA/EA/MEA is 28/28/27/17 (% weight).By toluene being added in the block copolymer solution that obtains and polymer concentration is diluted to 14.6% weight, and to wherein add 196g right-toluenesulphonic acids.Then, by the atmosphere in the nitrogen replacement reactor, and at room temperature whole inclusion was stirred 3 hours.To reaction solution sampling and confirm this solution be colourless and transparent after, make reaction terminating.Then, give off solution, and carry out solid-liquid and separate, to remove solid.In the block copolymer solution of 50L, add 150 gram Kyowad 500SH, then,, and at room temperature whole inclusion was stirred 3 hours by the atmosphere in the nitrogen replacement reactor.To after the reaction solution sampling and confirming that this solution is neutrality, make reaction terminating.Then, give off solution, and carry out solid-liquid and separate, to remove sorbent material.
Therefore, obtained target segmented copolymer (M-3).
Preparation embodiment 4
MMA-b-'s (BA-co-HEA)-b-MMA type segmented copolymer (below be abbreviated as MHBAM) is synthetic
After the inside with the aggregation container of 5 liters of separable flasks of nitrogen replacement, take by weighing 11.6g (80.7mmol) cupric bromide and add in the described container, and to wherein adding 180 milliliters of acetonitriles (carrying out bubbling with nitrogen).Under agitation after 70 ℃ of whole heating 30 minutes, to wherein adding 5.8g (16.1mmol) initiator, 2,5-dibromo diethylene adipate and 832.5 milliliters of (5.8mol) BA and 67.5 milliliters of (0.65mol) HEA.Under agitation, in 85 ℃ to mixture heating up after, to wherein adding, 1.68 milliliters of (8.1mmol) ligands, five diethylenetriamine are with initiated polymerization.Begin at set intervals from polymerization, polymeric solution is taken a sample about 0.2 milliliter, and determine the transformation efficiency of BA and HEA by the gas chromatographic analysis of sample solution.As required, regulate rate of polymerization by adding triamine.Transformation efficiency at BA reaches 94%, and the transformation efficiency of HEA reaches at 97% o'clock, adds 558.8 milliliters of (75.2 moles) MMA, 8.0g (80.7mmol) cupric chloride, 1.68 milliliters of (8.1mmol) diethylenetriamine and 1105 milliliters of toluene (using nitrogen bubble).Transformation efficiency at MMA reaches 63%, and the transformation efficiency of BA is 97% o'clock, adds 1300 milliliters of toluene, and make reactor cooling in water-bath, so that termination reaction.
With 5L dilution with toluene reaction solution, and to wherein add 18.4g right-the toluenesulphonic acids monohydrate, at room temperature stirred then 3 hours.After removing the insoluble part that is settled out, add sorbent material Kyowad 500SH, and then at room temperature stirred 3 hours by the filtration of Kinyama funnel.Filter out sorbent material by the Kinyama funnel, thereby obtain colourless, transparent polymers soln.Solution is carried out drying desolvate and residual monomer, obtained target segmented copolymer (M-4) whereby to remove.
According to the gpc analysis to the gained segmented copolymer, number-average molecular weight Mn is 118,400, and molecular weight distribution mw/mn is 1.69.The ratio of component of the BA/HEA/MMA that measures according to the transformation efficiency of gas chromatographic analysis is 65/7/28 (% weight).
Preparation embodiment 5
(MMA-co-TBMA)-synthetic and functional group's conversion reaction of b-BA-b-(NMA-co-TBMA) type segmented copolymer
After the inside with the aggregation container of 5 liters of separable flasks of nitrogen replacement, weighing 11.6g (80.7mmol) cupric bromide adds in the described container, and to wherein adding 180 milliliters of acetonitriles (carrying out bubbling with nitrogen).Under agitation after 70 ℃ of whole heating 30 minutes, to wherein adding 5.65g (15.7mmol) initiator, 2,5-dibromo diethylene adipate and 900 milliliters of (6.28mol) BA.Under agitation, in 85 ℃ to mixture heating up after, to wherein adding, 1.64 milliliters of (7.9mmol) ligands, five methyl diethylentriamine is with initiated polymerization.Begin at set intervals from polymerization, polymeric solution is taken a sample about 0.2 milliliter, and determine the transformation efficiency of BA by the gas chromatographic analysis of sample solution.As required, regulate rate of polymerization by adding triamine.Transformation efficiency at BA reaches at 95% o'clock, adds the MMA of 234mL (1.44mol) TBMA and 154mL.Similarly, the transformation efficiency of TBMA and MMA is measured.The transformation efficiency of TBMA reach 89% and the transformation efficiency of MMA reach at 84% o'clock, add 1300 milliliters of toluene, and in water-bath, make reactor cooling, so that termination reaction.With 5L dilution with toluene reaction solution, and to wherein add 26.9g right-the toluenesulphonic acids monohydrate, at room temperature stirred then 3 hours.After removing the insoluble part that is settled out, add 12.0g sorbent material Kyowad 500SH (making), and then at room temperature stirred 3 hours by Kyowa Kagaku K.K. by the filtration of Kinyama funnel.Filter out sorbent material by the Kinyama funnel, thereby obtain colourless, transparent polymers soln.Solution is carried out drying desolvate and residual monomer, obtained target segmented copolymer (M-5) whereby to remove.
According to the gpc analysis to the gained segmented copolymer, number-average molecular weight Mn is 113,600, and molecular weight distribution mw/mn is 1.44.The ratio of component of the BA/MMA/TBMA that measures according to the transformation efficiency of gas chromatographic analysis is 72/11/17 (% weight).
The segmented copolymer (M-5) that 100 grams are obtained is dissolved in the 1.0L toluene, and to wherein adding the right-toluenesulphonic acids monohydrate of 3.0 grams.Under agitation, in 120 ℃ oil bath to whole heating 3 hours, so that make tertiary butyl ester change into carboxyl.Dilute this mixture and restrain Kyowad 500SH with methyl alcohol, stir then to wherein adding 2.0.Then, be removed, and carry out this filtrate of vacuum-drying, so that obtain the final carboxyl segmented copolymer that contains at 80 ℃ by filtration.
By IR (infrared absorption spectrum) and 13C-NMR (NMR (Nuclear Magnetic Resonance) spectrum) can confirm that tert-butyl ester position has changed into carboxyl.That is to say, in IR, by after transforming, the wide absorption spectrum that derives at about 3400 to 3000cm-1 places by carboxyl and confirming. 13Among the C-NMR, the disappearance of signal that derives when the 82ppm by the methine carbon of the tertiary butyl and methyl carbon deutero-signal during at 28ppm and being confirmed.
With with preparation embodiment 5 similar modes, synthetic (MMA-co-TBMA)-b-BA-b-(MMA-co-TBMA) segmented copolymer (M-5 '), its number-average molecular weight Mn is 122,900, molecular weight distribution mw/mn is 1.46, and the component of TBMA/MMA/BA is 8.3/21.6/70.1 (a % weight).
Preparation embodiment 6
The preparation that in hard segment, has the block polymer of anhydride group
In plastomill, mediated 20 minutes under the revolution of 240 ℃ design temperature and per minute 100 times according to (MMA-co-TBMA)-b-BA-b-(MMA-co-TBMA) segmented copolymer of preparation embodiment 5 preparation, thereby obtain final acid anhydrides type segmented copolymer (M-7).By IR (infrared absorption spectrum) and 13C-NMR (NMR (Nuclear Magnetic Resonance) spectrum) has confirmed that tert-butyl ester position changes into carboxylic acid anhydride.That is to say, in IR, by after transforming, by acid anhydrides at about 1800cm -1The absorption spectrum state that derives of place and confirming. 13Among the C-NMR, the disappearance of deutero-signal when deutero-signal and methyl carbon are at 28ppm when the 82ppm by the methine carbon of the tertiary butyl and being confirmed.
＜thermoplastic resin composition's preparation 〉
(3) embodiment 1-31 and Comparative Examples 1-15
(hardness)
Hardness (JIS A or JIS D) when measuring 23 ℃ according to JIS K6253.
(breaking tenacity and elongation at break)
Tensile elongation when measuring 23 ℃ according to JIS K6251.Described elongation is the distance at chuck, and this distance is 20 millimeters, and the elongation of extensibility when being 200 or 500 mm/min.
(oil-proofness)
Oil-proofness in the time of relevant 70 ℃ was immersed in exemplar among 70 ℃ the transformer oil B 4 hours, and according to the percentage ratio of changes in weight before and after the JIS C232 experiment with measuring.Oil-proofness in the time of relevant 150 ℃ was immersed in exemplar in 150 ℃ the IRM903 oil 70 hours, and according to the percentage ratio of changes in weight before and after the ASTM D638 experiment with measuring.
(Vicat softening point)
According to JIS K7206, the exemplar that is cut into the 2cm square is immersed in the silicone oil that remains on 50 ℃ in advance, and is utilized the weight of 1kg to measure softening temperature.Temperature rise rate is 50 ℃/hour.
(flowability)
Utilize the die head of 1mmx10mm, the load of 60kgf heats resin (1.25 gram) from 80 ℃ with 6 ℃/minute speed, and measures the temperature when beginning to flow and the temperature when finishing of flowing.
(utilizing transmission electron microscope observation)
With oxygenant such as RuO4, wait that from moulded product observing the ultrathin section that cuts of part dyes, and observes then on transmission electron microscope to utilizing slicing machine.
Embodiment 1
Will (Duranex 2002 as the polybutylene terephthalate of crystalline thermoplastic resin, by Polyplastics Co., Ltd. make) (below be also referred to as the PBT resin) and mix as the MMA-BA-MMA-type segmented copolymer (M-1) of segmented copolymer, so that total amount is 100 weight parts.Under the rotating speed that 240 ℃ design temperature per minutes 50 change, in plastomill, subtend is wherein added the mixture kneading 5 minutes that 0.3 weight part Topanol CA-SF as stablizer (being made by REPRE Topanol K.K.) and 0.3 weight part PEP-36 (being made by Asahi Denka Kogyo K.K) obtained in addition, to obtain caked sample.Under 240 ℃ design temperature, on thermocompressor, the sample that obtains is carried out mold pressing, with the thickness that obtains to be used to estimate physicals 2 millimeters moulded product.
After moulded product perforation that will obtain or being cut into independently predetermined shape, measure the physicals of gained moulded product according to aforesaid method.
Embodiment 2
Prepare and assess moulded product with the mode that is similar to embodiment 1, different is, with MMA-(EA/BA/MEA)-MMA type segmented copolymer (M-3) as the segmented copolymer among the embodiment 1.
Comparative Examples 1
Prepare and assess moulded product with the mode that is similar to embodiment 1, different is not add any segmented copolymer among the embodiment 1.Yet because this moulded product is too hard, the dumbbell body that is used for tension test can not be perforated.
Embodiment 3
Prepare and assess moulded product with the mode that is similar to embodiment 1, different is, with nylon 6 resins (UBE nylon 1013B, by Ube Industries, Ltd. manufacturing) (the following PA resin that also is called) is as crystalline thermoplastic resin, and also use in addition the AO-80 (making) as stablizer, 0.2 weight part and the TPS (by Sumitomo Chemical Co., the Ltd. manufacturing) of 0.5 weight part by AsahiDenka Kogyo K.K..
Embodiment 4
Prepare and assess moulded product with mode similar to Example 3, different is, with MMA-(EA/BA/MEA)-MMA type segmented copolymer (M-3) as the segmented copolymer among the embodiment 3.
Embodiment 5
Prepare and assess moulded product with the mode that is similar to embodiment 4, different is further to add the carbon black (carbon black 35 is made by Mitsubishi Chemical Corporation) of 0.5 weight part in embodiment 4.
Comparative Examples 2
Prepare and assess moulded product with the mode that is similar to embodiment 3, different is not add the segmented copolymer among any embodiment 1.Yet because this moulded product is too hard, the dumbbell body that is used for tension test can not be perforated.
Comparative Examples 3
Under the rotating speed of 220 ℃ design temperatures and per minute 50 commentaries on classics, in plastomill, to the elastomerics based on ester, PELPRENE P46D01 (by Toyobo Co., Ltd. makes) mediated 5 minutes, to obtain caked sample.Prepare and assess moulded product with the mode that is similar to embodiment 1, different is under 220 ℃ design temperature, on thermocompressor the sample that obtains to be carried out mold pressing.
Comparative Examples 4
Prepare and assess moulded product with the mode that is similar to Comparative Examples 3, different is to use the elastomerics DAIAMIDE E47-S1 (being made by DAICEL-Huels Ltd.) based on acid amides.
Comparative Examples 5
Under the rotating speed of 210 ℃ design temperatures and per minute 50 commentaries on classics, in plastomill, to the elastomerics based on carbamate, Elastollan PC9OA1O (being made by BASF Polyurethane) mediated 5 minutes, to obtain caked sample.Prepare and assess moulded product with the mode that is similar to embodiment 1, different is under 210 ℃ design temperature, on thermocompressor the sample that obtains to be carried out mold pressing.
Assessment result is shown in Table 1.
Table 1
Mixing element, amount Dimension block-regulations (Vicat) Oil-proofness Hardness Tensile property
1kg 70℃4hr 150℃72hr JISD Breaking tenacity Elongation at break
Resin Part Block polymer Part 1mm/2mm Swelling capacity Shape Immediately 15 seconds Mpa ％
Embodiment 1 PBT 33 MBAM 67 Trans fixing 5.2％ 34.2％ Dissolving 23 15 4.5 151
PBT 40 MBAM 60 Trans fixing 4.7％ -18.1％ Be partly dissolved 35 21 5.0 76
PBT 50 MBAM 50 102 3.0％ -1.6％ Be partly dissolved 50 39 9.6 31
PBT 67 MBAM 33 208 0.2％ 1.2％ Hold its shape 63 55 20.6 15
Embodiment 2 PBT 33 M3AM 67 Trans fixing 0.7％ 5.2％ Distortion 41 25 3.5 81
PBT 40 M3AM 60 212 0.6％ 5.0％ Partial variation 56 44 8.0 23
PBT 50 M3AM 50 210 0.6％ 4.3％ The part distortion 57 47 8.7 14
PBT 67 M3AM 33 207 0.2％ 1.8％ Hold its shape 57-71 45-65 18.8 6
Comparative Examples 1 PBT 100 - 211 0.0％ 0.5％ Hold its shape 83 81 -
Embodiment 3 PA 40 MBAM 60 77 3.0％ -0.6％ Be partly dissolved 46 31 8.9 75
PA 50 MBAM 50 185 1.7％ -2.6％ Be partly dissolved 55 41 11.6 64
Embodiment 4 PA 40 M3AM 60 201 0.6％ 3.0％ Hold its shape 56 42 8.7 90
PA 50 M3AM 50 202 0.2％ 3.5％ Hold its shape 66 57 12.8 51
Embodiment 5 PA 40 M3AM 60 200 0.4％ 4.3％ Hold its shape 58 46 11.6 84
PA 50 M3AM 50 199 0.2％ 4.6％ Hold its shape 65 54 12.9 52
Table 1 (continuing)
Be mixed into component Dimension block-regulations (Vicat) Oil-proofness Hardness Tensile property
1kg 70℃4hr 150℃72hr JISD Breaking tenacity Elongation at break
Resin Part Block polymer Part 1mm/2mm Swelling capacity Shape Immediately 15 seconds Mpa ％
Comparative example 2 PA 100 - 214 0.0％ 0.1％ Hold its shape 84 81 -
Comparative example 3 TPEE 100 - 165 4.1％ 7.8％ Hold its shape 46 42 34.9 721
Comparative example 4 TPAE 100 - 136 1.9％ 7.9％ Fracture 52 45 30.4 618
Comparative example 5 TPU 100 - 138 0.3％ 2.4％ Hold its shape 49 43 50.7 836
According to embodiment 1,2,3 and 4 and the result of Comparative Examples 1 and 2 as can be seen, when comparing with independent crystalline resins, composition exhibiting of the present invention goes out elastomerics shape performance, has the hardness of reduction and good oil-proofness, and can keep good thermotolerance.In addition, by Comparative Examples 3,4 and 5 as can be seen, composition of the present invention has excellent thermotolerance for the engineering plastics based elastomeric.
In addition, when the total amount of PBT and MBAM was 100 weight parts, by embodiment 1 as can be seen, with regard to thermotolerance and oil-proofness, the content of PBT was preferably greater than 40% weight, more preferably 50 weight parts.
In addition, when the total amount of PBT and M3AM was 100 weight parts, by embodiment 2 as can be seen, with regard to thermotolerance and oil-proofness, the content of PBT was preferably greater than 33% weight, more preferably 40 weight parts.
In addition, when the total amount of PA and MBAM was 100 weight parts, by embodiment 3 as can be seen, with regard to thermotolerance and oil-proofness, the content of PA was preferably greater than 40% weight, more preferably 50 weight parts.
In addition, when the total amount of PA and M3AM was 100 weight parts, by embodiment 4 and 5 as can be seen, with regard to thermotolerance and oil-proofness, the content of PA was preferably greater than 40% weight.In addition, even when mixed carbon black, find also can obtain gratifying physicals.
Embodiment 6
To mix with MMA-BA-MMA type segmented copolymer (M-1) as polybutylene terephthalate resin 50 weight parts (DURANEX 2002, and by Polyplastics Co., Ltd. makes) of crystalline thermoplastic resin.Utilization is equipped with vapor opening, and (32 millimeters, twin screw extruder L/D=25.5) is extruded and is mediated mixture under 240 ℃ design temperature, carries out extrusion molding with the round mouth die head then, thereby obtains the line material.Then the line material is carried out outward appearance assessment and tension test.
Embodiment 7
Prepare and assess moulded product with mode similar to Example 6, different is, with nylon 6 resins (UBE Nylon 1013B, by Ube Industries, Ltd. makes) as the resin among the embodiment 6.
Assessment result is listed in the table 2.
The tension test (20mm/min) of table 2 line material
Test number Be mixed into component Tensile property (flow direction)
Fracture position Breaking tenacity Elongation at break Between the mark Young's modulus
Resin 1 g Resin 2 g MPa ％ Mpa
Embodiment 6 PBT 50 MBAM 50 Outside the mark 4.4 70 69 3.4
Embodiment 7 PA 50 MBAM 50 Outside the mark 5.5 52 46 5.7
When with hand these line material being pushed on the SU5316 metallic surface when discharging then, can confirm does not have composition to adhere on the metallic surface.
By transmission electron microscope the inside of these line material is carried out finding when discrete state is analyzed: the line material has " sea-island " structure, and wherein about 1 submicron resin swims in the marine of segmented copolymer.
Therefore, although rubber constituent is about 35 parts of 100 parts of compositions, each line material all has excellent flexibility, cleanliness and good surface properties, and also demonstrate such feature in addition, promptly it is a softish, but hardening when stretching.These materials needing can be preferred in the application of snappiness and intensity, as cord material, medical material, or the like and requirement do not have resistates to stay in the lip-deep application of metallic contact, as be used for the cementing agent of semiconductor wafer conveyer.
Embodiment 8-13
Prepare and assess moulded product with the mode that is similar to embodiment 1, different is, according to following table, will (DURANEX 2002 as the polybutylene terephthalate resin of crystalline thermoplastic resin, by Polyplastics Co., Ltd. make), UBE Nylon 1013B is (by Ube Industries, Ltd. make), or UBESTA (by Ube Industries, Ltd. make) and in an embodiment as MMA-BA-MMA type segmented copolymer (M-1) or MMA-(EA/BA/MEA)-MMA type segmented copolymer (M-3) mixing of segmented copolymer.
Table 3
Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 Embodiment 13
Resin PBT DURANEX 2002(g) PA6 UBE 1013B(g) PA12 UBE STA 3024U(g) 7.5 7.5 7.5 7.5 7.5 7.5
Block MMA-BA-MMA(g) MMA-(BA/EA/MEA)-MMA(g) 37.5 37.5 37.5 37.5 37.5 37.5
Stablizer Irganox 1010(g) Topanol CASF(g) PEP-36(g) AO80(g) TPS(g) 0.2 0.2 0.2 0.23 0.2 0.2 0.2
Physicals Hardness A hardness D 39 64 23 40 61 21 43 17 64 23
The elongation at break (%) of breaking tenacity (MPa) between mark 6.3 197 7.1 272 5.1 255 7.2 289 7 209 5.6 345
150 ℃ of oil-proofness swelling capacity (%) -22.6 23.8 -97.9 21.7 88.4 23.2
70 ℃ of Cset 22 hours (%) 42.2 58.9 67.5 74.6 45.8 70.5
Therefore, have found that,, obtained composition pliable and tough and that tensile property is excellent by mixing segmented copolymer greater than amount of resin.Particularly, find that when M-3 was used as segmented copolymer, oil-proofness was excellent.
Embodiment 14-20
Prepare and assess moulded product with mode similar to Example 1, different is that the MMA-BA-MMA type segmented copolymer (M-2) that will contain epoxy group(ing) mixes as segmented copolymer and according to following table.
Table 4
Embodiment 14 Embodiment 15 Embodiment 16 Embodiment 17 Embodiment 18 Embodiment 19 Embodiment 20
Resin PBT DURANEX 2002(g) PA6 UBE 1013B(g) PA12 UBE STA 3024U(g) 7.5 7.5 7.5 21 21 28 28
Block MMA-BA-MMA(g) MMA-(BA/EA/MEA)-MMA(g) 37.5 37.5 37.5 21 21 14 14
Stablizer Irganox 1010(g) Topanol CASF(g) PEP-36(g) AO80(g) TPS(g) 0.2 0.2 0.2 0.126 0.126 0.084 0.21 0.126 0.126 0.084 0.21
Physicals Hardness A hardness D 59 13 28 35 24 26 35 37
The elongation at break (%) of breaking tenacity (MPa) between mark 4 103 3.5 207 2.4 115 3.2 75 2.9 68 1.6 25 The depression depression
150 ℃ of oil-proofness swelling capacity (%) 107.9 53.2 58 55.8 26.5 22 11.9
70 ℃ of Cset 22 hours (%) 53.2 31.3 36.9 - - - -
Therefore, have found that the better moulded product of moulded product snappiness when the MMA-BA-MMA type segmented copolymer that contains epoxy group(ing) by utilization has obtained Billy with M-1.
Embodiment 21-22
Under the rotating speed of 230 ℃ design temperatures and per minute 100 commentaries on classics, in plastomill, ratio shown in the following table, to nylon 6 (UBE nylon as crystalline thermoplastic resin, by Ube Industries, Ltd. manufacturing) and as (MMA/MA)-BA-(MMA/MA) type segmented copolymer (M-6) of segmented copolymer mediated 15 minutes, to obtain caked sample.Under 230 ℃ design temperature, on thermocompressor, the sample that obtains is carried out mold pressing, with the thickness that obtains to be used to estimate physicals 2 millimeters moulded product.
After moulded product perforation that will obtain or being cut into independently predetermined shape, measure the physicals of gained moulded product according to aforesaid method.
Measure compression set according to following method.
(compression set)
For the compression set of composition, according to JIS 6301, under the state of 25% compression ratio, cylindrical moulded product was kept 22 hours at 70 ℃, shelved 30 minutes in room temperature then.Then, the thickness of measurement mode goods and calculate the residual strain degree.That is to say that 0% compression set has been equivalent to recover whole strains, not recover and 100% compression set is equivalent to state of strain.
Embodiment 23
With preparing with embodiment 21 similar modes and assess moulded product, different is, with MMA-(BA/HEA)-MMA type segmented copolymer (M-4) as the segmented copolymer among the embodiment 21.
Assessment result is listed in the table 5.
Table 5
Be mixed into component Treatment temp Hardness Tensile property Oil-proofness Compression set Mobile
JIS A JIS D Breaking tenacity Elongation at break 150℃ 72hr 70℃ 22h 100℃ 22h Flow and begin Flow and finish
Resin 1 Part Resin 2 Part Resin 3 Part ℃ Immediately Immediately MPa ％ Weight increases % Shape ％ ％ ℃ ℃
Embodiment 21 PA 7.5g M-6 37.5g Ti(oBu) 4 100μl 230 3.01 158.8 24.1 The part depression 68.6 84.4 113.6
Embodiment 22 PA 6g M-6 30g 230 29 2.42 142.8 12.1 The part depression 84.5
Embodiment 23 PA 7.5g M-4 25g 230 45 1.92 113.8 41.4 Almost remain unchanged 55.1
Mobile: the 60kg-loading
Therefore, obtained flexible moulded product already.When outward appearance is observed,, therefore, be understandable that nylon 6 with the MMA-BA-MMA type segmented copolymer that contains carboxylic acid reaction has taken place on DSC because the fusing point of nylon 6 does not observe.In addition, these compositions can suitably be used as compatibility enhancer.
(DSC: dsc is measured)
(50 (being made by Shimadzu Corporation) flow down at nitrogen, with 20 ℃/minute temperature rise rate, 2 milligrams of samples are heated to 300 ℃ to utilize DSC-50.
Embodiment 24
Under the rotating speed of 240 ℃ design temperatures and 100 rev/mins, in plastomill, (number-average molecular weight Mn is 122 to (MMA-co-TBMA)-b-BA-b-(MMA-co-TBMA) segmented copolymer (M-5 ') of 100 weight parts, 900, molecular weight distribution mw/mn is 1.46) and the composition of TBMA/MMA/BA=8.3/21.6/70.1 mediated 20 minutes, thereby convert it into acid anhydrides type segmented copolymer (M-7 ').
Under the rotating speed of 240 ℃ design temperatures and 100 rev/mins, in plastomill, subtend is wherein added 100 weight part polybutylene terephthalate resins, and (Duranex 2002, by PolyplasticsCo., Ltd. manufacturing) mixture that is obtained was mediated 20 minutes, to obtain caked sample.Under 240 ℃ design temperature, on thermocompressor, the sample that obtains is carried out mold pressing, with the thickness that obtains to be used to estimate physicals 2 millimeters moulded product.
After moulded product perforation that will obtain or being cut into independently predetermined shape, measure the physicals of gained moulded product according to aforesaid method.
Embodiment 25
With preparing with embodiment 24 similar modes and assessing moulded product, different is, change into acid anhydrides type segmented copolymer (M-7 ') afterwards using with embodiment 24 similar modes, add DaiamideE47-S1 (making) by Daicel-Huels Ltd., and under 190 ℃ design temperature and 100 rev/mins of rotating speeds, in plastomill, this mixture was mediated 20 minutes and carried out mold pressing at 190 ℃ design temperature in thermocompressor.
Embodiment 26
With preparing with embodiment 24 similar modes and assessing moulded product, different is, change into acid anhydrides type segmented copolymer (M-7 ') afterwards using, add 100 weight part UBE STA 3012U (by Ube Industries, Ltd. makes) with embodiment 24 similar modes.
Assessment result is listed in the table 6.
Table 6
Be mixed into component Processing temperature Hardness Pull resistance Oil-proofness Compression set Mobile
JIS A JIS D Breaking tenacity Elongation at break 150℃ 72hr 70℃ 22h 100℃ 22h Flow and begin Flow and finish
Resin 1 Part Resin 2 Part Resin 3 Part ℃ Immediately Immediately MPa ％ Weight increases % Shape ％ ％ ℃ ℃
Embodiment 24 M-7’ 100 PBT 100 240 74 6.1 52 43.8 Be partly dissolved - 134.8 189.7
Embodiment 25 M-7’ 100 Daiamide 100 240→190 61 3.2 71 72.5 Swelling - 124.3 153.6
Embodiment 26 M-7’ 100 UBESTA 3012U 100 240→190 79 2.7 14 29.3 Slight swelling - 161.1 179
Therefore, obtained already to have and wished tensile property, flexible moulded product.In embodiment 24 and 25, based on the measurement of acetone insoluble matter, resin as if with the acid anhydrides block copolymer reacting.In addition, these compositions can suitably be used as compatibility enhancer.
Embodiment 27
Under the rotating speed with 240 ℃ design temperatures and 100 rev/mins, in plastomill, MMA-(BA-co-HEA)-MMA segmented copolymer and 20 weight part crystalline thermoplastic resins to 100 weight parts hydroxyl in soft segment, (Duranex 2002 for polybutylene terephthalate resin, by PolyplasticsCo., Ltd. makes) mixture mediated 3 minutes.Then, as transesterification catalyst, to wherein adding 0.00107 weight part tetrabutyl titanium oxide monomer, and to whole kneading 7 minutes, to obtain caked sample.Under 240 ℃ design temperature, on thermocompressor, the sample that obtains is carried out mold pressing, be that 2 millimeters sheet material and diameter is that 30 millimeters height are 12 millimeters cylindrical molded bodies with the thickness that obtains to be used to estimate physicals.Assess with mode similar to Example 1.
Comparative Examples 6
With preparing with embodiment 27 similar modes and assessing moulded product, different is in embodiment 27, to use the not segmented copolymer of hydroxyl.
Assessment result is listed in the table 7.
Table 7
Be mixed into component Processing temperature Hardness Pull resistance Oil-proofness Compression set Mobile
JIS A JIS D Breaking tenacity Elongation at break 150℃ 72hr 70℃ 22h 100℃ 22h Flow and begin Flow and finish
Resin 1 Part Resin 2 Part Resin 3 Part ℃ Immediately Immediately MPa ％ Weight increases % Shape ％ ％ ℃ ℃
Embodiment 27 M-4 100 PBT 20 Ti(oBu) 4 1.07E-03 240 63 - 4.8 78 27.1 Keep 38.1 - 215.5 235.6
Comparative example 6 M-1 100 PBT 20 Ti(oBu) 4 1.07E-03 240 52 - 7.2 173 81.8 Swelling 45.9 - 140 192.4
Can know that by embodiment 27 and Comparative Examples 6 composition exhibiting of the present invention goes out elastomerics shape performance, and keep hardness, also demonstrate satisfactory compression set in addition, thermotolerance, and oil-proofness.
Embodiment 28
Utilize 6 inches rollers of 190 ℃, to 100 parts of poly-(vinylchlorid) (KANEVINYL S1007, by Kanegafuchi Chemical Industries Co., Ltd. make), 1.5 part contains the MMA-BA-MMA type segmented copolymer (M-2) (processing characteristics improving agent) of epoxy group(ing), 2.0 part stablizer (TVS#8831 based on the tin octylate sulfydryl, by Nitto Kasei Co., Ltd. make), 1.0 part lubricant (Kalcol8668, make by Kao Corporation) and the mixture of 3.0 parts of DOP mediate.The spalling resistance from the roll surface relatively after 10 minutes.
Assess with three point (Three-points) methods, and based on following judging criterion, 3 is the maximum of spalling resistance, and 1 is Schwellenwert.
3: sheet material and roll surface keep the time of the state that peels off not to be shorter than 3 minutes.
2: sheet material and roll surface keep the time of the state that peels off not to be shorter than 2 minutes but no longer than 3 minutes.
1: sheet material and roll surface keep peeling off the time of state no longer than 2 minutes.
Spalling resistance is kept the score with 3.
Comparative Examples 7
Assess with the mode that is similar to embodiment 28, different is, does not add any processing auxiliary agent, and spalling resistance is 1 minute.
Comparative Examples 8
Assess with the mode that is similar to embodiment 28, different is that with dealing with auxiliary agent, spalling resistance is 2 minutes with MMA-BA-MMA type segmented copolymer (M-1).
Comparative Examples 9
Assess with the mode that is similar to embodiment 28, different is that with dealing with auxiliary agent, spalling resistance is 2 minutes with PA-100 (by Kanegafuchi Chemical Industries, Co., Ltd. manufacturing).
By embodiment 28 and Comparative Examples 7,8 and 9 can know, the MMA-BA-MMA type segmented copolymer (M-2) that contains epoxy demonstrates as being used for vinyl chloride resin handles the effect of auxiliary agent, and should act on the effect greater than MMA-BA-MMA type segmented copolymer and commodity processing auxiliary agent.
Embodiment 29
Under 230 ℃ design temperatures and 100 rev/mins of rotating speeds, in plastomill, to 84 weight part methacrylic resins as crystalline thermoplastic resin, Parapet G100 is (by KURAUYCo., Ltd. make) and mix the mixture that is obtained as the MMA-BA-MMA type segmented copolymer (M-2) that 16 weight parts of impact modifying agent contain epoxy and mediated 5 minutes, to obtain caked sample.
Under 230 ℃ design temperature, on thermocompressor, the sample that obtains is carried out mold pressing, with the thickness that obtains to be used to estimate physicals 2 millimeters moulded product.
After moulded product perforation that will obtain or being cut into independently predetermined shape, measure the transparency and the dispersiveness of gained moulded product according to following method.
(transparency)
Transparency with the naked eye judges, and with the transparency of independent methacrylic resin moulded product be 5 minutes and opaque fully be that 0 fen such mode is assessed.
(dispersiveness)
Utilize transmission electron microscope, measure segmented copolymer divided particles system.
Transparency must be divided into 4 fens, and dispersion diameter is 100 nanometers or littler, and therefore, composition of the present invention has satisfactory performance.
Comparative Examples 10
With preparing with embodiment 29 similar modes and assess moulded product, different is, utilizes MMA-BA-MMA type segmented copolymer (M-1), and transparency must be divided into 3 fens, about 200 nanometers of dispersion diameter, because of, said composition is poorer than embodiment's 29.
In methacrylic resin, can know according to embodiment 29 and Comparative Examples 10, the MMA-BA-MMA type segmented copolymer that contains epoxy group(ing) demonstrates: compare with MMA-BA-MMA type segmented copolymer, moulded product becomes near transparent function, and this is owing to the dispersiveness of improving.Therefore, as under the situation of properties-correcting agent, can give shock-resistance, and not damage the transparency of methacrylic resin as far as possible.
Embodiment 30
The MMA-BA-MMA type segmented copolymer (M-2) that will contain epoxy group(ing) as 10 weight parts of impact modifying agent with as 100 weight part polycarbonate resin Lexan 141R-111 of thermoplastic resin (by Nippon GE Plastics Co., Ltd. make), as 0.3 weight part Topanol CA of stablizer (by Lipre Co., Ltd. make), mediate with Adekastab PEP-36 (deriving from Asahi Denka Kogyo K.K.), and under 240 ℃ design temperature, by being equipped with (32 millimeters of vapor openings, L/D=25.5) twin screw extruder is mediated this mixture and to be extruded and to make pellet.At 80 ℃ to dry 15 hours of the pellet that obtains.When being measured as the eddy current of molding fluidity index, found that to be 705 millimeters according to following method.In addition, when the gained moulded product is observed, do not observe any molding defect, as peeling off or burn in inside.
(eddy current)
At 1500kgf/cm 2Injection pressure and the injection pressure of 50mm/min, barrel temperature is set in 280 ℃, and die temperature is under 400 ℃, the square spiral of injection moulding 10mm * 3mm thickness; And by its length (mm) assessment molding flowability.
Comparative Examples 11
Prepare moulded product with the mode that is similar to embodiment 30, different is not add impact modifying agent.Found that eddy current is 443 millimeters.In addition, do not observe any molding defect.
Comparative Examples 12
With preparing moulded product with embodiment 30 similar modes, different is, with the acrylonitritrile-styrene resin resin (by Kanegafuchi Chemical Industries, Co., Ltd. make F85000H, vinyl cyanide/vinylbenzene=29/71 (weight ratio)) as impact modifying agent.Found that eddy current is 575 millimeters.In addition, do not observe any molding defect.
Comparative Examples 13
With preparing moulded product with the similar mode of embodiment 3-30, different is that MMA-BA-MMA type segmented copolymer (M-1) is used as impact modifying agent.
Found that eddy current is 855 millimeters.Yet, observe the serious inside of moulded product and peel off and burn.
According to embodiment 30 and Comparative Examples 11,12 and 13 can know, the MMA-BA-MMA type segmented copolymer that contains epoxy group(ing) has demonstrated the processing characteristics improvement effect that does not damage under the molding performance, and should act on the effect greater than MMA-BA-MMA type segmented copolymer and acrylonitritrile-styrene resin resin.
Embodiment 31
(Mn is 100 will to contain the MMA-BA-MMA type segmented copolymer (M-2 ') of epoxy group(ing) as 10 weight parts of impact modifying agent, 800, Mw/Mn is 1.46, and the component of BA/MMA/GMA=73/26/1 (% weight)) with (Duranex 2002 as 90 weight part polybutylene terephthalate resins of thermoplastic resin, by Polyplastics Co., Ltd. make) mix, and under 240 ℃ design temperature, by being equipped with (32 millimeters of vapor openings, L/D=25.5) twin screw extruder is mediated this mixture and to be extruded and to make pellet.80 ℃ of dryings 15 hours, and under 240 ℃ design temperature, and utilize 50 ℃ mould to carry out injection moulding, the pellet that obtains to obtain to be used to estimate the moulded product (1/4 inch of thickness) of physicals.
When measuring the Izot shock strength of gained moulded product for 23 ℃, its intensity is 12kg-cm/cm.In addition, when being measured as the melt viscosity of molding fluidity index according to following method, this viscosity is 2800 pools.
(melt viscosity)
According to the method described in the JIS K-7199, utilize capillary rheometer, with 1216s -1Shearing rate measure melt viscosity.
Comparative Examples 14
With preparing moulded product with embodiment 31 similar modes, different is that (the core-shell polymer modifiers, Rohm and Haas Co. is Ltd.) as impact modifying agent with EXL 2330.When measuring the Izot shock strength of gained moulded product for 23 ℃, its intensity is 8kg-cm/cm.In addition, melt viscosity is 2500 pools.
Comparative Examples 15
With preparing moulded product with embodiment 31 similar modes, different is that MMA-BA-MMA type segmented copolymer (M-1) is used as impact modifying agent.
When measuring the Izot shock strength of gained moulded product for 23 ℃, its intensity is 9kg-cm/cm.In addition, melt viscosity is 1500 pools.
Can know by embodiment 31 and Comparative Examples 14 and 15, when comparing with the core-shell polymer modifiers, the MMA-BA-MMA type segmented copolymer that contains epoxy group(ing) is more excellent aspect the shock-resistance improvement effect of polybutylene terephthalate resin and the mobile improvement effect of molding.Will also be appreciated that in addition the balance between the mobile improvement effect of shock-resistance improvement effect and molding can control, this is because the melt viscosity of polybutylene terephthalate resin can be controlled by the content of epoxy group(ing).
(2) embodiment (2-1)-(2-3) and Comparative Examples 2-1
Embodiment 2-1
25 weight parts are contained the MMA-BA-MMA type segmented copolymer (M-2) of epoxy to be mixed mutually with the regenerative PET resin as crystalline thermoplastic resin of 75 weight parts (by the flaky resin that separates, pulverizes, washs and the dry reuse beverage bottle of being made by polyethylene terephthalate obtains), and under 280 ℃ design temperature and 50 rev/mins of rotating speeds, in plastomill, this mixture was mediated 10 minutes, to obtain caked sample.
In pulverizer, pulverize the sample of gained, and be 1900 pools 280 ℃ melt viscosity.
(melt viscosity)
According to the method described in the JIS K-7199, utilize capillary rheometer, with 61s -1Shearing rate measure melt viscosity.
Embodiment 2-2
With assessing with the similar mode of embodiment 2-1, different is that the segmented copolymer (M-7) that will contain anhydride group is as the segmented copolymer among the embodiment 2-1.
280 ℃ melt viscosities is 2300 pools.
Embodiment 2-3
With assessing with the similar mode of embodiment 2-1, different is will contain its polymers of carboxyl block (M-6) as the segmented copolymer among the embodiment 2-1.
280 ℃ melt viscosities is 500 pools.
Comparative Examples 2-1
With assessing with the similar mode of embodiment 2-1, different is not use segmented copolymer in embodiment 2-1.280 ℃ melt viscosities is 6 pools.
By embodiment 2-1, the result of 2-2 and 2-3 and Comparative Examples 2-1 contains epoxy group(ing) as can be seen, anhydride group, or the segmented copolymer of carboxyl has thickening power to regenerative PET.In these segmented copolymers, the segmented copolymer that comprises epoxy group(ing) or anhydride group has more excellent effect.
Industrial applicibility
Thermoplastic resin composition of the present invention can provide such mechanograph, and it demonstrates excellent physical property balance, and such as resistance to impact, molding is mobile, and processing characteristics, and keeps the intrinsic performance of thermoplastic resin, such as against weather and heat endurance.
In addition, thermoplastic resin composition of the present invention can provide such mechanograph, and it can be used as the elastomer of physical property balance excellence. More particularly, the present invention can provide and demonstrate superior physical properties such as hardness, elastomer performance, and the mechanograph of processing characteristics balance, and kept the intrinsic performance of thermoplastic resin, such as heat endurance and oil resistivity.
Therefore, thermoplastic resin composition of the present invention can be suitably for the production of different mechanographs, such as extrusion profile, comprise sheet material, film, sheet material and shape material, the Die goods, blow-molded article comprises bottle etc., and supply automobile or household appliances to be used as the various injection-molded items of packaging material, the material that is used for building and civil engineering is used for the material of automobile, is used for the material of household electrical appliance and for the material of other general goods, this shows that described composition has huge industrial value.

Claims (7)

1. thermoplastic resin composition, it comprises thermoplastic resin (a) and contains methacrylate polymer block (A) and the segmented copolymer (b) of acrylate copolymer block (B), in this segmented copolymer (b), in this methacrylate polymer block (A) and this acrylate copolymer block (B) polymer blocks one of at least, comprise reactive functional groups (C), and the quantity of this reactive functional groups (C) is every mole of segmented copolymer 0.1 or bigger.
2. according to the thermoplastic resin composition of claim 1, wherein, thermoplastic resin (a) is to be selected from poly-(vinylchlorid) resin, poly-(methyl methacrylate) resin, the acrylonitritrile-styrene resin resin, copolymer of methyl methacrylatestyrene resin, polycarbonate resin, the thermoplastic resin of vibrin and polyamide resin.
3. according to the thermoplastic resin composition of claim 1, wherein, reactive functional groups (C) is to be selected from epoxy group(ing) at least, hydrolysable silyl group, hydroxyl, amino, carboxyl, anhydride group, thiazolinyl, a kind of functional group of reactive chlorine group and oxazoline group.
4. according to the thermoplastic resin composition of claim 2, wherein, reactive functional groups (C) is to be selected from epoxy group(ing) at least, hydrolysable silyl group, hydroxyl, amino, carboxyl, anhydride group, thiazolinyl, a kind of functional group of reactive chlorine group and oxazoline group.
5. according to each thermoplastic resin composition in the claim 1～4, it comprises the thermoplastic resin (a) of 99.5-10% weight and the segmented copolymer (b) of 0.5-90% weight.
6. according to each thermoplastic resin composition in the claim 1～4, it comprises the thermoplastic resin (a) of 90-10% weight and the segmented copolymer (b) of 10-90% weight.
7. according to each thermoplastic resin composition of claim 1～4, wherein, produce segmented copolymer (b) by controlled radical polymerization.
CN 200710087791 2001-05-14 2002-05-14 Thermoplastic resin composition Pending CN101016400A (en)

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CN111051425A (en) * 2017-09-14 2020-04-21 共荣社化学株式会社 Thermosetting resin composition
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