CN1242791A - Process for preparing compositions based on thermoplastic polymers and polyamides - Google Patents

Process for preparing compositions based on thermoplastic polymers and polyamides Download PDF

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CN1242791A
CN1242791A CN 97181196 CN97181196A CN1242791A CN 1242791 A CN1242791 A CN 1242791A CN 97181196 CN97181196 CN 97181196 CN 97181196 A CN97181196 A CN 97181196A CN 1242791 A CN1242791 A CN 1242791A
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M·维贝尔
G·皮珀
H·菲施
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BASF SE
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Abstract

The invention concerns a process for preparing compositions containing at least one thermoplastic polymer A and at least one polyamide B by dissolving the thermoplastic polymer A in at least one lactam b and optionally further polyamide-forming monomers b, and subsequent polymerization of the monomers b. The monomers b are polymerized in the presence of between 0.001 and 5 wt % water, relative to the monomers b.

Description

Preparation of compositions method based on thermoplastic polymer and polymeric amide
The present invention relates to the improving one's methods of composition that a kind of preparation contains at least a thermoplastic polymer A and at least a polymeric amide B, described method be thermoplastic polymer A be dissolved at least a lactan b and, as needs, other forms among the monomer b of polymeric amide, makes monomer b polymerization then.The invention still further relates to composition, their purposes and blend polymer, moulded product, film or the fiber that contains this based composition by this method preparation.
Polymeric amide can prepare with several different methods.A kind of method that obtains polymeric amide is to make the polymerization of lactan generation ring opening hydrolysis.For example, describe a kind of improvement technology of this method among the DE-A 43 21 683, also can be used for large-scale commercial production.
The blend of the non-crystalline state plastics of polymeric amide and poly (arylene ether) sulfone or polyetherimide and so on is known already.Amorphous polymer disperses carefully more in polymeric amide, and then the mechanical property of blend is good more.
US 3,729, and 527 particularly point out, and this class blend can be by preparing the ε-Ji Neixianan polymerization reaction take place under the situation that has the poly (arylene ether) sulfone to exist.DE-A 41 02 996 advises that also the polymerization lactan prepares the superpolymer alloy under the situation that has amorphous polymer such as polysulfones, polyphenylene oxide, polyetherimide, polyamidoimide or styrol copolymer to exist.Polyreaction causes with highly basic.
If the component of blend polymer with melt-mixing, for example, in forcing machine, then generally all adds expanding material in component.According to EP-A 374 988, Mc Grath etc. people such as (1973) 1032 pages of " polymer manufacture " the 14th phases or Corning in " macromole and macromolecular chemistry collection of thesis " the 75th phase (1993) 159 pages argumentation, suitable expanding material is to contain polyamide segment and poly (arylene ether) sulfone segmental multipolymer, this multipolymer by the poly (arylene ether) sulfone is dissolved in the lactan melt and have highly basic to exist and anhydrous condition under implementing anionic lactam polymerisation is prepared.
For example, Van Buskirk etc. has delivered in " polymer manufacture " the 29th volume the 1st phase (1988) paper of the 557th page also that lactan carries out the research of anionic polymerisation in forcing machine when having polyetherimide or polysulfones to exist.
The shortcoming of described method is that the macromolecular chain of thermoplastic polymer can be subjected to the negatively charged ion that exists in the reaction mixture to attack and degrade.And anionoid polymerization needs special technical measures to come the controlled polymerization degree, because this reaction is generally all carried out very fastly, viscosity just increases suddenly in short duration.Therefore, obtain the i.e. product of regulation chain length or viscosity of regulation structure, even may, also be very difficult.In addition, product contains residual catalyzer and degraded product or by product, and they usually can not be removed.If polyreaction is carried out in forcing machine, then usually do not reach conversion completely, thereby still contain residual monomer in the end product.And generally can only obtain dark product, as brown.
Schnablegger etc. have described the reaction of ε-Ji Neixianan with the poly (arylene ether) sulfone of band phenalgin end group in " polymkeric substance journal " the 46th phase (1995) the 307th page of literary composition.Amino and ε-Ji Neixianan generation ring-opening reaction, thereby initiated polymerization.Reaction is carried out under anhydrous condition, can use phosphoric acid does catalyst.The shortcoming of this method is to have only the step by costliness just can make the pure poly (arylene ether) sulfone that two phenalgin end groups are arranged on the every macromolecular chain.
The present invention aims to provide a kind of improving one's methods, and can obtain many finely divided compositions based on thermoplastics and polymeric amide by this method, even the degraded of thermoplastic polymer wherein also only is degraded to unconspicuous degree.This is improved one's methods and also allows to control well the viscosity of the composition that will prepare.And, adopt this improve one's methods also may obtain good mechanical properties, be exactly pure in preparation or the product of purifying easily.
We find, can realize above-mentioned purpose by a kind of preparation method for compositions, described composition contains at least a thermoplastic polymer A and at least a polymeric amide B, described method be thermoplastic polymer A be dissolved at least a lactan b and, as needs, other forms among the monomer b of polymeric amide, makes monomer b polymerization then, and wherein the polyreaction of monomer b is to carry out under the condition that exists of the water at 0.001～5 weight % that monomer b weight is arranged.
Suitable thermoplastic polymer A is the mixture of all monomer b that are dissolved in lactan or lactan and other formation polymeric amide and the amorphous polymer that polyreaction is not had disadvantageous effect.According to the present invention, dissolving is interpreted as that preparation looks transparent melt, promptly polymer A can be physical dissolution or exist with finely divided form.Suitable amorphous polymer A comprises poly (arylene ether) such as poly (arylene ether) sulfone or polyphenylene oxide, polyetherimide, polyamidoimide, polystyrene and styrol copolymer such as styrene/acrylonitrile copolymer, vinylbenzene/diene copolymers, diene or acrylic elastomer base graft copolymer such as ABS (acrylonitrile/butadiene/styrene), ASA (vinyl cyanide/phenylethylene ethylene/propenoic acid ester) or AES (vinyl cyanide/ethylene/styrene), or other ethylene copolymer.The mixture of different polymer A also can be soluble.
The general formula of specially suitable poly (arylene ether) is (I):
Figure A9718119600051
In general formula I, t and q can be 0,1,2 or 3 separately.T, Q and Z are independently of one another, can be identical or different.They can be that a chemical bond or one are selected from-O--SO 2-,-S-, C=O, the group of-N=N-and S=O.In addition, T, Q and Z can be that general formula is-R aC=CR b-or-CR cR d-group, R wherein aAnd R bEach is hydrogen or C naturally 1-C 10-alkyl, R cAnd R dEach is hydrogen naturally, C 1-C 10-alkyl such as methyl, ethyl, n-propyl, sec.-propyl, the tertiary butyl or n-hexyl, C 1-C 10-alkoxyl group such as methoxyl group, oxyethyl group, positive propoxy, isopropoxy or n-butoxy, or C 6-C 18-aryl such as phenyl or naphthyl.R cAnd R dTogether with also can bonding getting up to form the cycloalkyl ring of 4-7 carbon atom with the carbon atom of their bondings.Wherein preferably cyclopentyl and cyclohexyl.Cycloalkyl ring can be unsubstituted or by one or more, preferred 2 or 3, and C 1-C 6The ring that-alkyl group replaced.The substituting group of preferred cycloalkyl ring comprises methyl.The preferred T that adopts, Q, Z respectively do for oneself-O-,-SO 2-, C=O, chemical bond or general formula are-CR cR d-the poly (arylene ether) of group.Preferred radicals R cAnd R dComprise hydrogen and methyl.At T, Q in the Z group, has at least one to be-SO 2-or C=O.If t and q are 0, then Z is exactly-SO 2-or C=O, preferred-SO 2-.Ar and Ar 1Each is C naturally 6-C 18-aryl is as 1,5-naphthyl, 1,6-naphthyl, 2,7-naphthyl, 1,5-anthryl, 9,10-anthryl, 2,6-anthryl, 2,7-anthryl or xenyl, particularly phenyl.These aromatic groups are preferably unsubstituted.But they also can have one or more, as 2, and substituting group.Suitable substituents is C 1-C 10-alkyl such as methyl, ethyl, n-propyl, sec.-propyl, the tertiary butyl or n-hexyl, C 6-C 18-aryl such as phenyl or naphthyl, C 1-C 10-alkoxyl group such as methoxyl group, oxyethyl group, positive propoxy, isopropoxy or n-butoxy and halogen.Wherein preferred substituted comprises methyl, phenyl, methoxyl group and chlorine.
Some suitable repeating units are as follows:
Figure A9718119600071
Figure A9718119600081
Has repeating unit (I 1), (I 2) or (I 8) poly (arylene ether) be particularly preferred.They comprise, for example, and repeating unit (I 1) account for 0～100 mole of % and repeating unit (I 2) account for the poly (arylene ether) of 0～100 mole of %.
Poly (arylene ether) also can be multipolymer or the poly (arylene ether) segment wherein be arranged and other thermoplastic polymer segmental segmented copolymer.Described other thermoplastic polymer such as polyester, aromatic polycarbonate, polyestercarbonate, polysiloxane, polyimide or polyetherimide.Block in the multipolymer or grafted number-average molecular weight are generally 1000～30, the 000g/ mole.The block that structure is different can replace or randomly arrange.The weight content of poly (arylene ether) generally is at least 10 weight % in multipolymer or the segmented copolymer, reaches as high as 97 weight %.Preferred polyarylene ether content is up to multipolymer or the segmented copolymer of 90 weight %.Preferred especially polyarylene ether content is multipolymer and the segmented copolymer of 20～80 weight %.
Other suitable poly (arylene ether) is with the monomer modified poly (arylene ether) that contains acidic group or anhydride group.For example, this class poly (arylene ether) can begin preparation from the monomer that contains acidic group or anhydride group accordingly.Also can be by these are monomer-graftedly gone to obtain to the poly (arylene ether) chain.Suitable acidic group comprises carboxylic acid group, sulfonic group or phosphate.Preferred especially acidic group is made the poly (arylene ether) of ordered distribution or random distribution on whole macromolecular chain, for example, can be bonded to acidic group on arylene group or the alkylidene group middle shot.For example, with fumaric acid, toxilic acid, maleic anhydride or preferred especially 4, the poly (arylene ether) sulfone of 4 '-dihydroxy-acid modification is suitable.For example, some examples of this poly (arylene ether) sulfone in EP-A 185 237, have been provided.
Also can be with the mixture of two or more different poly (arylene ether) sulfones.
In general, the number-average molecular weight M of poly (arylene ether) nBe 5,000～60,000g/mol, relative viscosity is 0.20～0.95dl/g.The solubleness that depends on poly (arylene ether), relative viscosity can with polymkeric substance the N-methyl than pyrrolidone in, in the mixed solvent of phenol and dichlorobenzene or the concentration in 96% sulfuric acid be that 1% solution is measured, under any circumstance probe temperature is 20 ℃ and 25 ℃.
The poly (arylene ether) that contains repeating unit I is well-known, available known method preparation.
For example, they are that the polycondensation of the basic metal double salt by aromatics dihalide compound and aromatic bisphenols forms.For example, they also can be by the self-condensation reaction preparation of an alkali metal salt of aromatic halophenols when having catalyzer to exist.The poly (arylene ether) that contains the carbonyl functional group also can pass through electrophilic (friedel-crafts) polycondensation and obtain.In the electrophilic polycondensation; the carbonyl bridge is to be reacted by dicarbapentaborane muriate or phosgene and the aromatic substance that contains the hydrogen atom of 2 energy and electrophilic substituent exchange to form, perhaps makes to contain the chloride of acid group simultaneously and form with the aromatics carbonyl chloride generation self-condensation reaction that can replace hydrogen atom.
The preferred processing condition of synthetic poly (arylene ether) for example, has been described in EP-A-113 112 and 135 130.Particularly suitable be monomer in aprotonic solvent, in N-Methyl pyrrolidone, having anhydrous alkali metal carbonate particularly to react in the presence of the salt of wormwood especially.Proved already that it was favourable that monomer is reacted in molten state.
The poly (arylene ether) of general formula I can contain such as hydroxyl, chlorine, preferably include methoxyl group, the phenoxy group mixture at end groups such as interior alkoxyl group, amino or acid anhydrides or described end group.
Thermoplasticity amorphous polymer A also can be the compound based on the particularly disubstituted polyphenylene oxide that replaces, in the described polyphenylene oxide, and the benzene nucleus keyed jointing of unitary ether oxygen atom and adjacent cells.The preferred polyphenylene oxide that on 2 and/or 6, replaces with respect to Sauerstoffatom that adopts.Substituent example has halogen such as chlorine or bromine, the chain alkyl of maximum 20 carbon atoms such as the short-chain alkyl of dodecyl and octadecyl and 1-4 carbon atom, does not wherein preferably have alkyl such as methyl, ethyl, propyl group or the butyl of α tertiary hydrogen atoms.Alkyl chain can replace by halogen such as chlorine or bromine or by the hydroxyl list again or be polysubstituted.Also having some possible substituting group examples is alkoxyl groups, the alkoxyl group of preferred 1-4 carbon atom, perhaps not replacement or by halogen and/or C as defined above 1-C 4-alkyl list replaces or polysubstituted phenyl.The multipolymer of different phenols is as 2,6 dimethyl phenols and 2,3, and the multipolymer of 6-trimethylammonium phenol also is suitable.Certain also mixture of available different polyphenylene oxide.
According to the present invention, the example of available polyphenylene oxide has
Poly-(2, the two dodecyls-1 of 6-, 4-phenylene ether)
Poly-(2,6-phenylbenzene-1,4-phenylene ether)
Poly-(2,6-dimethoxy-1,4-phenylene ether)
Poly-(2,6-diethoxy-1,4-phenylene ether)
Poly-(2-methoxyl group-6-oxyethyl group-1,4-phenylene ether)
Poly-(2-ethyl-6-octadecane Oxy-1,4-phenylene ether)
Poly-(2,6-two chloro-1,4-phenylene ether)
Poly-(2-methyl-6-phenyl-1,4-phenylene ether)
Poly-(2,6-dibenzyl-1,4-phenylene ether)
Poly-(2-oxyethyl group-1,4-phenylene ether)
Poly-(2-chloro-1,4-phenylene ether)
Poly-(2,5-two bromo-1,4-phenylene ether)
The polyphenylene oxide that the preferred polyphenylene oxide that adopts is replaced by the alkyl of 1-4 carbon atom, as
Poly-(2,6-dimethyl-1,4-phenylene ether)
Poly-(2,6-diethyl-1,4-phenylene ether)
Poly-(2-methyl-6-ethyl-1,4-phenylene ether)
Poly-(2-methyl-6-propyl group-1,4-phenylene ether)
Poly-(2,6-dipropyl-1,4-phenylene ether) and
Poly-(2-ethyl-6-propyl group-1,4-phenylene ether).
For realizing purpose of the present invention, also polyphenylene oxide is interpreted as the polyphenylene oxide of the monomer modified mistake of using fumaric acid, toxilic acid or maleic anhydride and so on.
In WO 87/00540, this class polyphenylene oxide has been described especially.
The polyphenylene oxide that is used for this composition is weight-average molecular weight M particularly wBe 8,000～70,000, preferred 12,000～50,000,20,000～49,000 polyphenylene oxide particularly.
These molecular weight are corresponding to being 0.18～0.7dl/g in 25 ℃ of limiting viscosities that record in chloroform, preferred 0.25～0.55dl/g, particularly 0.30～0.50dl/g.
The molecular weight of polyphenylene oxide is generally all used gel permeation chromatography (Schodex separator column: 0.8 * 50cm, A 803 types, A 804 types and A 805 types are elutriant with the tetrahydrofuran (THF), at room temperature measure).The polyphenylene oxide sample is dissolved in the tetrahydrofuran (THF) in 110 ℃ under super-atmospheric pressure, sample injection amount: 0.16ml, weight concentration is 0.25% solution.
Generally detect with ultraviolet rays detector.The polyphenylene oxide sample that pillar had been measured with GPC/ laser light scattering coupling technique with the absolute molecular weight distribution is demarcated.
Suitable other thermoplasticity amorphous polymers A is the blend of polyetherimide or different polyetherimides.
In principle, used polyetherimide can be an aliphatics or aromatic.The polyetherimide that contains aliphatic series and aromatic group on the main chain simultaneously also is suitable.For example, can be with containing the polyetherimide that repeating unit is general formula I I
Figure A9718119600121
Wherein Q ' is selected from, for example,
Figure A9718119600122
With
Figure A9718119600123
Z ' and R ' are independently of one another, can be identical or different.For example Z ' and R ' can be C 1-C 30-alkylidene group.Alkylidene group can be linear or branching, or seals into ring.Their example has methylene radical, ethylidene, positive propylidene, isopropylidene, cyclohexylidene and positive inferior decyl.But Z ' and R ' also can be C 7-C 30-alkyl arylene.The example is diphenylene methane, diphenylene ethane and 2,2-diphenylene propane.Z ' and R ' can also be C 6-C 18-arylidene is as phenylene or biphenylene.Above-mentioned group can be replaced by one or more substituting group again or be separated by heteroatoms or heteroatoms group.Particularly preferred substituting group is a halogen, preferred chlorine or bromine, perhaps C 1-C 10-alkyl, particularly methyl or ethyl.Preferred heteroatoms or heteroatom group comprise-SO 2-,-O-and-S-.Provide some suitable group Z ' and R ' with example below:
Figure A9718119600124
Wherein Q " can be-C yH 2y-,-CO-,-SO 2-,-O-or-S-, q is 0 or 1, p is 0 or 1, y is 1～5 integer.R " can be C 1-C 10-alkyl or C 1-C 10-alkoxyl group, r can be 0 or 1.In addition, polyetherimide can also contain the imide unit except the unit that contains general formula I I.General formula I I for example 1And II 2Unit or their mixture be suitable.
Figure A9718119600131
The preferred employing contains the polyetheramides that general formula is the repeating unit of III Wherein the connotation of Z " with R " is identical with Z ' and R '.
Particularly preferred polyetherimide contains Z " is
Figure A9718119600133
And R " is selected from
Figure A9718119600134
With
Figure A9718119600135
Repeating unit.Especially very preferably polyetherimide contains general formula (III 1)
Figure A9718119600141
Repeating unit.
Number-average molecular weight (the M of polyetherimide n) be generally 5000～50,000, preferred 8000～40,000.Molecular weight or known, perhaps available known method is measured.
Therefore, the generation polyetherimide that suitable dianhydride and suitable diamines can be reacted.In general, this reaction is carried out in 100～250 ℃ under condition of no solvent or in inert solvent.Particularly suitable solvent is neighbour-dichlorobenzene and meta-cresol.Polyetherimide also can be at 200～400 ℃, preferred 230～300 ℃, melt in prepare.Be the preparation polyetherimide, generally with dianhydride and diamines with etc. mol ratio react.But, the excessive of certain mole can be arranged, for example the excessive 0.1～5mol% of dianhydride or diamines.
According to the present invention, also can be with polystyrene as polymer A.Particularly suitable monomer be vinylbenzene and nuclear go up or side chain by alkylation vinylbenzene.Example has chlorostyrene, alpha-methyl styrene, vinylbenzene, p-methylstyrene, Vinyl toluene and right-t-butyl styrene.But preferably adopt independent vinylbenzene.
Homopolymer is general with well-known mass polymerization, solution polymerization or suspension polymerization preparation (with reference to Ullmanns Enzyklopadie der techn.Chemie, the 19th rolls up, and 265～272 pages, Verlag Chemie press, Weinheim 1980).The weight-average molecular weight M of homopolymer wCan be 100～300,000, available traditional method be measured.
In addition, thermoplasticity amorphous polymer A can be to be based copolymers with vinylbenzene, according to the present invention, also can be interpreted as it with other vi-ny l aromatic monomers such as alpha-methyl styrene or other substituted phenylethylene such as C 1-C 10The multipolymer of-ring-alkylated styrenes such as vinyl toluene, or the blend of differing ethylene base aromatic monomer.For example contain 50～95 weight %, preferred 60～80 weight % vinylbenzene, alpha-methyl styrene or substituted phenylethylene, N-phenylmaleimide or their mixture and 5～50 weight %, the styrene copolymerized compound of preferred 20～40 weight % vinyl cyanide, methacrylonitrile, methyl methacrylate, maleic anhydride or their mixture is suitable.
Styrol copolymer is arborescens, thermoplasticity and does not contain rubber.Particularly preferred styrol copolymer be vinylbenzene and vinyl cyanide and, as needs, the multipolymer of methyl methacrylate, alpha-methyl styrene and vinyl cyanide and, as needs, the multipolymer of methyl methacrylate, vinylbenzene and alpha-methyl styrene and vinyl cyanide and, as needs, the multipolymer of methyl methacrylate, and the multipolymer of vinylbenzene and maleic anhydride.Also can adopt multiple described styrol copolymer simultaneously.These styrol copolymers are well-known also can pass through Raolical polymerizable, particularly letex polymerization, 3 polymerizations that suspend, solution polymerization and mass polymerization preparations.It is about 40～160 that their viscosity number is generally, corresponding weight-average molecular weight M WBe about 40,000～2,000,000.
In this novel method, also can adopt the styrol copolymer of vi-ny l aromatic monomers such as vinylbenzene or alpha-methyl styrene and conjugated diolefine.Specially suitable vi-ny l aromatic monomers is a vinylbenzene.Especially with divinyl or isoprene, preferably use divinyl, be conjugated diolefine., make this product carry out the multipolymer that hydrogenation reaction obtained then and also can be used as styrol copolymer usefulness vi-ny l aromatic monomers and conjugated diolefine generation polymerization by at first.
This quasi-styrene multipolymer especially can obtain by the anionic polymerisation of vi-ny l aromatic monomers and conjugated diolefine.This method mainly provides the segmented copolymer of these comonomers.The method for preparing this quasi-styrene multipolymer generally is known (US-A 3,595,942).
Used styrol copolymer can have any required structure, and the cladodification that preferably has the segmented copolymer of three block structures and have many block structures is star structure.From the method for the synthetic star block copolymer of vi-ny l aromatic monomers and diene monomers is the await the reply theme of application DOS 1,959,922 of Germany.And be DE 25 50 226 and US-A3 with the method for the synthetic star block copolymer of multiple initiation, 639,517 theme.
Suitable monomers and initiator have also been described in described publication.Preferably especially be vi-ny l aromatic monomers with vinylbenzene and be the segmented copolymer of conjugate diene monomer based on divinyl and/or isoprene.The ratio of vi-ny l aromatic monomers is generally 25～95 weight % in used styrol copolymer, preferred 40～90 weight %.
Used thermoplastic polymer A can also be a graft copolymer, and it preferably is made up of following component:
a 1) about 40～80 weight %, preferred about 50～70 weight %, comprise the grafting base material that second-order transition temperature is lower than 0 ℃ elastomer polymer;
a 2) about 20～60 weight %, the grafting layer of preferred about 30～50 weight %, it comprises
a 21) about 50～95 weight %, the vinylbenzene of preferred about 60～80 weight % or substituted phenylethylene or methyl methacrylate or their mixture of aforementioned formula III, and
a 22) about 5～50 weight %, vinyl cyanide, methacrylonitrile, methyl methacrylate, maleic anhydride or their mixture of preferred about 20～40 weight %.
Be suitable for use as grafting base material a 1) polymkeric substance be that second-order transition temperature is lower than 10 ℃, particularly be lower than 0 ℃, preferably be lower than-20 ℃ polymkeric substance.They are, for example, natural rubber, based on the mixture of the synthetic rubber of conjugated diolefine or they and other multipolymer, and with acrylic acid C 1-C 8-alkyl ester is the elastomerics on basis, wherein also can contain other comonomer.
Preferred grafting base material a 1) be polyhutadiene and divinyl and cinnamic multipolymer.
Preferred grafting base material a 1) composed as follows:
a 11) 70～99.9 weight %, at least a alkyl acrylate of preferred 99 weight %, wherein alkyl group has 1～8 carbon atom, and preferred n-butyl acrylate and/or 2-ethylhexyl acrylate are unique alkyl acrylate with n-butyl acrylate particularly.
a 12) monoene class unsaturated monomer such as divinyl, isoprene, vinylbenzene, vinyl cyanide, methyl methacrylate and/or the vinyl methyl ether of further copolymerization of 0～30 weight %, particularly 20～30 weight %, and
a 13) 0.1～5 weight %, but polyfunctionality monomer a kind of copolymerization of preferred 1～4 weight %, that influence degree of crosslinking, preferred two functionality or three-functionality-degree monomer.
Two functionality that this class is suitable or polyfunctionality cross-linking monomer a 13) be preferably to contain 2, also can contain more than 3 or 3 as needs can copolymerization but be not the monomer of conjugated alkene double bond on 1,3 position.The example of suitable cross-linking monomer has Vinylstyrene, toxilic acid diallyl ester, fumaric acid diallyl ester, diallyl phthalate, cyanuric acid alkatriene propyl diester and isocyanuric acid triallyl ester.Proved already that the acrylate of tricyclo decene alcohol was a kind of particularly advantageous cross-linking monomer (consulting DE-A-12 60 135).
This class grafting base material also is well-known, existing in the literature the description.
Preferred grafting layer a 2) be a wherein 21) be the polymkeric substance of vinylbenzene or alpha-methyl styrene.The preferred especially monomer mixture that adopts is vinylbenzene and vinyl cyanide, alpha-methyl styrene and vinyl cyanide, vinylbenzene, vinyl cyanide and methyl methacrylate, vinylbenzene, N-phenylmaleimide and maleic anhydride.The grafting layer can pass through component a 21) and a 22) copolyreaction obtain.
Every graft copolymer contains the grafting base material a that is made up of polybutadiene polymers 1) time, just with this term of ABS rubber.
As everyone knows, graft copolymerization can carry out in solution, suspension or preferred emulsion.When preparing ABS rubber and in emulsion, carrying out grafting, soft section average particulate diameter (d on the quality integral distribution curve in the graft copolymer 50Value) be preferably 0.08 μ m.By increasing the particulate size, for example obtain emulsion by congregation or with the inoculation emulsion method, then can be d 50Value is brought up to 0.2～0.5 μ m.In this graft copolymerization, just in the polymeric monomer, having a part and polymeric rubber generation chemical bonding at least.Bonding may occur on two keys contained in the rubber.So just have monomer-grafted having arrived on the rubber of a part at least, promptly with covalent linkage form and linear rubber molecule bonding.
Grafting also can multistep be carried out: at first grafting forms the grafting shell on a part of monomer, and then grafting on all the other monomers.
If the grafting base material a of graft copolymer 1) by component a 11), as needs, and a 12) and a 13) form, then use term ASA rubber.Their preparation wood body is known, perhaps also can prepare with the known method of wooden body.
The grafting layer of graft copolymer can be synthetic with single stage method or two step method.
Under the situation of the synthetic grafting layer of single stage method, with monomer a 21) and a 22) by desired weight ratio, 95: 5～50: 50, preferred 90: 10～65: 35, the blended mixture was at elastomerics a 1Existence under, with known method polymerization, preferred emulsion polymerization.
At the synthetic grafting layer a of two step method 2) situation under, the first step generally accounts for a 2) 20～70 weight %, preferred 25～50 weight %.Preferably, only use monoene class unsaturated aromatic hydrocarbon (a in the preparation 21).
In second step of grafting layer, generally account for a 2) 30～80 weight %, particularly 50～75 weight %.Used described monoene class unsaturated aromatic hydrocarbon a in the preparation 21) and monoene class unsaturated monomer a 22) weight ratio, i.e. a 21)/a 22), be generally particularly 80: 20～70: 30 90: 10～60: 40.
The optimum principle of conditions of graft copolymerization is that to make the particle size of formation be 50～700nm (d on the quality integral distribution curve 50Value).Adequate measures are known.
Can directly prepare the coarse grain rubber dispersion with the inoculation emulsion method.
In order to obtain the good product of toughness, the blend of the graft copolymer that at least two kinds of particle sizes of usefulness are different usually is favourable.
In order to realize this point, improve the size of rubber grain with known method such as congregation, make latex have that bimodal (for example 50～180nm and 200～700nm) forms.
Other example of thermoplasticity amorphous polymer A is the multipolymer of alpha-olefin.Alpha-olefin normally contains the monomer of 2-8 carbon atom, optimal ethylene and propylene.Proved already, alcohol from 1-8 carbon atom, preferred alcohol, butanols or ethylhexanol, the alkyl acrylate or the alkyl methacrylate of deriving out with reactive comonomer such as vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride or glycidyl methacrylate and vinyl ester, particularly vinyl-acetic ester are suitable for use as comonomer.Also can use the monomeric mixture of different copolymer.Verified, the ethylene copolymer that ethene and ethyl propenoate or butyl acrylate and vinylformic acid and/or maleic anhydride and so on form is specially suitable as comonomer.
This analog copolymer can also can pass through copolymerization single with the high-pressure process preparation of 400～4500 crust
Body is grafted to poly-alpha olefins and gets on and prepare.The amount of alpha-olefin is generally 99.95～55 weight % in the multipolymer.
For example, can use ε-Ji Neixianan, oenantholactam, spicy inner formyl amine and laurolactam and their mixture, preferred ε-Ji Neixianan is as lactan b.
Can be used as other monomeric compound that forms polymeric amide for example has alkane di-carboxylic acid such as hexanodioic acid, pimelic acid, suberic acid, nonane diacid or sebacic acid and the terephthalic acid and the m-phthalic acid of di-carboxylic acid such as 6-12 carbon atom, a particularly 6-10 carbon atom; Diamine such as C 4-C 12-alkyl diamine, particularly the alkyl diamine of 4-8 carbon atom is as 1,6 hexanediamines and 1,4 butanediamine, 1,8 octamethylenediamine and m-xylylene amine, two-(4-aminophenyl) methane, 2,2-two (4-aminophenyl) propane or two (4-aminocyclohexyl) methane, and the mixture of dicarboxylic acid and diamines, every kind all in the combination of any required ratio, but best equal proportion each other, for example, hexanodioic acid 1,6 hexanediamine salt, terephthalic acid 1,6 hexanediamine salt or hexanodioic acid 1,4 butanediamine salt, preferred hexanodioic acid 1,6 hexanediamine salt and terephthalic acid 1,6 hexanediamine salt.Polycaprolactam and have special industrial significance by hexanolactam, 1,6 hexanediamine and hexanodioic acid, m-phthalic acid and/or terephthalic acid synthetic polymeric amide.
In a preferred embodiment, ε-Ji Neixianan and hexanodioic acid 1,6 hexanediamine salt (AH salt) have been adopted.
General 30～100 weight % with monomer b total amount, the lactan of preferred 35～100 weight %, and 0～70 weight % of monomer b total amount, other of preferred 0～65 weight % forms the monomer of polymeric amide.AH salt uses with the form of the aqueous solution usually, and its concentration is generally 30～75 weight %, preferred 35～70 weight %, the aqueous solution.Usually, the weight ratio of lactan and AH salt is chosen to be 4: 1～and 20: 1, preferred 5: 1～15: 1.
According to the present invention, the monomer b of the formation polymeric amide of dissolve polymer A is a polymeric in the presence of the water of 0.001～5 weight % that accounts for monomer b weight.Preferably, this polyreaction is to have more than the 0.005 weight %, and for example, the water of 0.01～5 weight % carries out under existing.Particularly preferably be 0.1～4.5 weight %, the particularly water of 0.5～4 weight % of monomer b weight.Under these conditions, polymerization rate is enough high, and thermoplastic polymer A shockingly still is in solution state or disperses very carefully.
Can add water in the solution of thermoplastic polymer A in the monomer b that forms polymeric amide.If this class solution has contained water, for example, then needn't add water in addition or only add less water because AH uses with the form of the aqueous solution, make the ratio of Total Water and monomer b amount fall within the scope of the invention.
Generally be thermoplastic polymer A to be joined among the monomer b that forms polymeric amide go.But, also might get polymer A earlier, then the monomer b that forms polymeric amide is added.The amount of thermoplastic polymer A is generally 1～75 weight % in the solution.Therefore the monomeric amount that forms polymeric amide is 25～99 weight %.Preferably, solution contains 2～75 weight %, particularly the thermoplastic polymer A of 3～70 weight % and 25～98 weight %, particularly the monomer b of the formation polymeric amide of 30～97 weight %.
Depend on the monomeric fusing point that forms polymeric amide, polymer A at 50～300 ℃, preferred 80～290 ℃, is dissolved among the monomer b.In order to make the solution component thorough mixing, preferably the mixture with A and b stirs.For example, stirring tank is applicable to this purpose.Then, adding entry, generally is once to add entirely, and piecemeal adds or adds continuously.The temperature of the while or the solution that raises subsequently generally is raised to 180～330 ℃, preferred 220～310 ℃.Before or after temperature raises, or before or after adding entry, solution can remain in its container of preparation, also can transfer in another reactor.
The composition that can prepare this novelty in many ways.Therefore,, can in pipe, under super-atmospheric pressure, polyreaction be proceeded to certain transformation efficiency to form prepolymer, then prepolymer be carried out aftercondensated according to EP-A 129 195 and 129 196.United States Patent (USP) 2,241,322 disclose a kind of two-step approach, and this method also is applicable to the composition of this novelty of preparation.Suitable aftercondensated condition is for example having description among the EP-A 38 094.
Generally, preferred technology is carried out in the following manner: the aqueous solution that will be preheating to 75～90 ℃ leads to into reactor, this reaction mixture is heated to 220～310 ℃, preferred 240～290 ℃.
Baffle plate such as orderly hybrid element are preferably arranged (for example in the reactor, the Sulzer filler) or unordered hybrid element such as filler (for example Raschig ring, ball or Pall ring), like this, just preferred assurance has been shortened monomer in the time (purpose is to realize high conversion) that molten state is detained as far as possible, and has avoided melt not carry therein or only a small amount of zone (dead angle) and back-mixing of carrying as far as possible.
Usually, the selection principle of reaction pressure is that reaction mixture is existed with single liquid phase.It is favourable doing like this, because the formation of air bag can cause the mobile pulsation usually, thereby causes back-mixing and uneven polyreaction.Pressure is generally 5～30 crust herein, preferred 8～18 crust (absolute value).Residence time, depend on the water-content in temperature, pressure and the reaction mixture basically, generally elect 2～4 hours as, preferred 2～2.5 hours.Be shorter than 2 hours and water-content when being lower than 1 weight % when the reaction times, generally can only obtain to be lower than 86% transformation efficiency.Reaction times can make space-time yield reduce when surpassing 4 hours usually, and space-time yield is also relevant with the bigger reactor with technical complexity.
When adopting hexanolactam, behind first reaction zone, can obtain to contain molecular weight usually is 3000～9000g/mol, the composition of the polycaprolactam of preferred 5000～6700g/mol.Total end group concentration is generally 220～670mmol/kg, preferred 300～400mmol/kg, and melt viscosity is 100～10,000mPas, preferred 200～4000mPas (270 ℃).
According to the present invention, transformation efficiency is (with the cubage of extract: the content of transformation efficiency=100-extract) be at least 85%, be preferably greater than or equal 87%, be preferably greater than especially or equal 89%.
Generally, the adiabatic ground step-down of the reaction mixture under the super-atmospheric pressure, promptly allow pressure lower at second reaction zone, its method is: do not provide evaporation required heat from the outside, generally, the pressure in second reaction zone is elected 0.1～1.1 crust, preferred 500～1050 millibars as.Generally, in this step, the reaction mixture that comes from first reaction zone is cooled to 215～300 ℃, preferred 235～265 ℃.
And, can remove volatile constituent with steam expediently at second reaction zone, as used lactan b1 and other monomeric unit and their steam volatilization oligopolymer.In another preferred embodiment, volatile constituent is recycled in the technology continuously and quantitatively, promptly preferably is recycled to first reaction zone.
Residence time at second reaction zone is generally elected 2～60 minutes as, preferred 3～30 minutes.
When using hexanolactam, preferred technology forms behind second reaction zone usually that to contain molecular weight be 3000～14, and 000g/mol is preferred 6000～12, the composition of the hexanolactam of 000g/mol.At this moment, the end group total concn is generally 140～670mmol/g, preferred 170～330mmol/g, and melt viscosity is 100～10,000mPas, preferred 200～4000mPas (270 ℃).
With the composition of this novel method preparation, remove and contain from the mixture of the polymeric amide B of b acquisition or different polyamide B, also contain at least a thermoplasticity amorphous polymer A.And, thus obtained composition contain because of polymer A and monomer b or with polymer B or the compound that reacts and derive out with their mixture.Polymer A only has small amount of degradation, if degraded is arranged.So the chain length of polymer A remains unchanged substantially.
Generally, the composition that obtains behind second reaction zone can change fritter into traditional method, for example, with the discharging of composition melt, makes it then by water-bath cooling, granulation then.
The composition that obtains by the present invention can be with known method extracting.Polymeric amide B contained in the composition can be converted into subsequently or simultaneously higher molecular weight or high-molecular weight polymeric amide B.
For example, available counter-current water extracting composition (with reference to DD-A 206999).The desired viscosity number of final product is generally 80～350ml/g, and viscosity number can be with known method by regulating in high temperature drying or solid phase polycondensation.
Another kind of possible further working method is gas phase extracting (with reference to EP-A 284968), improves molecular weight simultaneously, and in the method, available superheated vapour carries out extracting and heating simultaneously.At this moment, the viscosity number of desired final product generally also is 80～350ml/g.
This composition can contain additive.Additive generally before granulation and/or before the monomer b polyreaction, between the reaction period or reaction back adds, and adds after the preferred reaction.
Composition can contain and accounts for composition total weight 0～40 weight %, and one or more rubber impact modifiers of preferred 1～30 weight % are additive.
For example, can be with the conventional impact properties-correcting agent that is suitable for polymeric amide and/or polymer A.
Increase polymeric amide flexible rubber and generally have two basic characteristics: they contain second-order transition temperature and are lower than-10 ℃, preferably are lower than-30 ℃ elastomeric component, they contain at least a can with the interactional functional group of polymeric amide.There are for example groups such as carboxyl, carboxylic acid anhydride, carboxylicesters, carboxylic acid amide, carboxylic acyloxy imines, amino, hydroxyl, epoxy compounds, urethano and oxazoline in suitable functional group.
It is as follows to improve blend flexible examples of rubbers:
With above-mentioned grafted EP of functional group and EPDM rubber.Suitable grafting agent is, for example, and maleic anhydride, itaconicacid, vinylformic acid, glycidyl acrylate and glycidyl methacrylate.
These monomers can get on there being or not having the polymkeric substance that is grafted in melt or the solution when radical initiator such as cumyl hydroperoxide exist.
That describes under the title of polymer A also can be used as rubber particularly including ethylene copolymer at interior alpha-olefin copolymer, rather than makes polymer A, thereby can mix with novel compositions.
The suitable elastomerics of another combination contains core-shell joint branch rubber.They are the graft rubbers that prepare in emulsion and comprise at least a hard component and a kind of soft component.Hard component is generally understood as the polymkeric substance that second-order transition temperature is at least 25 ℃, and soft component is meant that second-order transition temperature is no more than 0 ℃ polymkeric substance.The structure of this class product comprises a nuclear core and one deck shell at least, and this structure depends on monomeric addition sequence.Soft component generally from divinyl, isoprene, alkyl acrylate, alkyl methacrylate or siloxanes and, as needs, other comonomer-derived.For example, the preparation of suitable siloxanes nuclear core can start from ring-type oligomerisation prestox tetrasiloxane or tetrem thiazolinyl tetramethyl-tetrasiloxane.These compounds can with γ-sulfydryl propyl group methyl dimethoxysilane generation open loop cationoid polymerisation, preferably under the condition that sulfonic acid exists, carry out polymerization, form the soft core of siloxanes.This siloxanes can be crosslinked, and method is for example, polyreaction for example to be carried out in the presence of tetraethoxysilane, methyltrimethoxy silane or the phenyltrimethoxysila,e at the silane that contains hydrolysable group such as halogen or alkoxyl group.The example of suitable here comonomer is that vinylbenzene, vinyl cyanide and cross-linking monomer or the grafting with an above polymerizable double bond are connected monomer, as diallyl phthalate, Vinylstyrene, butylene glycol diacrylate or (different) cyanuric acid alkatriene propyl diester.Hard component generally is the comonomer-derived of preferably mentioning from vinylbenzene, alpha-methyl styrene and multipolymer thereof, vinyl cyanide, methacrylonitrile and methyl methacrylate etc. and coming.
Preferred core-shell joint branch rubber contains a soft core and duricrust or hard core, the first layer soft shell and another layer duricrust at least.Here, the adding of functional group such as carbonyl, carboxyl, anhydride group, amide group, imide, carboxylicesters, amino, hydroxyl, epoxy group(ing), oxazoline, urethano, urea groups, lactan or halogenophenyl etc. preferably realizes by add suitable functionalized monomer during the outermost shell polyreaction.Suitable functionalized monomer's example has monoesters or diester, (methyl) tert-butyl acrylate, vinylformic acid, (methyl) glycidyl acrylate and the vinyl oxazoline of toxilic acid, maleic anhydride, toxilic acid.Band monomer's amount is generally 0.1～25 weight % of core-shell joint branch rubber gross weight, preferred 0.25～15 weight %.Soft component was generally preferred 3: 7～8: 21: 9～9: 1 with the weight ratio of hard component.
It is known that this class increases polymeric amide flexible rubber, and is for example having description among the EP-A 208 187.
Another kind of suitable impact modifying agent comprises thermoplastic polyester elastomer.Polyester elastomer is meant and contains the long-chain section and lack the segmental block copolyether ester that described long-chain section is generally derived from poly-(alkylidene group) ether glycol, and described short chain section is generally derived from low molecular weight diols and dicarboxylic acid.This class product is well-known, in the literature, and for example existing description among the US-A 3 651 014.Suitable product has commodity selling, and its commodity are called Hytrel  (E.I.Du Pont Company), Arnitel  (Akzo company) and Pelprene  (Toyobo company limited).
Certainly also can adopt the mixture of different rubber.
Composition of the present invention can also contain filler or toughener, and its consumption is generally 0～40 weight % of composition total weight.
The example of bat wool or toughener has carbon fiber, potassium titanate crystal whisker, Kevlar and preferred especially, glass fibre.When adopting glass fibre, can handle it, to improve the consistency of fiber and body material with sizing material and short stick.In general, the used carbon fiber and the diameter of glass fibre are 6～20 μ m.
Glass fibre can add with staple fibre and rove form.In the injection-molded item of forming, the mean length of glass fibre is preferably 0.08～0.5mm.
Carbon fiber and glass fibre also can use with forms such as cloth, pad or glass rovings.
Suitable particulate filler is soft silica, carbonate such as magnesiumcarbonate (chalk), Powdered quartz, mica, various silicate such as clay, white mica, biotite, suzoite, toxilic acid tin, talcum powder, chlorite (chlorite), phlogopite, feldspar and Calucium Silicate powder such as wollastonite or kaolin, particularly burnt kaolin.
In an especially preferred embodiment, adopt particulate filler, wherein, measure, have 95 weight % at least with final product, the particle of preferred at least 98 weight % has less than 45 μ m, preferably less than the diameter (overall dimension) of 40 μ m, and, measure with final product, length-to-diameter ratio is 1～25, preferred 2～20.
For example, particle diameter can be measured by the electron photomicrograph of record blend polymer thin slice, and with at least 25 filler particles, preferably at least 50 particles are estimated.Particle diameter also can be measured with sedimentation analysis by the 491st page of literary composition of Transactions of ASAE (1983).Diameter also can use sreen analysis (screen analysis) method to measure less than the weight fraction of the filler of 40 μ m.Length-to-diameter ratio is the ratio of particle diameter and thickness (overall dimension and minimum size).
Particularly preferred particulate filler is talcum powder, kaolin such as burnt kaolin or wollastonite, or the mixture of two kinds or all these fillers.Wherein, particularly preferably being diameter is the talcum powder that 1.5～25 particle accounts for 95 weight % at least less than 40 μ m, length-to-diameter ratio, all measures with final product in each case.The preferred diameter of kaolin is that 1.2～20 particle accounts for 95 weight % persons at least less than 20 μ m and length-to-diameter ratio.In each case, all measure with final product.
The example of other additive has processing aid, stablizer and oxidation inhibitor, thermo-stabilizer, ultra-violet stabilizer, lubricant and releasing agent, fire retardant, dyestuff and pigment and softening agent.Their consumption generally mostly is most 40 weight % of composition total weight, preferably is no more than 15 weight %.
The content of pigment or dyestuff is generally 0～4 weight %, preferred 0.5～3.5 weight %, particularly 0.5～3 weight %.
It generally is known being used to make the painted pigment of thermoplastics, for example, with reference to R.Gachter and H.Muller at Taschenbuch der Kunststoffadditive, Carl HanserVerlag, 1,983 494～510 pages paper.One group of first-selected pigment comprises white pigment such as zinc oxide, zinc sulphide, white lead (2PbCO 3Pb (OH) 2), lithopone, stibium trioxide and titanium dioxide.In the modification crystal (rutile and anatase octahedrite) of two kinds of the most frequently used titanium dioxide, make this novel moulding material have white with granular rutile.
According to the present invention, the available black pigment is iron oxide black (Fe 3O 4), spinel black (Cu (and Cr, Fe) 2O 4), manganese black (mixture of Manganse Dioxide, silicon oxide and ferric oxide), cobalt black and antimony black and, preferred especially, carbon black, generally (here with furnace treated black or channel black, with reference to the Pigmente fur Anstrichmittel of G.Benzing, Expert-Verlag (1988) is from the 78th page).
According to the present invention, certainly obtain certain tone with inorganic colourant such as chromoxide green or organic colorant such as azo pigment and phthalocyanine.This class pigment generally all has commodity selling.
Using described pigment or dyestuff with the formation of mixture, for example carbon black is mixed use with CuPc, also may be favourable, because generally this all helps the dispersion of pigment in thermoplastics.
According to the present invention, the oxidation inhibitor and the thermo-stabilizer that can join in the thermoplastic material have, for example the halogenide of I family metal such as sodium halide, potassium halide and lithium halide in the periodictable if necessary, also are used in combination as cupric chloride (I), cupric bromide (I) and cupric iodide (I) with copper halide (I).Halogenide, particularly copper halide may also contain electron rich π ligand.The example of this class copper complex be copper halide (I) with, for example, the title complex of triphenyl phosphine.Also can use zinc fluoride and zinc chloride.Further, also available space hindered phenol, quinhydrones (being Resorcinol), substituent this compounds, secondary aromatic amine are arranged, as needs, also be used with phosphorated acid or their salt, the also mixture of available this compounds, preferred concentration is no more than 1 weight % of mixture total weight amount.
The example of ultra-violet stabilizer be have various substituent Resorcinols, salicylate, benzotriazole and benzophenone.Its consumption generally is no more than 2 weight %.
Can join the ester that lubricant in the thermoplastic material and releasing agent have stearic acid, Stearyl alcohol, stearic acid alkyl ester and stearylamide and tetramethylolmethane and longer chain fatty acid to form, its consumption generally is no more than 1 weight %.Also available stearic calcium salt, zinc salt or aluminium salt and and dialkyl ketone such as distearyl ketone.
The advantage that this novel method is better than well-known technology is particularly: the chain length of thermoplastic polymer A only slightly shortens, if shortening is arranged, and polymer A consequently makes composition have the good mechanical performance to disperse to such an extent that very thin form is present in the composition.Especially said composition that outstanding is has good rigidity, good mobile and good characteristics such as toughness.
Another advantage is: with the light true qualities of composition band of this novel method acquisition.
Owing to contain polymer A and the polymeric amide B of cutting apart carefully especially with the composition that this novel method obtained, be suitable between component incompatible each other but with said composition in polymer A or the compatible blend of polymeric amide B in make expanding material.
In polymer A compatible polymers blend in the composition, the example of suitable component α is a described component under the A title.Component α can contain a kind of polymkeric substance or two or more mixture of polymers.The selection principle of component α is to make it be equivalent to polymkeric substance or polymer A in the composition.But component α can be different with A.Therefore, α can be a kind of polyphenylene oxide, and A is a kind of styrene polymer, and perhaps, α can be a kind of polyphenylene oxide with certain structure, and A is a kind of different poly (arylene ether) of forming.Polymer A also can be different with α, for example, has different molecular weight or molecular weight distribution.In general, the content of component α in blend polymer is 1～97 weight % of blend polymer gross weight, preferred 5～90 weight %.
As mentioned above, suitable component β be with composition in all compatible polymkeric substance of polymeric amide B.Can be with the mixture of a kind of polymkeric substance β or two kinds or multiple different polymkeric substance β.What especially preferably adopt is polyamide thermoplastic.This class polymeric amide is well-known, comprises that weight-average molecular weight is at least semi-crystalline state and the amorphous resin of 5000g/mol, is referred to as nylon usually.This class polymeric amide is as United States Patent (USP) 2,071, description all arranged in 250,2,071,251,2,130,523,2,130,948,2,241,322,2,312,966,2,512,606 and 3,393,210.
Polymeric amide β can pass through, for example, with the saturated or aromatic diamines saturated or aromatic dicarboxylic acid and maximum 14 carbon atoms of 4～12 carbon atoms etc. the mole polycondensation prepare, perhaps prepare by the polycondensation of omega-amino-carboxylic acid or the polyaddition reaction of corresponding lactan.
The example of this class polymeric amide has polyhexamethylene adipamide (nylon 66), polyhexamethylene azelaoyl amine (nylon 69), polyhexamethylene sebacoyl amine (NYLON610), polyhexamethylene lauramide (nylon 612), polymeric amide that obtains by the lactan open loop such as polycaprolactam and nylon 12 and, further, the amino undecanoic acid of poly-11-, and from the polymeric amide of two (right-aminocyclohexyl) methane with the dodecanedioic acid acquisition.
Also can be with the multipolymer of the multipolymer by making polymeric amide that two kinds or multiple above-mentioned polymkeric substance or their component copolycondensation prepare such as hexanodioic acid, m-phthalic acid or terephthalic acid and hexamethylene-diamine or hexanolactam, terephthalic acid and hexamethylene-diamine as component β.This class partially aromatic copolyamides generally contain 40～90 weight % from unit that terephthalic acid and hexamethylene-diamine derive out.Can be with m-phthalic acid or other aromatic dicarboxylic acid, preferred carboxyl is in the dicarboxylic acid of contraposition, replaces a spot of terephthalic acid, preferably is no more than 10 weight % of used aromatic dicarboxylic acid total amount.
Other monomer that is applicable to preparation polymeric amide β is the cyclic diamine as general formula I V:
Figure A9718119600251
Wherein, R 1Be hydrogen or C 1-C 4-alkyl, R 2And R 3All be C 1-C 4-alkyl or hydrogen.
Particularly preferred diamines IV is two (4-aminocyclohexyl) methane, two (4-amino-3-methylcyclohexyl) methane, 2,2-two (4-aminocyclohexyl) propane and 2,2-two (4-amino-3-methylcyclohexyl) propane.
Other example of diamines IV has 1,3-and 1,4-cyclohexane diamine and isophorone diamine.
Except that containing from the unit that terephthalic acid and hexamethylene-diamine derive out, partially aromatic copolyamides also contains from the unit that ε-Ji Neixianan derives out and/or from unit that hexanodioic acid and hexamethylene-diamine derive out.
The unitary content of deriving out from ε-Ji Neixianan mostly is 50 weight % most, preferred 20～50 weight %, particularly 25～40 weight %, and from unit that hexanodioic acid and hexamethylene-diamine derive out 60 weight % the most nearly, preferred 30～60 weight %, particularly 35～55 weight %.
Copolyamide also can contain the unit of ε-Ji Neixianan unit and hexanodioic acid and hexamethylene-diamine simultaneously.In this case, should guarantee not have the unitary amount of aromatic group to be at least 10 weight %, preferably at least 20 weight %.Be not subjected to any special restriction from the ratio of unit that ε-Ji Neixianan derives out and the unit of deriving out from hexanodioic acid and hexamethylene-diamine.
Proved already, contain 50～80 weight %, particularly 60～75 weight % are from unit that terephthalic acid and hexamethylene-diamine derive out with contain 20～50 weight %, the unitary polymeric amide β that derives out from ε-Ji Neixianan of preferred 25～40 weight % is to the purposes particularly advantageous of many expections.
Partially aromatic copolyamides β can be by for example EP-A-129 195 and EP 129 196 described method preparations.
Preferred partially aromatic polymeric amide β is tertiary amine unit wherein, and particularly two (hexa-methylene triamine) content is less than the polymeric amide of 0.5 weight %.Tertiary amine content is that 0.3 weight % or partially aromatic polymeric amide still less are particularly preferred.
Preferred employing fusing point is higher than 200 ℃ linear polymeric amide as component β.
Preferred polymeric amide β is polyhexamethylene adipamide, polyhexamethylene sebacoyl amine and polycaprolactam and polyamide 6/6T and polyamide 66/6T and the polymeric amide that contains the cyclic diamine comonomer.The solution that with the concentration of polymeric amide in 96% sulfuric acid is 1 weight % is in 23 ℃ of mensuration, and the relative viscosity of this class polymeric amide is generally 2.0～5, and corresponding number-average molecular weight is 15,000～45,000.Preferred employing relative viscosity is 2.4～3.5, particularly 2.5～3.4 polymeric amide.
For example, other example of component β is the polymeric amide (polymeric amide 4,6) that can be obtained by 1,4 diaminobutane and hexanodioic acid polycondensation at high temperature.The method for preparing the polymeric amide with this structure has among EP-A38 582 and the EP-A39 524 and describes at for example EP-A38 094.
The amount of component β can be 1～97 weight % of blend polymer gross weight in the blend polymer, preferred 5～90 weight %.
According to the present invention, the composition that uses as expanding material γ in blend polymer can just use with composition itself or after adding additive.Preferably make component γ with composition itself.The content of component γ is generally 2～80% of blend polymer gross weight in the blend polymer, preferred 5～70 weight %.
In addition, blend polymer also can contain other component δ, the mixture of promptly a kind of rubber impact modifiers or two kinds or multiple rubber impact modifiers.Suitable component δ is the aforementioned compositions additive.This component γ contains rubber impact modifiers, and extra contained component δ can be the same or different in the latter and the blend polymer.The amount of the contained component δ of blend polymer for example is generally the blend polymer gross weight, 0～30 weight %, preferred 0～25 weight %.
In a preferred embodiment, blend polymer contains filler or toughener ε.The example of appropriate filler or toughener is the filler and the toughener of foregoing.
Blend polymer for example can contain 0～40%, the component ε of preferred 0.5～20 weight %.
In addition, blend polymer can contain additive χ, as processing aid, stablizer, oxidation inhibitor, thermo-stabilizer, photostabilizer, lubricant or releasing agent, fire retardant, dyestuff and pigment or softening agent.Certainly, blend polymer also can contain the mixture of two kinds or multiple additives.The additive that can be used in the blend polymer comprises above-mentioned composition additive.Component χ may be different from additive used in the component.In general, the content of component χ is 0～30 weight % of blend polymer gross weight in the blend polymer, preferred 0～20 weight %.
For example, blend polymer can prepare with following method: at traditional mixing equipment such as mixing roll, kneader, forcing machine such as screw extrusion press, and preferred twin screw extruder, or in runner milling such as Banbury or the Brabender runner milling, each component is mixed, then mixture is extruded.
Usually extrudate will be through cooling and pelletizing after extruding.
Each component blended order can change.Therefore can with two kinds or, as needs, three kinds of component elder generation premixs, but also all components can be mixed together.
Thorough mixing helps obtaining moulding material very uniformly.In general, for realizing this purpose, requiring the average mixing time at 280～380 ℃ is 0.2～30 minute.
The most outstanding characteristics of this blend polymer are to have good toughness.Composition and blend polymer all are suitable for producing moulded product, film or fiber.The field that this class material is convenient to use especially is an automotive industry.
The characteristics of examples test
The unitary amount that contains acidic group among the poly (arylene ether) sulfone A2 is pressed people such as Parsons in Polymer the 34th phase (1994), described in 2836 page of one literary composition 1The H-nmr for the determination.
The viscosity number of poly (arylene ether) sulfone is that the solution of 1 weight % is in 25 ℃ of mensuration with its concentration in N-Methyl pyrrolidone.
The molecular weight of poly (arylene ether) is measured with gel permeation chromatography (by the described condition of explanation part).
The dried granules of composition is processed into small-sized bar-shaped sample, disk sample and the tension specimen of standard.Exsiccant blend polymer pellet is processed into bar-shaped sample of ISO and disk.At melt temperature is that 280 ℃, die temperature are to process under 80 ℃ the condition.
Melt volume index (MVI) is measured under 275 ℃ and 5kg load.
Young's modulus [N/mm 2] press DIN 53 457 initial slope from the tensile stress curve and measure, the test rate that acts on tension specimen is 1mm/min (getting the mean value of 10 test-results).
Notched Izod impact strength (a k[kJ/m 2]) measure by DIN 53 453 usefulness standard small samples: the standard small sample to free support imposes abrupt impact, measures to make the required energy of sample fracture (surveying 10 times).
Shock strength (a n[kJ/m 2]) press ISO 179 first parts and measure with the non-notch sample.
Penetrate total energy (W AlwaysN/m) pressing DIN 53 443 usefulness disk samples measures: with the disk of a piercing element with constant speed (4.5m/s) puncture clamping.Determine to penetrate total energy (surveying 5 times) from power-inflection curves.
The color of visually rank composition.The grade of color is divided into very shallow (1), taupe brown (2), light brown (3) to brown (4) and dark-brown (5).Amorphous polymer A1-A4A1: the poly (arylene ether) sulfone has the repeating unit of general formula I 2, with the viscosity number of 48ml/g
Be feature, for example the Ultrason  S1010 of BASF AG.A2: the poly (arylene ether) sulfone that contains acidic group
With 4 of the dihydroxyphenyl propane of the dichloro diphenylsulfone of 5.742kg, 4.374kg and 112g, 4 '-dihydroxy-acid is dissolved in the N-Methyl pyrrolidone of 29kg and adds the Anhydrous potassium carbonate of 2.820kg in nitrogen atmosphere.
Earlier reaction mixture is heated to 180 ℃ and kept 1 hour under 300 millibars of pressure, constantly boils off the water and the N-Methyl pyrrolidone of reaction generation simultaneously, reacted again 6 hours in 190 ℃ then.
After adding the 40kg N-Methyl pyrrolidone, the elimination inorganic component.Add the 50ml Glacial acetic acid with in and basic group.Then polymkeric substance is precipitated out from water.The water extract product, then with product in 140 ℃ of drying under reduced pressure.Obtain white powder.
Recording the unitary amount of band acidic group with the H nucleus magnetic resonance is 1.4 weight %, and the viscosity number of product is 38.1ml/g.A3: polyphenylene oxide: it is characterized by: with the chloroform is the weight average branch that solvent records with gel permeation chromatography
The son amount is 40,000g/mol.A4: the multipolymer of vinylbenzene and vinyl cyanide is characterized by: acrylonitrile content is 25 weight %, and is sticking
The degree value is that 80ml/g (is that 0.5% dimethyl formamide solution is in 25 ℃ with polymer concentration
Measure, for example, the Luran  358N of BASF AG).Addition of C 1: fiber thickness is 10 μ m and the glass fibre that has polyurethane compositions.C2: mean particle size is the talcum powder of 1.5 μ m.D:, it is characterized in that MFI is 3g/10 minute (recording in 230 ℃) under the effect of 2.16kg load with toxilic acid/maleic anhydride modified ethylene-propylene rubber(EPR) of 0.7 weight %.The preparation of composition 1 and comparison test V6 and V7
8kg polymer A 1 is dissolved in the 24kg hexanolactam.After adding 1000g water, this mixture is heated to 235 ℃ in stirring tank, interior pressure is 7.5 crust.After the precondensation 2 hours, in 1.5 hours, container pressure is lowered, carried out aftercondensated 2.5 hours at 235 ℃ then.
Then with melt discharging and granulation from still.With the resulting pellet of hot-water extraction.
The characteristic of the product of gained is shown in table 1.
Prepare composition 2-5 with similar approach, V6 and V7.Used amount and testing of characteristic gained the results are shown in table 1.
Comparative example
For comparison purpose, poly (arylene ether) A1 is mixed in 280 ℃ in forcing machine (ZSk 30 of Werner and Pfleiderer company) with polyamide 6, then with mixture pelleting, being characterized as of described polyamide 6: with its concentration in 96% sulfuric acid is that the viscosity number that 0.5% solution records is 146ml/g, (for example Ultramid B of BASF AG).With the pellet of gained 80 ℃ of drying under reduced pressure 6 hours.The results are shown in table 1 (V8).
Also with the similar approach preparation, only difference is: the processing of moulding compound V11 is to carry out under 250 ℃ melt temperature to moulding compound V9-V11.
Table 1
Composition 1 2 3 4 5 V6 V7 V8 V9 V10 V11
ε hexanolactam (kg) 24 27 24 24 24 24 24
A1(kg) 8 3 7 - - - - 1.5 1.31 - -
A2(kg) - - 1 - - - - - 0.19 - -
A3(kg) - 8 - -- - 1.5 -
A4(kg) - - - - 8 - - - - - 1.5
Water (kg) 1 1 1 1 1 0 5.5 - - - -
Polyamide 6 (kg) - - - 4.5 4.5 4.5 4.5
Preparation technology S S S S S S S E E E E
Performance
a n[kJ/m 2] 345 404 410 376 319 a) 103 78 210 67 120
W Always[Nm] 33.4 46.6 43.2 29.1 34.2 - 1.1 1.2 3.2 0.9 1.1
MVI [m1/10′] 178 234 246 231 248 - ＞250 145 149 178 201
Color 1 1 1 1 1 - 2 2 2 3 2
S: stirring tank E: forcing machine is no polyreaction a)
To in forcing machine under 280 ℃ melt temperature, the composition 1,2 and 5 of granulation mixes with glass fibre C or rubber D.Then with mixture pelleting and be processed into sample.
For comparison purpose, the polymer A 1 of granulation or the moulding compound of A4 and polyamide 6 are mixed (with reference to comparison example V15 and V16) in a similar manner with glass fibre C in forcing machine.The mechanical property of said composition and product is as shown in table 2.
Table 2
Example 12 13 14 V15 V16 17 18 19 ??V20
Component (weight %) composition 1 70 - - - - 80 - 67.5 -
Composition 2 - 70 - - - - - -
Composition 5 - 70 - - - 80 -
A1 - - 17.5 - - - 16.8
A4 - - - 17.5 - - -
Polyamide 6 - - 52.5 52.5 - - 50.7
C1 30 30 30 30 30 - - - -
C2 - - - - - - - 12.5 12.5
D - - - - - 20 20 20 20
Performance
a n[kJ/m 2] 80 67 59 55 32 - - 347 97
a k[kJ/m 2] - - - - - 56 49 17 5
Young's modulus [N/mm 2] 9200 9550 10100 9200 9700 2000 2150 2800 2900
W Always[Nm] - - - - - 78 69 78 2
MVI*) [ml/10′] 88 105 108 68 87 76 165 20 17
*) under 275 ℃ and the effect of 5kg load, measure.Blend polymer: component α 1: poly (arylene ether) A1 component α 2: styrene-acrylonitrile copolymer A4 component α 3: polyphenylene oxide A3 component β 1:
Polycaprolactam (polyamide 6, for example the Ultramid  of BASF AG) B 3, be feature (pressing DIN 53 727, is that the solution of 0.5 weight % records with its concentration in 96% sulfuric acid) with the viscosity number of 150ml/g.Component γ 1: composition 1 component γ 2: composition 3 component γ 3: composition 4 component δ 1: the preparation of rubber D blend polymer
Each component was mixed 250 minutes in 270～320 ℃ of productive rates with 10kg/h in twin screw extruder (ZSK 30 of Werner and Pfleiderer company), extrude, then granulation.Pellet injection moulding after drying is a sample.The weight of blend polymer is formed and mechanical test the results are shown in table 3.
Table 3
Example 21 V22 23 V24 25 V26 27 V28 V29 30
Component (weight %)
α1 - 10.6 - - - - - 9 30 27
α2 - - - 10.6 - - - - - -
α3 - - - - - 10.6 - - - -
β1 60 89.4 60 89.4 60 89.4 51 76 70 63
γ1 40 - - - - - 34 - - 10
γ2 - - - - - - - - - -
γ3 - - 40 - 40 - - - - -
δ1 - - - - - - 15 15 - -
Performance
a nkJ/m 2] 356 214 324 138 361 167 404 301 126 324
a k[kJ/m 2] 4.3 2.4 3.9 1.4 4.2 2.4 34.1 12.5 2.3 4.0
W s[Nm] 35.1 11.2 27.1 2.1 22.4 3.2 57.0 24.1 2.1 24.1
Table 3 (continuing)
Example V31 32 V33 34 35 V36 37 38
Component (weight %)
α1 25.5 23 - - - - - -
α2 - - 30 27 23 - - -
α3 - - - - - 30 27 23
β1 59.5 53.5 70 63 53.5 70 63 53.5
γ1 - 8.5 - - - - - -
γ2 - - - 10 8.5 - - -
γ3 - - - - - - 10 8.5
δ1 15 15 - - 15 - - 15
Performance
a n[kJ/m 2] 252 412 87 145 317 98 287 367
a k[kJ/m 2] 11.4 31.2 1.6 3.5 12.3 2.5 4.1 17.5
W s[Nm] 32.1 54.4 1.5 11.2 31.2 2.3 21.2 45.2

Claims (14)

1. one kind prepares the method for compositions that contains at least a thermoplastic polymer A and at least a polymeric amide B, described method be thermoplastic polymer A be dissolved at least a lactan b and, if desired, other forms among the monomer b of polymeric amide, make monomer b polymerization then, wherein at least a lactan b and, if desired, the monomer b that forms polymeric amide in addition is a polymeric under the condition that the water of 0.001～5 weight % that accounts for monomer b weight exists.
2. the method for claim 1, wherein used polymer A is polyetherimide, poly (arylene ether), polyphenylene oxide, polystyrene, styrol copolymer or ethylene copolymer.
3. method as claimed in claim 1 or 2, wherein used lactan b is a ε-Ji Neixianan.
4. as any one described method in the claim 1～3, wherein molecular weight is improved in further step.
5. method as claimed in claim 4, wherein the raising of molecular weight is that combination by extracting or heating or these two kinds of measures realizes.
6. according to the composition of any one described method preparation in the claim 1～4.
7. composition as claimed in claim 6, it comprises at least a rubber, filler or toughener or other additive or two or more mixture wherein.
The described composition of claim 6 in blend polymer as the purposes of expanding material.
9. the blend polymer that contains the described composition of claim 6.
10. blend polymer as claimed in claim 9, it contains filler or toughener.
11. blend polymer as claimed in claim 9, it contains the talcum powder as filler or toughener.
12. as any one described blend polymer in the claim 8～10, it contains
α) at least a and polymer A compatible polymers of 1～97 weight %
β) at least a and polymeric amide B compatible polymers of 1～97 weight %
γ) the described composition of the claim 6 of 2～80 weight %
δ) the rubber impact modifiers of 0～40 weight %
ε) filler of 0～60 weight % or toughener or their mixture
χ) the additive wherein wt percentage number average of 0～30 weight % is based on the gross weight of blend polymer.
13. the purposes that any one described blend polymer is used to produce moulded product, film or fiber among described composition of claim 6 or the claim 7-11.
14. contain the moulded product of the described composition of claim 6, film or fiber.
CN 97181196 1996-11-04 1997-10-21 Process for preparing compositions based on thermoplastic polymers and polyamides Pending CN1242791A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007134550A1 (en) * 2006-05-23 2007-11-29 Shanghai Genius Advanced Material Co., Ltd. A method for preparing nylon microsphere and the same
CN100406521C (en) * 2003-09-18 2008-07-30 旭化成化学株式会社 Resin composition excellent in stability to face impact
CN105263988A (en) * 2013-04-04 2016-01-20 巴斯夫欧洲公司 Polymerizable lactam composition containing a sulfonated polyaryl sulfone
CN116925543A (en) * 2023-09-13 2023-10-24 东华大学 Antistatic polyamide composition and preparation method and application thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100406521C (en) * 2003-09-18 2008-07-30 旭化成化学株式会社 Resin composition excellent in stability to face impact
WO2007134550A1 (en) * 2006-05-23 2007-11-29 Shanghai Genius Advanced Material Co., Ltd. A method for preparing nylon microsphere and the same
CN101077910B (en) * 2006-05-23 2010-06-09 上海杰事杰新材料股份有限公司 Method for preparing particle diameter controllable high molecular weight nylon micro-sphere
US8048967B2 (en) 2006-05-23 2011-11-01 Shanghai Genius Advanced Material (Group) Company, Ltd. Method for preparing nylon microspheres and nylon microspheres prepared thereby
CN105263988A (en) * 2013-04-04 2016-01-20 巴斯夫欧洲公司 Polymerizable lactam composition containing a sulfonated polyaryl sulfone
CN116925543A (en) * 2023-09-13 2023-10-24 东华大学 Antistatic polyamide composition and preparation method and application thereof
CN116925543B (en) * 2023-09-13 2024-01-02 东华大学 Antistatic polyamide composition and preparation method and application thereof

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