CN1040041A - Polymer composition - Google Patents
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- CN1040041A CN1040041A CN89106236A CN89106236A CN1040041A CN 1040041 A CN1040041 A CN 1040041A CN 89106236 A CN89106236 A CN 89106236A CN 89106236 A CN89106236 A CN 89106236A CN 1040041 A CN1040041 A CN 1040041A
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Abstract
But demonstrate the improvement character of shock strength and modulus in flexure by the mixture of the segmented copolymer of the local hydriding of the maleation of the polymkeric substance of a kind of carbon monoxide and at least one unsaturation ene compound preparing linear alternating and specific quantity.
Description
The present invention relates to a kind of improved polymer composition, it mainly comprises a kind of preparing linear alternating polymkeric substance that is made of carbon monoxide and at least a alefinically unsaturated compounds.
Following period of time in the past, people have known the polymer classes of relevant alkene and carbon monoxide.
Recently, the classification of the preparing linear alternating polymkeric substance that carbon monoxide and at least a alefinically unsaturated compounds constitute has caused people's very big interest, and some reasons are because the increasing use value of this polymkeric substance.These usually are known as polyketone class or polyketane polymers class, and known its repeating structure is-CO-(A)-, wherein A is the alefinically unsaturated compounds part that is polymerized through the unsaturated position of alkene.For example, when this compound was ethene, this polymkeric substance was by the repeat unit structure formula
Represent.Recently the general method of producing this base polymer disclosed in european patent application specification sheets 121965 and 181014.This method refers more particularly to the catalyst composition that the bidentate ligand of the negatively charged ion of a kind of compound by palladium, cobalt or nickel, strong non-haloid acid and phosphorus, arsenic or antimony forms.
The polymkeric substance that is generated is the higher thermoplastics of molecular weight.These plastics have been determined and have been used to produce moulded products, for example are used for the container of food and drink industry, and can be used for the inside and outside part of automobile, and these parts are made by processing polyketone base polymer according to known method.Have now found that, preferably how much has the character that some are different from those polyketane polymers for some special application requiring polymer composition, best is to keep the desirable character of polyketane polymers can improve other character again, especially should improve its impact strength and flexural modulus.
The mixture that has now found that a kind of polyketane polymers and certain segmented copolymer can provide this improved performance.
Therefore, the present invention relates to a kind of polymer composition, it is characterized in that it contains the preparing linear alternating polymkeric substance that a kind of carbon monoxide and at least a alefinically unsaturated compounds constitute, and the non-molten mixed mixture of another kind of (can be maleation) partially hydrogenated at least segmented copolymer, this segmented copolymer has an A block that mainly is polymerized by vinyl aromatic compounds at least and also has a B block that mainly is polymerized by conjugated alkadiene at least.
The polyketane polymers that is used in the present composition is the preparing linear alternating polymkeric substance that is made of carbon monoxide and at least a olefinically unsaturated compounds.This unsaturated compound can be a kind of hydrocarbon polymer or heterozygosis compound, for example, and esters of acrylic acid.Suitable ethylenically unsaturated hydrocarbons class as the polyketane polymers parent has until 20 carbon atoms (comprising 20), preferably have until 10 carbon atoms (comprising 10), they are that fatty compounds such as ethene comprise alpha-olefins such as propylene, butylene, iso-butylene, 1-hexene, 1-octene and 1-dodecylene with other, or on other aliphatic molecule, contain aromatic substituent, the aromatic yl aliphat compound of aromatic substituent on the carbon atom of the unsaturated position of alkene especially.The example of this back one class ethylenically unsaturated hydrocarbons have vinylbenzene ,-vinyl toluene, right-ethyl styrene and p-methylstyrene.Polyketane polymers is the multipolymer of carbon monoxide and ethene preferably, or carbon monoxide, ethene and have the terpolymer of the hydrocarbon polymer (the particularly alpha-olefins as the propylene) of 3 carbon atoms at least.
The structure of polyketane polymers is the preparing linear alternating polymkeric substance of carbon monoxide and ethylenically unsaturated hydrocarbons compound, and this polymkeric substance is whenever to contain the just corresponding hydrocarbon polymer part of carbon monoxide part on substantially.When mixture of the present invention uses the terpolymer of carbon monoxide, ethene and a kind of second hydrocarbon, have the unit of 2 unit that contain ethylene moiety at least to there being one to contain second kind of hydrocarbon polymer part, preferably have 10 to 100 unit that contain ethylene moiety then corresponding have only a unit that contains second kind of hydrocarbon polymer part.The structural formula of this polymer chain is expressed as:
Wherein D is the second kind of hydrocarbon polymer part that is polymerized by the unsaturated position of alkene.Have found that
The unit and
The unit is random through polymer chain, and the ratio of y: x is not more than 0.5.In this modification, be used for the carbon monoxide of mixture of the present invention and the multipolymer of ethene and can not contain second kind of hydrocarbon polymer, at this moment be used for representing y=0 in the said structure formula of this polymkeric substance.When y was other value of non-zero, when promptly using terpolymer, the ratio of y: x was preferably from 0.01 to 0.1.Whether the end group of polymkeric substance or " cap " depend on the material that occurs in the production processes of polyalcohol and are how with polymer purification.The accurate physical properties of polymkeric substance does not depend on the discrete end group to a great extent, so the complete available above-mentioned polymer chain structural formula of this polymkeric substance is represented.
Interesting especially is that molecular-weight average is 1000～200000 polyketone, especially by the GPC(gel permeation chromatography) molecular weight of mensuration is those polyketone of 20000～90000.The physical properties of polymkeric substance depends in part on molecular weight, and this polymkeric substance is copolymer or terpolymer.Having is exactly the relative ratios of second kind of hydrocarbon polymer in terpolymer again.The representational fusing point of this polymkeric substance is from 175 ℃ to 300 ℃, more commonly from 210 ℃ to 270 ℃.With the capillary viscosity measuring apparatus of standard under 60 ℃ in-intrinsic viscosity (LVN) of measuring polymkeric substance in the cresols is 0.5 to 10, is generally 0.8 to 4.Preparing linear alternating polymkeric substance and second kind of component produce synergy, and be all the more so when especially LVN is in 1.5 to 2.0 scope.
Now having become general a kind of method of producing this polymkeric substance is that carbon monoxide is contacted in the presence of a kind of catalyst composition with hydrocarbon polymer, and this catalyst composition is to be formed by a kind of palladium compound, the negatively charged ion of non-haloid acid (its PKa is less than about 6 greatly) and a kind of bidentate ligand of phosphorus.A kind of like this method of producing polyketone exists, for example illustrates among the EP-A-222454.
Second kind of segmented copolymer that component is a kind of modification in the present composition, it by partial hydrogenation and can, but preferably, further be grafted to and carry out further modification on the segmented copolymer chain by the maleinization compound." segmented copolymer one speech is used for representing a kind of thermoplastic elastomer, it is characterized in that it has a block at least is the block (A block) that at least mainly is polymerized by vinylaromatic hydrocarbon and to also have another block at least be the main at least block (B block) that is polymerized by alkadiene.
Vinylaromatic hydrocarbon as A block parent has a vinylidene, i.e. one＞C=CH
2Base, this base directly are connected on the aromatic nucleus, and this vinylaromatic hydrocarbon has until 12 carbon atoms (comprising 12).This vinyl aromatic compound is vinylbenzene and vinylbenzene homologue preferably, as those compounds of representing by following structural formula:
Wherein R may optionally be hydrogen or until 4 carbon atoms alkyl of (comprising 4).The example of this compound have vinylbenzene, alpha-methyl styrene, α-ethyl styrene, p-methylstyrene, right-ethyl styrene ,-propylstyrene and α, the 4-dimethyl styrene, and vinylbenzene and alpha-methyl styrene have constituted vinyl aromatic compound classification preferably, and especially vinylbenzene is good especially.
The A block of segmented copolymer at least mainly is polymerized by vinyl aromatic compound, and the block of homopolymerization preferably.Yet on the other hand, monomer that one or more A blocks are some of them B block and the main monomer of block A carry out the block that copolymerization forms.Such block is called as " wedging " and contains the 85(mole at least) %, preferably contain the 93(mole at least) % polymeric vinylaromatic hydrocarbon, all the other are the conjugated alkadiene of B block.The block A that contains the vinyl aromatic hydrocarbon monomer mixture also is suitable for, but not so good.The molecular-weight average of block A is generally 5,000 to 125,000, and be 7000 to 125,000 o'clock better.
Each B block at least mainly is polymerized by conjugated alkadiene.Alkadiene monomer as the B block is that the structural formula of this class conjugated alkadiene is until 8 carbon atoms conjugated alkadiene of (comprising 8):
The definition of R wherein is same as above.The example of this class alkadiene has divinyl, isoprene, 2,3-dimethylbutadiene, 1,3-octadiene, 1,3-pentadiene and 2-methyl isophthalic acid, 3-hexadiene.Being preferably divinyl and isoprene in the alkadiene, especially is best with the divinyl.Under the situation of wedging block, each B block at least mainly is to be polymerized by alkadiene, and promptly the B block has the 85(mole at least) %, preferably have the 93(mole at least) % polymeric alkadiene, remaining is the vinylaromatic hydrocarbon of A block.Though polymeric combination chain diene block and wedging block also are gratifying, but still are the best with the homopolymerization block as the B block.Usually two kinds of possible aggregation schemes in polymeric alkadiene block, have been observed.Be called in 1,4 polymerization, two carbon-to-carbon double bonds of conjugated diolefine are all relevant with polymerization, and each carbon atom that forms two keys all is combined in the polymer chain, and comprise two carbon atoms that connected by ethylenic linkage.In 1,2 polymerization, polymerization only relates to a carbon-carbon double bond of conjugated alkadiene, so only adds two carbon atoms in the polymer chain.The carbon atom that is not combined in the conjugated alkadiene in the polymer chain forms one or more side groups that may contain an ethylenic linkage usually.
Segmented copolymer preferably those wherein about unit of 25% to 55% of each B block be the polymkeric substance that is generated by 1,2 polymerization.The molecular-weight average of B block is 10,000 to 300,000 comparatively suitable, and is preferably 30,000 to 150,000.
In segmented copolymer, the total content of A block should be the 2(weight of segmented copolymer gross weight) % to 55(weight) %, be preferably 10(weight) % to 30(weight) %.The total molecular weight average out to 25,000 to 350,000 of segmented copolymer is preferably 35,000 to 300,000.The molecular-weight average of these multipolymers is measured with conventional art, for example tritium counting process or osmolarity measuring method.
The structure of segmented copolymer depends on the polymerization process that is used for producing segmented copolymer.In a kind of modification body, segmented copolymer is called as linear, is to produce by the sequential polymerization of block.In producing the example of triblock copolymer, the vinylaromatic hydrocarbon of A block is to carry out polymeric using under a kind of catalyzer situation that is preferably alkyl lithium compounds.Introduce the conjugated alkadiene of B block then, then introduce forming second vinylaromatic hydrocarbon that the A block is required.This multipolymer be characterized as ABA.The method of producing two blocks or two block polymers is to use lithium initiator to carry out polymerization A block, is introduced as then to form the required alkadiene of B block.This polymkeric substance be characterized as AB.Before introducing the monomer of next block, real finish each monomeric polymerization, its result will produce the block of homopolymerization.If a kind of monomer of block under before any block is finished polymerization, introducing again, its result block that will obtain wedging so.The product of producing with similar sequential polymerization technology is characterized as ABABA, ABAB, ABABABA or even the segmented copolymer of higher block number.Producing segmented copolymer, when especially producing the multipolymer of quite high block number, also needing to carry out the polymer chain that coupling or connection are increasing with coupling agent.Use the difunctionality coupling agent, for example alkylene dihalide will cause generating simple linear polymer, and use 3 or the coupling agent of polyfunctionality more, and for example the alkyl ester of four halo silicon or dicarboxylic acid will cause generating respectively and be called " radial " or " branched " polymkeric substance.
These segmented copolymers all are that prior art is known, and the feature of this polymkeric substance and production method are illustrated in United States Patent (USP) 3251905,3390207,3598887 and 4219627.
As the block polymer of present composition component (parent) simple linear polymer of following type preferably: polystyrene-poly divinyl (SB), polystyrene-poly isoprene (SI), polystyrene-poly divinyl-polystyrene (SBS), polystyrene-poly isoprene-polystyrene (SIS), poly-(alpha-methyl styrene)-polyhutadiene-poly-(alpha-methyl styrene) and poly-(alpha-methyl styrene)-polyisoprene-poly-(alpha-methyl styrene).Wherein the segmented copolymer of SBS type is especially good.Now these segmented copolymers have been general, manyly can buy from the shop.
Each component for production mixture of the present invention makes the segmented copolymer partial hydrogenation, preferably further carries out modification subsequently again by reacting with a kind of maleinization compound.The hydrogenization of segmented copolymer is also known in the prior art, the catalytic hydrogenation under the precious metal element in small, broken bits that it is included in Raney nickel or platiniferous or palladium exists.Common this hydrogenation will make hydrogenation occur in great majority, otherwise be exactly the unsaturated position that occurs in the aromatic nucleus of whole A block end groups go up and the unsaturated position of aliphatics B block on.Yet when each component of production mixture of the present invention, just partly hydrogenation is carried out in the unsaturated position of most of aliphatics B blocks and hydrogenation is not carried out in the unsaturated position of the aromatic nucleus of A block.This method for hydrogenation is open in United States Patent (USP) 3113986 and 4226952, and is hereby incorporated by reference.Partially hydrogenated segmented copolymer is those multipolymers preferably, and promptly wherein unsaturated ratio that is hydrogenated of aromatic nucleus is not higher than 25%, preferably is not higher than 5%, and wherein the unsaturated position of residue of mid-block accounts for 0.5% to 20% of hydrogenation unsaturated position in the past.
Partially hydrogenated segmented copolymer is usually used " outward appearance " structure of the structure of segmented copolymer parent and aliphatic hydrocarbon block and is discerned.Therefore the partial hydrogenation effect of SBS block polymer occurs in by 1, the result will produce that a kind of to have obviously be the polymkeric substance of poly hydrogenant mid-block under the unitary situation of mid-block that 4 polymerizations produce, and occur in by producing ethylene/butylene copolymers under the unitary situation of mid-block that 1,2 polymerization produces at high proportion.These segmented copolymers can be expressed as SES and SEBS respectively.Corresponding diblock polymer is called as SE or SEB.When 1, the 4 structure SIS segmented copolymer of the high level in the middle block was carried out partial hydrogenation, the polymkeric substance that is produced was called as the SEPS polymkeric substance, because this is that the situation of ethylene/propene copolymer is similar to the mid-block unit.
In order to produce maleation, partially hydrogenated segmented copolymer is as the component of mixture of the present invention, and partially hydrogenated SES/SEBS type segmented copolymer preferably mid-block unit has 45% to 65% E type mid-block, and remainder is an EB type mid-block.The partial hydrogenation segmented copolymer of these types is known in the prior art, many commodity that become, and for example, some partially hydrogenated segmented copolymer is sold as " thermoplastic elastomer ".
As the preferably a kind of partially hydrogenated segmented copolymer of partially hydrogenated segmented copolymer of the maleation of component of mixture of the present invention and the affixture of a maleinization compound.The maleation material is to produce like this, by in the addition of the hydrogen atom on the allyl group carbon atom carbon-to-carbon double bond of partially hydrogenated unsaturated position of segmented copolymer residue mid-block and maleinization compound being combined and form C-C between maleinization compound and partially hydrogenated segmented copolymer chain.
Be applicable to and carry out maleation, the maleinization compound of partial hydrogenation segmented copolymer has: the monoamide and the maleimide of the mono alkyl ester of toxilic acid, maleic anhydride, toxilic acid (wherein alkyl is meant carbonatoms until 4, comprises 4 alkyl), toxilic acid.Certainly preferably use maleic anhydride.
Maleation, its production method of partial hydrogenation segmented copolymer is the same all to be well known in the prior art.In general, the production process of maleation product is a grafting process, and wherein the maleinization compound is grafted on the partially hydrogenated segmented copolymer middle-of-chain block.In its a modification body, partially hydrogenated segmented copolymer contacts in the presence of radical initiator (preferably a kind of superoxide) with the maleinization compound.
The maleation degree of partially hydrogenated segmented copolymer depends on the unsaturated bit position of residue of polymkeric substance aliphatics block.With regard to above-mentioned polymkeric substance, the segmented copolymer of enough maleinization compounds and local hydriding is reacted to produce a kind of derivative of maleation, and this derivative contains 0.02(weight) % to 20(weight) %(is based on the gross weight of polymkeric substance) and be grafted to derivative moiety on the polymkeric substance fat block by the maleinization compound.Still based on aforementioned total polymer weight, the polymkeric substance of maleation preferably contains 0.1(weight) % to 10(weight) the maleinization compound part of %, and the most best be to contain 0.2(weight) % to 5(weight) the maleinization compound part of %.
Generally speaking, solvent-free " extrusion type " maleation method is best.Open and the maleation product of these class methods can be referring to United States Patent (USP) 4292414,4427828, and 4628072,4659970 and 4657971.Additive method can be referring to United States Patent (USP) 4578429 and 4670173.
The partially hydrogenated segmented copolymer of some maleation is to produce in enormous quantities, and is sold by the company relevant with the applicant.A kind of partially hydrogenated segmented copolymer of good especially maleation is KRATON G 1901 * thermoplastic elastomer (KRATON is a sales trademark), the segmented copolymer that it is characterized in that the maleation of SES/SEBS type has a maleic functionality, and institute's grafted maleic anhydride is a 2(weight) %.
Be applicable to that composition of the present invention contains by the polyketane polymers of larger proportion and the mixture of forming than (maleation) partially hydrogenated segmented copolymer of small proportion.The amount of modified block copolymer depends on wants the shock strength that reaches and the character of polyketane polymers component.The amount of modified block copolymer is 0.5% to 40%(by weight) (is benchmark with whole mixture weight) but the time impact intensity and polyketone component Young's modulus improve to some extent: when the amount of modified block copolymer is benchmark with whole mixture to use 2% to 20%(by weight) for well.
A kind of very suitable compositions comprises a kind of like this segmented copolymer, and wherein: each A block is selected from one group of monomer being made up of vinylbenzene and alpha-methyl styrene, the molecular-weight average of each A block from 5,000 to 125,000;
Each B block in the segmented copolymer is selected from one group of monomer being made up of divinyl and isoprene, the molecular-weight average of each B block from 10,000 to 300,000;
The weight of A block is 2% to about 55% of whole segmented copolymer weight;
The amount of the unsaturated position of remaining B block is 0.5% to 20% of the unsaturated position of the original B block of said segmented copolymer in the segmented copolymer;
And be benchmark with the total polymer, the amount that segmented copolymer contains the maleinization compound part that is grafted on the A block is 0.02% to 20%(by weight).
As long as can produce the uniform mixture of each component, the method for producing polyketane polymers and the mixture of (can maleation) partially hydrogenated segmented copolymer so then is not vital.The block copolymer mixture of polyketone/modification is a kind of not miscible mixture and has partially hydrogenated segmented copolymer, this polymkeric substance exists as a discontinuous phase in polyketone matrix, phase size has more representational size and is about 0.3～0.4 micron from 0.2 micron to 2 microns.Therefore mixture is not a homogeneous, but the distribution of the segmented copolymer of modification in the polyketone matrix is still uniform substantially.The method of mixing each component is the traditional method that is used to be difficult for the mixed polymerization objects system.Polymer materials is to make the blended extrudate through modification in the twin screw extruder that a corotation changes.In the alternative modification of another kind, component is mixed in a mixing device that demonstrates high shear force before injection molding.
Composition can suitably contain a kind of annexing ingredient, ceramic fiber.
The fortifying fibre that is applicable to the present composition is called as refractory ceramic fibre, (RCF) also can be described as ceramic fiber or aluminium oxide-silicon oxide fibre.Representational RCF is made up of silicon oxide that waits umber and aluminum oxide.With silicate glass (as E-glass, or mineral fiber) by comparison, RCF has the trace or the oxide compound of the basic metal of a large amount (as sodium), alkaline-earth metal (as calcium) slightly, and the oxide compound of other metal (as titanium and iron).The very a spot of highly basic that exists among the RCF can make its surperficial alkali free metal ion exchange usually and interact, and makes it have bigger wet fastness to moisture.Although a small amount of monovalent cation is arranged, still have some silanol bases (Si-OH) to provide surface modification to the fiber interface at fiber surface.
Refractory ceramic fibre normally prepares in melting operation, and soon starting material melt in electric arc furnace and make melt flow stream.Melt flow stream under high pressure by air spray or drop onto reel off raw silk from cocoons the wheel on, the latter is minimum fragment with fluid separation.Fragment forms fiber and is cooled off rapidly.Also produce the molten drop that some are called Ballet Shop in melting process, they are spheroidal particle and be not converted into fiber, can bullet wherein be removed by the processing to RCF, and especially bullet content can not have a bit injury to all character of ceramic fiber.RCF can buy and be used in the high temperature use, as the insulating material as stove with mat or form of fabric according to tradition from the shop.Fiber also can be used as the strongthener of polymeric articles and be used for commercial.Yet the physical size and the fiber of ceramic fiber have or not rubber cement or coupling agent in discrete is used, and the characteristic of rubber cement or coupling agent all has some importance to successfully utilizing.
In the present invention's polyketone/maleation preferably, can provide the ceramic fiber of wanting the performance that needs most to composition in partially hydrogenated segmented copolymer/ceramic fiber composition is the ceramic fiber that has shredded of circular cross section.The mean diameter of fiber is from 1 micron to 10 microns, preferably 2 microns to 4 microns.Fiber slightly larger or slightly smaller diameter can satisfy application.But the fiber that diameter is too little can not reach desirable intensity, and the too big fiber weight for formed intensity of diameter is too big, is uneconomic therefore.Although in some applications, very short ground ceramic fiber or long continuous ceramic fiber all are gratifying, but preferably use the short ceramic fiber of chopping in better composition of the present invention, the length of ceramic fiber is advisable with 0.35 millimeter to 15 millimeters.A little longer or shorter slightly fiber can use, but oversize ceramic fiber impairs the processing characteristics of composition, and too short fiber can not reach desirable intensity.The physical length of ceramic fiber will depend on fusion to a certain extent or mix the method for each component in the composition as can be seen, because may reduce the length of ceramic fiber owing to mechanically fractureing in this process.
The ceramic fiber that is used to strengthen thermoplastic material has a kind of rubber cement or coupling agent coating that can often exchange use when being supplied by manufacturing firm.The characteristic of rubber cement or coupling agent will influence the interface shear strength of fiber and polymeric matrix, i.e. polymkeric substance and ceramic fiber adherent degree.The bonding of higher degree between polymkeric substance and fiber, occur and will cause mechanical property, as the improvement of tensile strength.Exert an influence to polymer composition strength, the interface shear strength of polymkeric substance is equally matched with the shearing resistance grade of polymkeric substance at least, just can make have between polymkeric substance and the ceramic fiber good bonding.The interface shear strength of polymkeric substance is influenced by its polar, and therefore concerning some polymkeric substance, certain rubber cement or coupling agent are better than other.For the mixture that contains polyketane polymers, various rubber cements all are suitable for.The general characteristic of this rubber cement is to characterize by the overall characteristic of rubber cement rather than by special chemical structure, and this is patented for ceramic fiber manufacturing firm.The rubber cement that is suitable for comprises aqueous dispersions, material such as vinyl silanes, alkyl trimethoxysilane, the aminosilane of water miscible liquid, lubricant and the tensio-active agent of lubricating oil and starch, may also contain the Trimethoxy silane and the nonpolarity hydrocarbon of urea alkane, acrylate (salt) or epoxy functionalities.The ceramic fiber that contains this class rubber cement can be bought from the shop.The weight content of pottery reinforce is 0.1% to 45% better (weight with whole mixture is benchmark), preferably from 0.5% to 35%.
In addition, can also select the third (or the 4th kind) component to join in this composition.The add-on of this component may be up to the 5(weight of processing aid) %, for example multipolymer of alpha-olefin and unsaturated carboxylic acid.The amount that adds can be from 0.1(weight) % to 5(weight) %, for example 1%, 2% or 5%.Alkene-unsaturated acid the multipolymer that can mix with the present composition is with ethene and α, and the multipolymer of β-alkene unsaturated carboxylic acid is advisable.Although various α up to 10 carbon atoms (in some cases can more than 10), β-hydrocarbon belongs to unsaturated carboxylic acid can be as the component of multipolymer, for example, the 2-caproic acid, α-octylenic acid and 2-nonene diacid, and up to those unsaturated acid of 4 carbon atoms for well, as vinylformic acid, methacrylic acid and Ba Dousuan.Especially vinylformic acid and methacrylic acid are best unsaturated acid copolymer components.
Ethene-unsaturated acid multipolymer is meant that those ethene account for larger proportion and unsaturated acid accounts for the multipolymer than small proportion.Typical ethylene copolymer is α contained when being benchmark with total multipolymer weight, and β-ethylenically unsaturated carboxylic acids is 10% to 95%(by weight), be preferably 5% to 12%(by weight).
The method of producing multipolymer is not main, and the ethene of produced in several ways-unsaturated acid multipolymer may be used in the mixture of the present invention.Many ethylene-acrylic acid copolymers and ethylene-methacrylic acid copolymer all can be bought from the shop.About the argumentation of producing alkene-unsaturated acid multipolymer can be referring to United States Patent (USP) 3520861 and 4351931.
Mixture of the present invention also can comprise the additive that some are common, as oxidation inhibitor, stablizer, fire retardant material, toughener, releasing agent and can improve the tinting material that the polymer processing performance maybe can be improved the mixture character that is generated.These additives can be according to the conventional method at polyketane polymers with before segmented copolymer maleation, partially hydrogenated mixes, blended joins in this mixture simultaneously or after mixing.
Mixture of the present invention is characterised in that to compare with polyketane polymers has increased Young's modulus.This mixture is specially adapted to produce those and still needs in the particular product of toughness and intensity when being placed on reduced temperature and contrast physical stress condition.This mixture can adopt general technology to process (as extruding or injection molding) and make sheet material, film, fiber, sheet material and molded article.As the illustration of these application the production of the internals and the exterior part of carrier and relevant industries and the production that is applied to building slab in the building industry are arranged.
The present invention further is illustrated by following examples.
Example 1
A), at negatively charged ion and 1 by acid chloride, trifluoroacetic acid, the catalyst composition that two (=(2-p-methoxy-phenyl) phosphino-) propane of 3-constitute exists down makes carbon monoxide, ethene and propylene contact the terpolymer for preparing them, the fusing point of this terpolymer is 220 ℃, under 60 ℃ of conditions in-to record its intrinsic viscosity (LVN) with the standard capillary viscosity determinator in the cresols be 1.96.
B), the polyketane polymers that front A step is made mixes with the partially hydrogenated segmented copolymer of the maleation of various quantity and can obtain the thermoplastic elastomer applied for.This hydrogenant segmented copolymer is the SES/SEBS type, and it contains 28(weight) vinylbenzene end block and 72(weight about %) hydrogenated butadiene mid-block about %.The unsaturated position of residue of using mid-block is with 2(weight) maleic anhydride graft of % is aggregated on the partially hydrogenated segmented copolymer.The proportion of polymkeric substance is 0.91 grams per milliliter, and tensile strength is 34.5MPa, the polymkeric substance of the soltion viscosity in the time of 25 ℃ (20(weight in toluene) %) be 6,000CP.
During the preparation mixture, the particle of dried mixed polymer component changes melting mixing in the twin screw extruder with each component at the corotation of (screw diameter an is) 30mm then earlier, and this forcing machine is divided into seven sections, and total slenderness ratio (L/D) is 27/1.The melt temperature of head remains on 260 ℃, and barrel zone temperature is about 240 ℃, and mixture is removed fugitive constituent under vacuum condition in the district adjacent with head.The residence time in forcing machine is approximately 1 minute.
With blend sample injection molding is the ASTM test rod, carries out v-notch with the method for ASTM-256 and ASTM-790 respectively and tests and test and subdue modulus.The residence time is about 45 seconds in injection mould, and temperature out is about 270 ℃.The test value of the segmented copolymer of various concentration is listed in the table I in the polyketane polymers, and the test value of the polyketane polymers of unmixed is also listed in the same table.
The table I
Segmented copolymer V-type-breach, room temperature is subdued modulus
(% weight) is (MPa) (Kgm/m)
The 0(Comparative Examples) 26 1655
5 107 2013
10 21 2013
15 9.8 2013
20 7.6 2013
Example 2
The production process of application examples 1B, different is the extruder head of using a modification, to produce the blend sample that contains a small amount of segmented copolymer.List in the table II from the data of the polyketane polymers of data that these samples obtained and unmixed.
The table II
Segmented copolymer v-notch (Kgm/m) is subdued modulus
(% weight) room temperature-29 ℃ (MPa)
The 0(Comparative Examples) 22 6.0 1793
2 86 8.2 1800
5 105 26 2158
7 124 23 2000
Example 3
The program of application examples 1B, different is biased sample injection molding on different injection moulding machines.It is 2.2/1 that this injector has compression ratio, and diameter is the screw rod of 45mm.Be 30 seconds the cycling time of entire sample.Add about 0.5(weight) Ethanox330(Ethanox of % is a kind of trade mark) to improve stability.Before carrying out the v-notch shock strength and subduing the modulus test, the sample after the moulding was put into a loft drier aging 24 hours immediately.The result who is mixed with the polyketone of the test result of segmented copolymer of maleation of various concentration and unmixed in the polyketane polymers all lists in the table III.The composition that contains stablizer as can be seen still has same mechanical property after aging.
The table III
Segmented copolymer is subdued modulus V-type impact value (Kgm/m)
(% weight) is room temperature-29 ℃ (MPa)
The 0(Comparative Examples) 1,793 22 6.0
2 1800 86 8.2
5 2158 105 26
7 2000 124 23
10 1703 21
15 1255 9.8
20 903 7.6
Example 4
According to the tensile property of ASTM D-638 method test sample after 2 weeks of placement in 100 ℃ of ageing ovens, gained the results are shown in the table IV (this sample is respectively the mixture of polyketone/5% segmented copolymer that has just prepared in polyketone and the example 3).
The table IV
Segmented copolymer tensile strength (MPa) elongation %
(% weight) breaking yield breaking yield
The 0(Comparative Examples) 63 56 125 19.5
5 60 56 87 29.0
Behind ageing oven:
0 55 64 26.1 16.3
5 50 66 29.5 14.6
Example 5
Program by example 3 is investigated the influence of polyketone LVN on shock strength in the block copolymer mixture of maleation, and LVN is respectively the Different Effects of 1.74,1.57 and 1.31 polyketone.The segmented copolymer relativity of the maleation of shock strength and different content is referring to the figure I.Especially LVN a kind of nonlinear state that has been respectively 1.57,1.74 and 1.96 polyketone mixture for several is according to the show expressed best synergistic effect.
The test of subduing modulus and tensile strength is to carry out in the materials flow direction of injection molding sample, and the test of shock strength then is to carry out in the vertical direction of materials flow.Injection molding polymkeric substance especially presents anisotropy, yet the block copolymer mixture of polyketone/maleation of the present invention is in the nondirectional sign influence of the aspect of performance of being surveyed.These samples also further demonstrate along with the increase of the content of segmented copolymer it and subdue modulus and also increase, and this is obvious abnormal phenomena for typical polymkeric substance/block copolymer mixture.
Example 6(contrast)
According to the identical mode of example 3 programs, produce a kind of composition, different is is added to the ethylene acid copolymer (hereinafter referred to as EAA) of 1% (by weight) in the polyketone, and does not use segmented copolymer or stablizer.Test result is listed the table V in.
Example 7(contrast)
Produce a kind of composition according to the mode identical with example 6 programs, difference is to use 5%(by weight) EAA, rather than 1%(by weight), test result sees Table V.
Example 8
Produce according to the mode identical and to contain 5%(by weight with example 3 programs) composition of the segmented copolymer of maleation, but also will be by weight with 1%() EAA be added in the mixture, and stablizer not, test result sees Table V.
Example 9
Produce a kind of composition according to the mode identical, the different 5(weight that are to use with example 8) EAA of %, test result sees Table V.
Example 10
Produce a kind of composition according to the mode identical with example 3 programs, yet the terpolymer of preparing linear alternating is changed to another kind of polymkeric substance, the catalyzer that this polymkeric substance uses in preparation process is by the negatively charged ion of acid chloride, trifluoroacetic acid and 1, and two (=(2-p-methoxy-phenyl) phosphino-) propane of 3-form.The fusing point of this terpolymer is 228 ℃, and between under 60 ℃ of conditions-cresols in its LVN of test be 1.5.Then with 83.50(weight) terpolymer and the 0.5(weight of %) the aforementioned stable agent of %, and 5(weight) the partially hydrogenated SES/SEBS type segmented copolymer of the maleation of % (this multipolymer has the vinylbenzene of 28% weight, and the maleic anhydride graft that 2% weight arranged is on the mid-block of segmented copolymer) mixes.Again that (is benchmark with total mixture weight) of 10% weight is broken in addition ceramic fiber adds in the mixture.The staple length of used refractory ceramic fibre is about 13mm, and average fibre diameter is the 2-3 micron, and proportion is 2.73 gram per centimeters
3, fusing point is 1790 ℃.These ceramic fibers are with commercial rubber cement starching, this rubber cement can use phenol, epoxy, nylon, melamine and polyurethane system.In addition, the EAA of 1% weight is added in the mixture, test result sees Table V.
Example 11
Produce a kind of composition according to the mode identical with example 10, yet be that terpolymer with 79.50% rather than 83.5% weight mixes with the EAA of 5% rather than 1% weight, test result sees Table V.
Example 12
The composition that uses a kind of and example 10 used same way as to make, difference is that mixture is a kind of mixture of three components, i.e. the stablizer of the fragment ceramic fiber of 5% weight, 0.5% weight, all the other are polyketone.Test result sees Table V.
Example 13-14
Prepare composition according to the mode identical with example 12, however the add-on of ceramic fiber be increased to respectively 10% and 15%(weight), and the amount of corresponding minimizing polyketane polymers.Test result sees Table V.
Example 15
Prepare a kind of composition as example 13, difference is 10%(weight) never gluing of ceramic fiber.Test result sees Table V.
Example 16(contrast)
Prepare a kind of composition and test by example 10 described methods, said composition contains the terpolymer described in the example 10 of 99.5% weight and the stablizer of 0.5% weight.Test result sees Table V.
The table V
Notch shock tensile modulus modulus in flexure adds moral and impacts
ASTM （mKg/m） （MPa） （MPa） （Cm/Kg）
D-256 D-638 D-790 D-3029
20 ℃-29 ℃ of examples
6 38 - - 1751 ＞1790
7 40 - - 1551 615
8 109 - 51 1951 -
9 19 - ND（＞50%） 1593 -
10 21 - 55 2799 95
11 15 - - 2062 50
12 6.0 - - 2220 224
13 6.5 - - 2572 179
14 7.0 - - 2861 101
15 7.0 - - 2227 -
16 22 6.0 - 2027 -
ND=is uncertain
Find out that from the table V segmented copolymer that adds 2-7% weight can fully improve notched izod impact strength.Impact data (Gardener Impact Data) and also can find out by adding moral, the processing materials such as EAA with 1% promote cavitation and improve shock-resistance thereby add and be dispersed in the submicron level in the polymeric matrix.Composition of the present invention preferably uses this kind processing material.
Example 17
A), the terpolymer of making the preparing linear alternating of another kind of carbon monoxide, ethene and propylene in the presence of a kind of catalyst composition is being arranged, (this catalyst composition is by the negatively charged ion of acid chloride, trifluoroacetic acid and 1, and two (two (2-p-methoxy-phenyl) phosphino-) propane of 3-form.) fusing point of this polymkeric substance is 220 ℃, the intrinsic viscosity of this polymkeric substance (LVN) for 1.29(under 60 ℃ of conditions in-measure in the cresols).
B), a kind of mixture by front A step polyketane polymers and 10% weight (is benchmark with whole mixture weight) hydrogenant segmented copolymer, (this multipolymer is SEBS type polymkeric substance at last, molecular weight be about 57,000 and 32% vinylbenzene arranged) this preparation process of mixture is at N with each polymeric constituent
2Do reinforced Haake forcing machine down, under 270 ℃ of conditions, operate by a 30mm.The gained mixture is uniform.Detect a kind of with an electron microscope by the painted cold cut blend sample of ruthenium tetroxide.The hydrogenant segmented copolymer is at this moment as a kind of disperse phase (the phase diameter is about 0.7 micron).
By compression molding this mixture is made platelet, and detect with a kind of center notched izod Impact Test technology.The numerical value of the numerical value of used polyketane polymers and mixture is all listed in the table VI in the mixture.
The table VI
Izod (J/M)
Material RT-izod (20 ℃)
Polyketone 94 47
Mixture 164 73
Claims (14)
1, polymer composition, be characterised in that it comprises a kind of mixture of nonmiscibility, this mixture comprises a kind of preparing linear alternating polymkeric substance by carbon monoxide and at least a ethylenic unsaturation hydrocarbon compound, and a kind of can maleation, at least the segmented copolymer of local hydriding (this multipolymer have at least one mainly be the A block of polymeric vinyl aromatic compounds block and to have one at least mainly be the B block of polymeric conjugated alkadiene block).
2, a kind of composition as claimed in claim 1, wherein the polymkeric substance of preparing linear alternating is represented with following structural formula:
Wherein D is a kind of derivative moiety of the unsaturated olefin by at least 3 carbon atoms, and the ratio of y: x is no more than 0.5.
3, a kind of as the composition as described in the claim 2, wherein D is the part of propylene.
4, a kind of as the composition as described in the claim 2, wherein y=0.
5, a kind of as the composition as described in each in the claim 1 to 4, wherein segmented copolymer is maleation.
6, a kind of as the composition as described in the claim 5, wherein:
Each A block of segmented copolymer is selected from one group of monomer being made up of vinylbenzene and alpha-methyl styrene, the molecular-weight average of each A block from 5,000 to 125,000;
Each B block of segmented copolymer is selected from one group of monomer being made up of divinyl and isoprene, the molecular-weight average of each B block from 10,000 to 300,000;
The weight of A block is 2% to 55% of whole segmented copolymer weight;
B block unsaturation position remaining in the segmented copolymer is 0.5% to 20% of the original B block of described segmented copolymer unsaturation position.
Segmented copolymer is in 0.02(weight) % to 10(weight) %, be as the criterion with total polymer weight, be grafted to the maleinization compound part on the A block.
7, a kind of as each described composition in the claim 1 to 6, wherein the concentration of segmented copolymer whole mixture weight 2% and 20% between.
8, a kind of composition as claimed in claim 7, wherein the concentration of segmented copolymer is in 2% to 7%(weight) between, the LVN of preparing linear alternating polymkeric substance is between 1.5 to 2.0.
9, a kind of as each described composition in the claim 1 to 8, wherein the ceramic fiber reinforce exists as a kind of additional ingredients.
10, a kind of as the composition as described in the claim 9, wherein the concentration of fiber is that benchmark is from 0.1(weight with the gross weight of mixture) % to 45(weight) %.
11, a kind of as the composition as described in each in the claim 1 to 10, wherein processing aid exists as a kind of additional ingredients.
12, a kind of as the composition as described in the claim 11, wherein processing aid is a kind of α-alkene and a kind of α, the multipolymer of β-olefinic unsaturation carboxylic acid.
13, a kind of composition as claimed in claim 12, wherein α-alkene is ethene, unsaturated carboxylic acid is acrylic or methacrylic acid.
14, a kind of as the composition as described in each in the claim 11 to 13, wherein the concentration of processing aid is that benchmark is from 0.1(weight with the weight of mixture) % to 5(weight) %.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/203,975 US4868242A (en) | 1988-06-08 | 1988-06-08 | Composition comprising a blend of an ethylene-carbon monoxide interpolymer and a maleated, partially hydrogenated block copolymer |
| US203,959 | 1988-06-08 | ||
| US239.095 | 1988-08-31 | ||
| US239,095 | 1988-08-31 | ||
| US239.094 | 1988-08-31 | ||
| US239,094 | 1988-08-31 | ||
| US07/239,094 US4904728A (en) | 1988-08-31 | 1988-08-31 | Polymer blends |
| US203,975 | 1989-06-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1040041A true CN1040041A (en) | 1990-02-28 |
| CN1020738C CN1020738C (en) | 1993-05-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 89106236 Expired - Fee Related CN1020738C (en) | 1988-06-08 | 1989-06-08 | Polymer composition |
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| CN109666256A (en) * | 2018-11-15 | 2019-04-23 | 广州敬信高聚物科技有限公司 | A kind of halogen-free flame-retardant thermoplastic elastomer composition and its preparation method and application |
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| CN100420508C (en) * | 2006-04-14 | 2008-09-24 | 江汉大学 | Microemulsion and its preparation process and use in treating industrial phenolic waste water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109666256A (en) * | 2018-11-15 | 2019-04-23 | 广州敬信高聚物科技有限公司 | A kind of halogen-free flame-retardant thermoplastic elastomer composition and its preparation method and application |
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| CN1020738C (en) | 1993-05-19 |
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