CN100473695C - Transparent polycarbonate-polysiloxane copolymer blend, method for the preparation thereof, and article derived therefrom - Google Patents
Transparent polycarbonate-polysiloxane copolymer blend, method for the preparation thereof, and article derived therefrom Download PDFInfo
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- CN100473695C CN100473695C CNB2004800400600A CN200480040060A CN100473695C CN 100473695 C CN100473695 C CN 100473695C CN B2004800400600 A CNB2004800400600 A CN B2004800400600A CN 200480040060 A CN200480040060 A CN 200480040060A CN 100473695 C CN100473695 C CN 100473695C
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Abstract
A composition includes a polycarbonate-polysiloxane block copolymer that has at least one polycarbonate block and at least one polysiloxane block, and a surface modifying agent that includes at least one polysiloxane segment. Increased levels of the surface modifying agent can be incorporated without compromising high transmittance and low haze. The compositions also exhibit improved hemocompatibility and are therefore useful for a variety of articles that may contact blood.
Description
The cross reference of related application
The rights and interests of the U.S. Provisional Application series number 60/519,370 that the application submitted on November 12nd, 1.
Background of invention
In order to change surface property, the polymkeric substance and the multipolymer that will contain siloxanes are coated on the various thermoplastic articles.For example, Deppisch etc. are at United States Patent (USP) 6,500, have described the coated article with the physiologically acceptable film that comprises the polydimethylsiloxane block in 549.Ward etc. are at United States Patent (USP) 5,589, have described the coated article with the polymkeric substance that contains the surfactivity end group in 563, and described polymkeric substance comprises the linear base polymer with capillary surfactivity end group of the described base polymer of change that covalency links to each other.Plunkett is at United States Patent (USP) 6,395, described a kind of coating that is used for microporous hollow fiber film blood oxygenators in 226, and described coating has improved fiber and stoped the ability of blood plasma by the micropore transmission, and described coating comprises organoalkoxysilane-alkyl silane multipolymer.The shortcoming of this method is to need independent processing and coating step to apply described surface modification multipolymer.
Also known polymkeric substance and the body thermoplastic resin surface property that can change thermoplastic resin by will containing siloxanes.For example Gaines etc. is at United States Patent (USP) 3,686, described the blend of base polymer and surface modified additive in 355, and described additive can be polycarbonate-polysiloxane block copolymers.But the amount that obtains the surface modified additive of required surface property needs reduces the required optical property of described basic multipolymer usually.
Therefore, need have required surface property, do not need the surface-coated step and do not diminish the blend polymer of the required optical property of described base polymer.
Summary of the invention
Above-mentioned and other shortcomings can be relaxed by composition as described below, described composition comprises: comprise the polycarbonate-polysiloxane block copolymers of at least one polycarbonate block and at least one polysiloxane block and the surface-modifying agent that comprises at least one polysiloxane segment, wherein said polycarbonate block comprises the repeating unit with following structure:
R wherein
1About 60-100% is for replacing or unsubstituted divalent aromatic organic group in the group sum, and 0-about 40% is aliphatic divalent group or divalence alicyclic group; Wherein said polysiloxane block comprises the repeating unit with following structure:
R wherein
2Independent separately is C
1-C
12Alkyl.
Other embodiments are described in detail in detail below, comprise described method for compositions of preparation and the goods that comprise described composition.
Detailed Description Of The Invention
The present inventor finds to have polycarbonate-polysiloxane block copolymers that the blend polymer of the surface property, particularly improved blood compatibility of modification can be by will comprising at least one polycarbonate block and at least one polysiloxane block and comprises that the surface-modifying agent blend of at least one polysiloxane segment makes.Compared with the thermoplastics with blood compatibility of market sale, described composition has improved shock strength.According to the purposes of expection, described polycarbonate-polysiloxane block copolymers can be opaque, translucent or transparent.Find that transparent especially polycarbonate-polysiloxane block copolymers can contain high-load surface-modifying agent and can devitrification and low haze (haze).
One embodiment of the invention are a kind of composition, described composition comprises: comprise the polycarbonate-polysiloxane block copolymers and the surface-modifying agent that comprises at least one polysiloxane segment of at least one polycarbonate block and at least one polysiloxane block, wherein said polycarbonate block comprises the repeating unit with following structure:
R wherein
1About 60-100% is for replacing or unsubstituted divalent aromatic organic group in the group sum, and 0-about 40% is aliphatic divalent group or divalence alicyclic group; Wherein said polysiloxane block comprises the repeating unit with following structure:
R wherein
2Independent separately is C
1-C
12Alkyl.
In above-mentioned polycarbonate block structure, preferred R
1Be the aromatics organic group, the group that more preferably has following structure:
-A
1-Y
1-A
2-
A wherein
1And A
2The monocycle divalent aryl of respectively doing for oneself, Y
1For separating A
1And A
2Have one or two atom bridged group.In an exemplary embodiment, by an atom separates A
1And A
2Y for example
1Can be-O-,-S-,-S (O)-,-S (O)
2-,-C (O)-or C
1-C
18Alkylene (hydrocarbylene).Representational C
1-C
18Alkylene comprises methylene radical, cyclohexyl-methylene radical, 2-[2.2.1]-Ya two suberyl, ethylidene, isopropylidene, inferior neo-pentyl, cyclohexylidene, inferior cyclopentadecane base, inferior cyclo-dodecyl and inferior adamantyl.No matter term used herein " alkyl " uses separately or as prefix, the suffix of another term or constitute arbitrary part of speech, all refers to only comprise the residue of carbon and hydrogen.Described residue can be aliphatic series or aromatics, straight chain, ring-type, dicyclo, side chain, saturated or undersaturated hydrocarbon part.Described residue also can comprise the combination of aliphatic series, aromatics, straight chain, ring-type, dicyclo, side chain, saturated or undersaturated hydrocarbon part.But when being called hydrocarbyl residue, then except the carbon of substituting group residue and hydrogen, also can comprise heteroatoms.Therefore, when indicating especially when comprising these heteroatomss, described alkyl or alkylene residue can comprise carbonyl, amino, hydroxyl etc., perhaps can comprise heteroatoms on the main chain of described hydrocarbyl residue.
Radicals R
1Can be the residue of aromatic dihydroxy compound.Some of suitable dihydroxy compound is exemplary, non-limiting instance has at United States Patent (USP) 4,217, the hydrocarbon by title or molecular formula (general formula or particular compound are open) disclosed dihydroxyl-replacement in 438.The non exhaustive specific examples of suitable dihydroxy compound comprises following compound: Resorcinol, 4-bromine Resorcinol, Resorcinol, 4,4 '-dihydroxybiphenyl, 1, the 6-dihydroxy naphthlene, 2, the 6-dihydroxy naphthlene, two (4-hydroxyphenyl) methane, two (4-hydroxyphenyl) ditan, two (4-hydroxyphenyl)-1-naphthyl methane, 1,2-two (4-hydroxyphenyl) ethane, 1,1-two (4-hydroxyphenyl)-1-diphenylphosphino ethane, 2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl) propane, two (4-hydroxyphenyl) phenylmethane, 2,2-two (4-hydroxyl-3-bromophenyl) propane, 1,1-two (hydroxyphenyl) pentamethylene, 1,1-two (4-hydroxyphenyl) hexanaphthene, 1,1-two (4-hydroxy-3-methyl phenyl) hexanaphthene, 1,1-two (4-hydroxyphenyl) iso-butylene, 1,1-two (4-hydroxyphenyl) cyclododecane, trans-2,3-two (4-hydroxyphenyl)-2-butylene, 2,2-two (4-hydroxyphenyl) diamantane (Adamantine), α, α '-two (4-hydroxyphenyl) toluene, two (4-hydroxyphenyl) acetonitrile, 2,2-two (4-hydroxyphenyl) propane, 2,2-two (3-methyl-4-hydroxyphenyl) propane, 2,2-two (3-ethyl-4-hydroxyphenyl) propane, 2,2-two (3-n-propyl-4-hydroxyphenyl) propane, 2,2-two (3-sec.-propyl-4-hydroxyphenyl) propane, 2,2-two (3-sec-butyl-4-hydroxyphenyl) propane, 2,2-two (the 3-tertiary butyl-4-hydroxyphenyl) propane, 2,2-two (3-cyclohexyl-4-hydroxyphenyl) propane, 2,2-two (3-allyl group-4-hydroxyphenyl) propane, 2,2-two (3-methoxyl group-4-hydroxyphenyl) propane, 2,2-two (4-hydroxyphenyl) HFC-236fa, 1,1-two chloro-2,2-two (4-hydroxyphenyl) ethene, 1,1-two bromo-2,2-two (4-hydroxyphenyl) ethene, 1,1-two chloro-2,2-two (5-phenoxy group-4-hydroxyphenyl) ethene, 4,4 '-dihydroxy benzophenone, 3,3-two (4-hydroxyphenyl)-2-butanone, 1,6-two (4-hydroxyphenyl)-1, the 6-hexanedione, ethylene glycol bisthioglycolate (4-hydroxyphenyl) ether, two (4-hydroxyphenyl) ether, two (4-hydroxyphenyl) thioether, two (4-hydroxyphenyl) sulfoxide, two (4-hydroxyphenyl) sulfone, 9,9-two (4-hydroxyphenyl) fluorenes (fluorine), 2,7-dihydroxyl pyrene, 6,6 '-dihydroxyl-3,3,3 ', 3 '-tetramethyl-spiral shell (two) indane (" the full bis-phenol of spirobindene "), 3,3-two (4-hydroxyphenyl) 1,3-dihydrobenzo [c] furans-2-ketone, 2,6-dihydroxyl dibenzo-p-dioxin, 2,6-dihydroxyl thianthrene, 2,7-dihydric phenol flavine, 2,7-dihydroxyl-9,10-dimethyl azophenlyene, 3,6-dihydroxyl diphenylene-oxide, 3,6-dihydroxyl dibenzothiophene, 2,7-dihydroxyl carbazole, 2-phenyl-3,3-two (4-hydroxyphenyl) benzo [c] pyrrolidone (PPP), 4,4 '-(six hydrogen-4,7-endo-methylene group-2,3-indane-5-subunit) biphenol (TCD or tristane bis-phenol), 1,1-two (4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane (bis-phenol TMC), 4-[1-[3-(4-hydroxyphenyl)-4-methylcyclohexyl]-the 1-methylethyl] phenol, 4,4 '-[1-methyl-4-(1-methylethyl)-1,3-encircles dihexyl] bis-phenol, phenolphthalein, 2-methyl-3,3-two (right-hydroxyphenyl) phthalic imidine, 2-butyl-3,3-two (right-hydroxyphenyl) phthalic imidine, 2-octyl group-3,3-two (right-hydroxyphenyl) phthalic imidine, 1,3-two (4-hydroxyphenyl)-1, (wherein said alkyl has 1-4 carbon atom to 3-dialkyl cyclic hexane, for example is described in United States Patent (USP) 5,344,999) etc. and the mixture that comprises above-mentioned dihydroxy compound.In one embodiment, be used to form described R
1The described aromatic dihydroxy compound of group comprises 2,2-two (4-hydroxyphenyl) propane (dihydroxyphenyl propane).
Described polycarbonate-polysiloxane block copolymers comprises the polysiloxane block of the repeating unit that comprises following structure and comprises the surface-modifying agent of at least one polysiloxane segment:
R wherein
2Independent separately is C
1-C
12Alkyl." polysiloxane segment " is defined as and comprises at least 3 monovalence or the divalence polysiloxane parts of repeating unit as defined above.Preferred described polysiloxane segment comprises at least 5 repeating units, more preferably at least 10 repeating units.In one embodiment, R
2Be methyl.
In one embodiment, described polysiloxane block has following structure:
R wherein
2Independent separately is C
1-C
12Alkyl; R
3Independent separately is C
6-C
30Alkylene; X is 0 or 1; D is about 5-about 120.In this scope, the D value can be at least 10 especially.In this scope, the D value also can be in particular and be up to approximately 100, is more particularly and is up to approximately 75, also is more particularly and is up to approximately 60, even is more particularly and is up to about 30.
In one embodiment, x is 0, R
3Independently have following structure separately:
R wherein
4Independent separately is halogen, C
1-C
8Alkyl or C
1-C
8-oxyl; M is 0-4; N is 2-about 12.Hydrogen atom occupies on the phenyl ring any not by R
4The position that replaces.In another embodiment, R
3Independent separately is the C of biphenol
6-C
30The arylidene residue.Suitable polysiloxane block comprises Kress etc. at United States Patent (USP) 4,746,701 and Okamoto etc. at United States Patent (USP) 5,502, those that describe in 134.More particularly, described polysiloxane block can be derived from having Kress etc. at United States Patent (USP) 4,746,701 the 2nd row, and the polydiorganosiloxane of the structure of the capable definition of 29-48:
Wherein group Ar is the identical or different arylidene that preferably has 6-30 carbon atom derived from biphenol; R and R
1Identical or different, expression straight chained alkyl, branched-chain alkyl, halo straight chained alkyl, halo branched-chain alkyl, aryl or halogenated aryl, but preferable methyl, described two organic silyloxy unit number (o+p+q sum) are about 5-about 120.Described polysiloxane block also can be derived from Okamoto etc. at United States Patent (USP) 5,502,134 the 4th row, and the polydimethylsiloxane of the capable definition of 1-9:
Wherein m is about 5-about 120.
In one embodiment, described polycarbonate-polysiloxane block copolymers is made up of polycarbonate block and polysiloxane block substantially.Phrase " substantially by ... form " do not get rid of the end group derived from chain terminator, for example phenol, tert.-butyl phenol, right-cumyl phenol etc.
Described polycarbonate-polysiloxane block copolymers comprises the polycarbonate block of about 99% weight of about 70-.In this scope, the content of polycarbonate block can be in particular at least 75% weight, is more particularly at least 85% weight, also is more particularly at least 90% weight.Described polycarbonate-polysiloxane block copolymers comprises the polysiloxane block of about 30% weight of about 1-.In this scope, the content of polysiloxane block can be in particular at least about 2% weight, is more particularly at least about 3% weight.In this scope, the content of polysiloxane block also can be in particular and be up to about 25% weight, is more particularly to be up to about 15% weight, also is more particularly to be up to about 10% weight.
Described composition comprises the described polycarbonate-polysiloxane block copolymers of about 99.9% weight of about 1-.In this scope, the amount of described polycarbonate-polysiloxane block copolymers can be in particular at least about 3% weight, is more particularly at least about 5% weight, also is more particularly at least about 10% weight.In this scope, the amount of described polycarbonate-polysiloxane block copolymers also can be in particular and be up to about 99% weight, is more particularly to be up to about 90% weight, also is more particularly to be up to about 50% weight
Described composition comprises the surface-modifying agent that comprises at least one polysiloxane segment.Described polysiloxane segment comprises at least three multiple dialkylsiloxane segments.Except at least one polysiloxane segment, preferred described surface-modifying agent also comprises the segment that at least one is selected from polyolefine, polyester, polyestercarbonate, polyethers and polyarylester.Suitable polyolefine segment comprises multipolymer and above-mentioned each polyolefinic mixture of polyethylene, polypropylene, poly-(vinyl chain alkanoic acid ester) (for example poly-(vinyl-acetic ester)), halogenated polyolefin (for example tetrafluoroethylene) etc., corresponding olefinic monomer.Suitable polyester segment comprises poly-(ethylene glycol terephthalate), poly-(terephthalic acid propylene diester), poly-(butylene terephthalate), poly-(cyclohexanedimethanol cyclohexane cyclohexanedimethanodibasic ester) etc. and composition thereof.Suitable polyestercarbonate comprises that those have the material of following repeating unit: (a) carbonate repetitive unit of the polycarbonate segment of above-mentioned polycarbonate-polysiloxane copolymer and (b) the ester repeating unit of above-mentioned polyester segment.Suitable polyethers comprises polyethylene oxide, poly(propylene oxide), polybutylene oxide etc. and the monomeric multipolymer of various corresponding alkylene oxides.Suitable polyarylester comprises that those comprise the material derived from the structural unit of following material: (a) one or more aromatic diols, for example Resorcinol or dihydroxyphenyl propane and (b) one or more aromatic dicarboxylic acids, for example m-phthalic acid, terephthalic acid or naphthalene-2,6-dioctyl phthalate etc.The method for preparing polyolefine, polyester, polyestercarbonate, polyethers and polyarylester is known in the art.The method that connects polysiloxane segment and above-mentioned polymer segment also is known in the art.For example, can have the polysiloxane of oxymethoxyallylbenzene end group, link to each other with polyester, polyestercarbonate or polyacrylic ester segment subsequently by the prepared in reaction that forms ester or formation carbonic ether.The surface-modifying agent that comprises polysiloxane and polyolefin block can prepare by olefin polymerization containing vinyl or containing in the presence of the allylic siloxanes.As another example, for example Austin etc. is at United States Patent (USP) 4,857,583 and Burkhart etc. at United States Patent (USP) 5,321, the hydrosilylation reactions of the metal catalytic described in 051 can be used for forming the polysiloxane with side group polyether group.
In one embodiment, described surface-modifying agent comprises the polyester-polysiloxane segmented copolymer.Described segmented copolymer can have diblock, three blocks, four blocks, block radially far away or similar structures.In a preferred embodiment, described surface-modifying agent comprises polyester-polysiloxane-polyester three-block multipolymer.Suitable polyester-polysiloxane-polyester three-block multipolymer comprises polycaprolactone-polydimethylsiloxane-polycaprolactone triblock copolymer.Described multipolymer can prepare according to methods known in the art, and commodity have for example available from Goldschmidt's
H-Si6440P.
Described composition can comprise the surface-modifying agent of about 50% weight of about 0.1-.In this scope, the amount of described surface-modifying agent can be in particular at least 0.25% weight, is more particularly at least 0.5% weight.In this scope, the amount of described surface-modifying agent also can be in particular and be up to about 30% weight, is more particularly to be up to about 10% weight, also is more particularly to be up to about 5% weight.
Described polycarbonate-polysiloxane copolymer and described surface-modifying agent are at least described composition and have contributed total content of siloxane.Total content of siloxane of described composition can be about 30% weight of about 0.1-.In this scope, described total content of siloxane can be in particular at least about 1% weight, is more particularly at least about 3% weight.In this scope, described total content of siloxane also can be in particular and be up to about 20% weight, is more particularly to be up to about 15% weight, also is more particularly to be up to about 8% weight.
Except described polycarbonate-polysiloxane block copolymers, described composition also can comprise other polymkeric substance, for example polycarbonate, polyestercarbonate, polyester, polyarylester etc. and composition thereof.In a preferred embodiment, described composition comprises polycarbonate.Suitable polycarbonate is referring in the relevant description to the polycarbonate segment of described polycarbonate-polysiloxane copolymer.When having other polymkeric substance, the consumption of described other polymkeric substance can account for about 0.1-about 95% of described composition total weight.In this scope, the amount of described polymkeric substance can be in particular at least about 1% weight, is more particularly at least about 20% weight, also is more particularly at least about 50% weight, also is more particularly at least about 70% weight, also is more particularly at least about 75% weight.In this scope, the amount of described polymkeric substance also can be in particular and be up to about 90% weight, is more particularly to be up to about 85% weight.
Described composition can be chosen wantonly and also comprise impact modifier.Suitable impact modifier comprises elastomer-modified graft copolymer, described multipolymer comprises (i) Tg less than 0 ℃, be more particularly-40 ℃ to-80 ℃ elasticity (being rubber-like) polymeric matrix and (ii) with described elastic polymer matrix grafted rigid polymer.As is known, elastomer-modified graft copolymer can prepare by the elastomeric polymer main chain at first is provided.In the presence of described main polymer chain,, be in particular two kinds of grafted monomer polymerizations subsequently, make described graft copolymer at least a.
According to the amount of elastomer-modified polymkeric substance, can make the external phase of independent matrix or non-grafting rigid polymer or multipolymer simultaneously with described elastomer-modified graft copolymer.Common described impact modifier comprises the elastomer-modified graft copolymer of the 40-95% that accounts for described impact modifier gross weight and graftomer or the multipolymer of 5-60%.In another embodiment, described impact modifier can comprise the 50-85% that accounts for described impact modifier gross weight, maybe can comprise the graft copolymer and the 15-50% of the modified rubber of 75-85%, is more particularly graftomer or the multipolymer of 15-25%.Described non-grafting rigid polymer or multipolymer also can prepare separately, for example by radical polymerization, particularly by letex polymerization, suspension polymerization, solution polymerization or mass polymerization preparation, add to described impact modifier compositions or polycarbonate compositions subsequently.The number-average molecular weight of described non-grafting rigid polymer or multipolymer can be 20,000-200,000 atomic mass unit.
Conjugated diene rubber, conjugated diolefine are arranged and be less than multipolymer, (methyl) vinylformic acid C of the copolymerisable monomer of 50% weight as the example of the suitable material of described elastomeric polymer main chain
1-C
8Alkyl ester elastomerics, olefinic rubber be ethylene-propylene copolymer (EPR) or ethylene-propylene-diene monomers (EPDM), silicon rubber, elasticity (methyl) vinylformic acid C for example
1-C
8Alkyl ester, (methyl) vinylformic acid C
1-C
8Alkyl ester and divinyl and/or cinnamic elastocopolymer or comprise at least a above-mentioned elastomeric combination.
The suitable conjugate diene monomer that is used to prepare described main polymer chain can have following formula:
X wherein
bIndependent separately is hydrogen, C
1-C
5Alkyl, chlorine, bromine etc.The example of available conjugate diene monomer has divinyl, isoprene, 1,3-heptadiene, methyl isophthalic acid, 3-pentadiene, 2,3-dimethyl-1,3-divinyl, 2-ethyl-1,3-pentadiene, 1,3-hexadiene, 2, the divinyl that 4-hexadiene, chloro-and bromo-replace be dichloroprene, bromoprene, dibromo divinyl etc. and the mixture that comprises at least a above-mentioned conjugate diene monomer for example.Conjugated diene homopolymers is particularly including polyhutadiene and polyisoprene.
For example also can use and to carry out the multipolymer of the conjugated diene rubber of moisture free-radical emulsion polymerization preparation with the monomer of its copolymerization by conjugated diolefine and one or more.Be suitable for comprising the mono vinyl aromatic monomer that comprises the fused aromatic rings structure, for example vinyl naphthalene, vinyl anthracene etc. or have the monomer of following formula with the monomer of described conjugated diolefine copolymerization:
X wherein
cIndependent separately is hydrogen, C
1-C
12Alkyl, C
3-C
12Cycloalkyl, C
6-C
12Aryl, C
7-C
12Aralkyl, C
7-C
12Alkaryl, C
1-C
12Alkoxyl group, C
3-C
12Cycloalkyloxy, C
6-C
12Aryloxy, chlorine, bromine or hydroxyl, R are hydrogen, C
1-C
5Alkyl, bromine or chlorine.The example of the mono vinyl aromatic monomer that available is suitable has vinylbenzene, 3-vinyl toluene, 3,5-diethylbenzene ethene, 4-n-propylbenzene ethene, alpha-methyl styrene, Alpha-Methyl Vinyl toluene, α-chloro-styrene, bromstyrol, dichlorostyrene, Dowspray 9, tetrachlorobenzene ethene etc. and combination thereof.Vinylbenzene and/or alpha-methyl styrene usually as can with the monomer of described conjugate diene monomer copolymerization.Also can use the mixture of above-mentioned mono-vinyl monomer and mono vinyl aromatic monomer.
Suitable impact modifier is known in the art.Non-limiting instance is described in U.S. Patent Application Publication No. 20020111428 A1 of the United States Patent (USP) 5,126,428 of the United States Patent (USP) 5,859,119 of Hoefflin and Freitag etc. and Gaggar etc.Described impact modifier comprises a kind of in several different rubber-like properties-correcting agent, for example combination of grafting or nuclear-shell rubber or two or more these properties-correcting agent usually.The example comprises following properties-correcting agent: acrylic rubber, ASA rubber, elastoprene, organopolysiloxane elastomer, silicon rubber, EPDM rubber, SBS or SEBS rubber, ABS rubber, MBS rubber and glycidyl ester sill.
That term " acrylic rubber modifier " can refer to is multistage, nuclear-shell, have the interpolymer properties-correcting agent of crosslinked or partial cross-linked (methyl) acrylate (being preferably butyl acrylate) rubber-like nuclear phase.With described crosslinked acrylate core bonded be the acrylic acid or the like of the described rubber-like nuclear phase of IPN or the shell of styrene resin, be preferably methyl methacrylate or vinylbenzene shell.For example vinyl cyanide or (methyl) vinyl cyanide also provide suitable impact modifier to mix a small amount of other monomers in described resin shell.In the presence of polymerization in advance and crosslinked (methyl) acrylic elastomer shape,, form interpenetrating(polymer)networks when the monomer polymerization of forming described resin phase with when crosslinked.
For certain embodiments of the present invention, preferred rubber is grafting or nucleocapsid structure, contains Tg less than about 0 ℃, is preferably-40 ℃ to about-80 ℃ rubber-like component approximately.These materials comprise poly-(alkyl acrylate) or the polyolefine of grafting PMMA (polymethylmethacrylate) or SAN (styrene-acrylonitrile).The content of preferred described rubber is at least about 40% weight, most preferably is about 90% weight of about 60-.Specially suitable rubber is divinyl core-shell polymer class, available from Rohm﹠amp; Haas, for example
EXL2600.
In certain embodiments, described impact modifier comprises the two-step approach polymkeric substance with bivinyl rubber shape nuclear, in second step with independent methyl methacrylate or methyl methacrylate and cinnamic polymerization mix.Other suitable rubber are the ABS type
336 and 415, available from GE Specialty Chemicals.Two kinds of rubber are all based on SBR rubber impact modifiers resin.
Though described impact modifier is most suitable, also can use many known properties-correcting agent of this polymer arts that are.Multiple factor is depended in the selection of usually concrete impact modifier.These factors comprise: cost, availability, room temperature and cryogenic erosion-resisting characteristics, refractive index, with the consistency and the required whole optical property and the physicals of described polymeric system of described polycarbonate-polysiloxane block copolymers and described surface-modifying agent.Can use the impact modifier of refractive index, then can as long as have the suitable transparency for about 1.51-about 1.58.The consumption of described impact modifier can be depending on multiple these identical factors.Usually the required amount of shock resistance is a principal element.In some cases, when having impact modifier in the described composition, its consumption can account for about 1-about 30% of described composition total weight.
Described composition can be chosen wantonly and also comprise additive.Described additive comprises filler, toughener, thermo-stabilizer, antioxidant, photostabilizer (particularly ultraviolet absorbers), gamma-irradiation stablizer, softening agent, tinting material, extender, static inhibitor, catalyst quenchers, lubricant, releasing agent, processing aid, whipping agent, fire retardant, anti-drops etc. and composition thereof.That described additive is known in the art and commercially available getting.Those of ordinary skill in the art knows how to select these additives and to determine its consumption according to the desired use of described composition.
When described composition is defined as when comprising various ingredients, be understood that each component chemically is being different, can realize can be considered the Special Circumstances that comprise various ingredients at single kind of compound more than a kind of situation of definition of component.
In one embodiment, described composition (or goods prepared therefrom) can have one or more following required performances: adopt ASTM D1003, measure the % transmission at the thick place of 3.2mm and be at least 70%, be at least 80% more especially; Employing ASTM D1003 measures the % mist degree at the thick place of 3.2mm and is less than or equal to 10%, is more particularly to be less than or equal to 6%; Under 23 ℃, it is about 1 for about 500-to adopt ASTM D256 to measure jagged beam type shock strength, 000J/m, the more special about 900J/m of 600-that is at least; Under 23 ℃, it is about 1 adopting ASTM D4812 to measure non-notch beam type shock strength, and 000-is about 3, and 000J/m is more particularly approximately 1, and 500-is about 2, and 400J/m also is more particularly approximately 2, and 000-is about 2,200J/m; Method according to ISO10993-4:2002 (E) and following embodiment 10 and 11 is measured, when blood in described composition than blood in being about 20 by weight-average molecular weight, 000-about 30, thrombocyte % keeps (retention) high at least 5% during composition that the bisphenol-a polycarbonate homopolymer of 000 atomic mass unit is formed, be more particularly highly at least by 10%, also be more particularly high at least 20%.Last performance is the objective indication of blood compatibility, term " high 5% ", " high 10% " and " high 20% " are meant blood in composition of the present invention absolute difference that 30 minutes thrombocyte % keeps to be kept with blood thrombocyte % of 30 minutes in polycarbonate homopolymer.For example adopt the real data of comparing embodiment 15 and embodiment 10, if blood is left 93.5% in the thrombocyte % of the present composition, blood is left 73.4% in the thrombocyte % of polycarbonate homopolymer, and then blood keeps in the thrombocyte % of the present composition and keeps high by 20.1% (93.5-73.4) than blood in the thrombocyte % of polycarbonate homopolymer.
One embodiment of the invention are a kind of composition, and described composition comprises: aromatic polycarbonate; The polyester-polysiloxane segmented copolymer; With the polycarbonate-polysiloxane block copolymers that comprises at least one polycarbonate block and at least one polysiloxane block; Wherein said polycarbonate block comprises the repeating unit with following structure:
A wherein
1And A
2Independent separately is the monocycle divalent aryl; Y wherein
1Be selected from-O-,-S-,-S (O)-,-S (O)
2-,-C (O)-and C
1-C
18Alkylene; Wherein said polysiloxane block has following structure:
R wherein
2Independent separately is C
1-C
12Alkyl; R
3Independent separately is C
6-C
30Alkylene; X is 0 or 1; D is 5-about 120.
Further embodiment of this invention is a kind of composition, described composition comprises: the bisphenol-a polycarbonate of about 95% weight of about 60-; The polycaprolactone of about 10% weight of about 0.1--poly-(dimethyl siloxane)-polycaprolactone triblock copolymer; The polycarbonate-polysiloxane block copolymers that comprises at least one polycarbonate block and at least one polysiloxane block with about 40% weight of about 5-; Wherein said polycarbonate block comprises the repeating unit with following structure:
Wherein said polysiloxane block comprises the repeating unit with following structure:
Wherein D is about 5-about 100.
Further embodiment of this invention is a kind of composition, described composition comprises: the bisphenol-a polycarbonate of about 90% weight of about 70-; The polycaprolactone of about 5% weight of about 0.2--poly-(dimethyl siloxane)-polycaprolactone triblock copolymer; The polycarbonate-polysiloxane block copolymers that comprises at least one polycarbonate block and at least one polysiloxane block with about 25% weight of about 10-; Wherein said polycarbonate block comprises the repeating unit with following structure:
Wherein said polysiloxane block comprises the repeating unit with following structure:
Wherein D is about 30-about 70.
Further embodiment of this invention is a kind of composition, described composition comprises: the bisphenol-a polycarbonate of about 85% weight of about 75-; The polycaprolactone of about 2% weight of about 0.5--poly-(dimethyl siloxane)-polycaprolactone triblock copolymer; The polycarbonate-polysiloxane block copolymers that comprises at least one polycarbonate block and at least one polysiloxane block with about 20% weight of about 15-; Wherein said polycarbonate block comprises the repeating unit with following structure:
Wherein said polysiloxane block comprises the repeating unit with following structure:
Wherein D is about 40-about 60.
Further embodiment of this invention is a kind of method for preparing thermoplastic compounds, described method comprises: will comprise the surface-modifying agent and the polycarbonate-polysiloxane block copolymers blend that comprises at least one polycarbonate block and at least one polysiloxane block of at least one polysiloxane segment, and form the intimate blending thing; Wherein said polycarbonate block comprises the repeating unit with following structure:
R wherein
1About 60-100% is for replacing or unsubstituted divalent aromatic organic group in the group sum, and 0-about 40% is aliphatic divalent group or divalence alicyclic group; Wherein said polysiloxane block comprises the repeating unit with following structure:
R wherein
2Independent separately is C
1-C
12Alkyl.
Other embodiments of the present invention comprise the goods that comprise any above-mentioned composition.For example described goods can comprise film, sheet material, molded object, film or matrix material, and wherein said film, sheet material, molded object, film or matrix material have the layer that one deck at least comprises described composition.Adopt thermoplastic method commonly used composition of the present invention can be converted into goods, described method is film and sheet material is extruded, injection moulding, gas aided injection mould, extrusion molding, compression moulding, blowing etc. for example.Film and sheet material extrusion molding can comprise fusion curtain coating (cast), blown-film extrusion and calendering.Can use coextrusion and laminating to form composite material by multilayer film or sheet material.Also can apply the single or multiple lift coating to give other performances, for example anti-zoned trace, ultraviolet light, requirement attractive in appearance etc. to described single or multiple lift ground.Can pass through standard application techniques applying coating, for example roller coat, spraying, dip-coating, brushing or flow coat.Film perhaps of the present invention and sheet material can by with described composition in suitable solvent solution or the suspension curtain coating at ground, on band or the roller, removing subsequently desolvates prepares.
The film of orientation can prepare by blown-film extrusion, perhaps uses conventional stretching technique, near thermal distorsion temperature by the stretching curtain coating or the film preparation of having rolled.For example stretch simultaneously, can use the radial drawing pantograph for multiaxis; Can use x-y direction stretching pantograph while or priority to stretch in plane x-y direction.Also can use equipment,, for example be equipped with the part of the friction-motion speed roller that is used for longitudinal stretching and be used for the machine of tensile tentering machine frame part in the other direction to obtain single shaft and biaxial stretch-formed with order uniaxial extension part.
Composition of the present invention can be converted into the multi-layer sheet that comprises first kind of sheet material and second kind of sheet material, wherein first kind of sheet material has first and second, wherein said first kind of sheet material comprises thermoplastic polymer, and first face of wherein said first kind of sheet material is arranged on first of a plurality of timbers; Described second kind of sheet material has first and second, wherein said second kind of sheet material comprises thermoplastic polymer, first face of wherein said second kind of sheet material is arranged on second of a plurality of timbers, wherein first of a plurality of timbers reverse side of second at a plurality of timbers.
Above-mentioned film and sheet material also can be processed into moulded products by moulding and moulding method, and described method is including, but not limited to thermoforming, vacuum forming, pressure forming, injection moulding and compression moulding.Multilayer formed article also can as described belowly come moulding by injection heat plastic resin on single or multiple lift film or sheet material ground:
1. for example adopt silk screen printing or infection protocol (transfer dye) to be provided to have on the described surface and choose any one kind of them or the single or multiple lift thermoplasticity ground of multiple color.
2. for example make described ground adapt to the structure of mould, subsequently ground is trimmed to 3D shape, described ground is assemblied in the mould with the surface of mating with the 3D shape of described ground by moulding.
3. in described die cavity, inject thermoplastic resin in the back of described ground, (i) produce the three-dimensional objects of permanent adhesive of monoblock or the pattern or the aesthetic that (ii) will print ground and be transferred to the described resin that has injected, remove the ground that has printed subsequently, therefore give described moulding resin aesthetic.
Those skilled in the art will also be understood that also and can use curing commonly used and surface modification method changing appearance and to give described goods other functions to said products, and described method comprises and is not limited to heat setting, decorative pattern, embossing, corona treatment, flame treating, Cement Composite Treated by Plasma and vacuum deposition.
All scopes disclosed herein comprise end points, and each end points can make up mutually.
Further specify the present invention by following non-restrictive example.
Comparing embodiment 1-5
These comparing embodiment explanations have damaged required high transmission and the low haze of polycarbonate resin when adding the surface-modifying agent of low amount.5 kinds of compositions that surface modification dosage is different have been prepared.It is about 30 that each composition comprises weight-average molecular weight, and the first kind of bisphenol-a polycarbonate (BPA-PC) of 000AMU and weight-average molecular weight are about 21, second kind of bisphenol-a polycarbonate of 800AMU.Comparing embodiment 1 does not comprise surface-modifying agent.Total weight-average molecular weight that comparing embodiment 2-4 comprises 0.10-1.0% weight is about 22, and 000AMU and polydimethylsiloxane content are the polycaprolactone-polydimethylsiloxane-polycaprolactone triblock copolymer (" LSL multipolymer ") of about 44% weight.This LSL multipolymer derives from Goldschmidt's
H-Si 6440P.All component and the melt-processed of blend prepare composition in forcing machine.The barrel zone temperature of melt-processed polycarbonate is 280 ℃, but can be 260-310 ℃.Injection moulding prepares the test sample of 8cm * 10cm * 0.32cm size.Adopt ASTM D1003, measure % transmission and mist degree at the thick place of 3.2mm.Adopt electronic spectroscopy chemical analysis (ESCA), measure surface silicon content with 15 ° of angle of pull.The result represents the surface silicon content of the dark test sample of about 2nm.Adopt ASTM D638, measure tensile modulus down at 23 ℃, with MPa (MPa) expression.Adopt ASTM D256, measure jagged beam type impact strength value down at 23 ℃, with joules per meter (J/m) expression.Composition and the results are shown in Table 1.The amount of all components is represented with weight part.The result shows although add the required effect that a spot of LSL has increases the molded article surface silicone content in bisphenol-a polycarbonate, also to have the undesired effect that reduces the % transmission and increase the % mist degree simultaneously.
Table 1
| Comparing embodiment 1 | Comparing embodiment 2 | Comparing embodiment 3 | Comparing embodiment 4 | Comparing embodiment 5 | |
| Composition | - | - | - | - | - |
| BPA-PC，30,000AMU | 18.00 | 18.00 | 18.00 | 18.00 | 18.00 |
| BPA-PC，21,800AMU | 82.00 | 82.00 | 82.00 | 82.00 | 82.00 |
| LSL | 0.00 | 0.10 | 0.25 | 0.50 | 1.00 |
| Performance | - | - | - | - | - |
| The % transmission | 914 | 87.6 | 71.9 | 53.7 | 44.3 |
| The % mist degree | 0.3 | 1.6 | 22.8 | 85.5 | 100.0 |
| Surface silicon content (% weight) | 0.0 | 0.3 | 0.4 | - | 1.3 |
| Tensile modulus (MPa) | 2,248 | 2,261 | 2,234 | 2,268 | 2,248 |
| Jagged beam type shock strength (J/m) | 747 | 731 | 721 | 737 | 747 |
Embodiment 1-6, comparing embodiment 6
These embodiment explanations comprise polycarbonate-polysiloxane block copolymers and contain the composition surface silicone content height of the surface-modifying agent of siloxanes, good in optical property simultaneously.Prepare 7 kinds and be mainly the amount difference of surface-modifying agent and the composition that has or do not exist polycarbonate homopolymer.Employing is similar to embodiment 2 described methods in U.S. Patent Application Serial 10/797418 such as DeRudder and prepares this polycarbonate-polysiloxane block copolymers.Its weight-average molecular weight is about 23,500AMU, and total polydimethylsiloxane content is 6% weight, polydimethylsiloxane segmental mean chain length is about 50 repeating units.Composition and performance are summarized in table 2.The result shows, the optical property of the embodiment 1-5 that is made up of polycarbonate-polysiloxane block copolymers and LSL triblock copolymer is similar to the comparing embodiment that does not contain any LSL.Embodiment 5 and 6 explanations are compared with the blend of polycarbonate homopolymer and LSL, and the composition that comprises polycarbonate-polysiloxane copolymer, carbonic ether homopolymer and LSL can contain more high-load LSL and not damage optical property.
Table 2
| Comparing embodiment 6 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Composition | |||||||
| BPA-PC， 30,000AMU | - | - | - | - | - | 10.5 | 9.9 |
| BPA-PC， 21,800AMU | - | - | - | - | - | 5.70 | 5.40 |
| Polycarbonate-polysiloxane | 100.00 | 99.50 | 99.25 | 99.00 | 98.50 | 78.60 | 74.50 |
| LSL | - | 0.50 | 0.75 | 1.00 | 1.50 | 5.00 | 10.00 |
| Performance | |||||||
| The % transmission | 86.1 | 84.6 | 87.5 | 87.3 | 86.7 | 71.2 | 53.5 |
| The % mist degree | 1.6 | 2.7 | 1.7 | 1.8 | 1.9 | 13.7 | 51.6 |
| Surface silicon content (% weight) | 4.5 | - | - | - | 6.5 | - | - |
Embodiment 7, comparing embodiment 7 and 8
These embodiment illustrate that surface-modifying agent LSL can not make the composition optical clear by opaque polycarbonate-polydimethylsiloxanecopolymer copolymer preparation.The kind of main variation polycarbonate-polysiloxane copolymer and the amount of consumption and surface-modifying agent have prepared 3 kinds of compositions.The multipolymer that uses in the material that is abbreviated as " transparent polycarbonate-polysiloxane copolymer " in the table 3 and the foregoing description is identical, be that its weight-average molecular weight is about 23,500 AMU, total polydimethylsiloxane content is 6% weight, polydimethylsiloxane segmental chain length is about 50 unit.The weight-average molecular weight that is abbreviated as the material of " opaque polycarbonate-polysiloxane copolymer " in the table 3 is about 30,000, and total polydimethylsiloxane content is 20% weight, and polydimethylsiloxane segmental chain length is about 50 unit.Composition and optical property see Table 3.The result shows that the LSL of adding 1% does not improve optical property (comparing embodiment 8 and comparing embodiment 7) in the composition that comprises opaque polycarbonate-polysiloxane copolymer.The result also shows, the blend optical property of polycarbonate homopolymer, transparent polycarbonate-polysiloxane copolymer and 1%LSL is fabulous.
Table 3
| Comparing embodiment 7 | Comparing embodiment 8 | Embodiment 7 | |
| Composition | |||
| BPA-PC，30,000 AMU | 37.5 | 37.5 | 16.0 |
| BPA-PC，21,800 AMU | 44.0 | 44.0 | 32.5 |
| Transparent polycarbonate-polysiloxane | 17.5 | 17.5 | 50.0 |
| Opaque polycarbonate-polysiloxane | 17.5 | 17.5 | - |
| LSL | 0.0 | 1.0 | 1.0 |
| Performance | |||
| The % transmission | 20.0 | 19.6 | 83.0 |
| The % mist degree | 100.0 | 99.5 | 3.1 |
Embodiment 8, comparing embodiment 9-11
Two kinds of blood compatibility responses of 4 kinds of thermoplastic compounds of test: with the variation of composition incubation platelet count after 1 hour and the variation of white corpuscle activity intensity.Instrument and testing method are specified in C.H.Gemmell etc. at J.Lab.Clin.Med.1995 the 125th volume, the 2nd phase, 276-287 page or leaf.Testing method is summarized as follows.Each thermoplastic compounds is as the test tube test of 25cm length * 1.57mm internal diameter.Use the silication rubber hose that test material is linked to each other with instrument.Sample to preparation adopts following steps.
1. before test, test tube was heated 30 minutes down in 37 ℃.
2. abandon first milliliter, in the syringe that 5 units heparin/ml is housed in advance, collect volunteer's blood.
3. material is connected in a low arm of shearing instrument.
4. by the pine end, use the 1ml syringe in pipe, to inject 450 μ l blood by silication rubber.Pine end is linked to each other with the low instrument of shearing, subsequently in 37 ℃ of following jogs 1 hour.
At the trial between in, under 37 ℃, remaining whole blood sample (400 μ l) is placed in the centrifuge tube of sealing.
6. during off-test, use filtered air that blood flow is gone in the micro-centrifuge tube.
7. from each sample, shift 30 μ l blood to micro-centrifuge tube, add 3 μ l platelet agonists, thrombin peptide (Serine-phenylalanine-leucine-leucine-arginine-l-asparagine subsequently; SFLLRN).Test tube is placed in 37 ℃ the incubator 20 minutes, with activated blood platelet.
8. immediately blood sample is carried out flow cytometry (seeing below).
9. use the part of detecting of irrigation with syringe phosphoric acid salt buffer salt solution (PBS), come out until all blood rinsings.
Use following steps to carry out flow cytometry.
1. use the PBS of calcic and magnesium to prepare the flow cytometry pipe to accept blood sample.
The thrombocyte analysis needs 2 cover test tubes:
Unicellular antibody (the FITC-CD41a that the fluorescein isothiocyanate of the anti-people CD41a of (test tube A) 50 μ l PBS+2 μ l is puted together; α IIb/IIIa)+3 unicellular antibody (PE-CD62P) solution (in PBS, diluting) (α P-selectin) puted together of the phycoerythrin of the anti-people CD62P of μ l with 1: 10
(test tube A ') is identical with test tube A, and difference is to accept the blood of 5 μ l aliquots from SF-activatory sample.
White corpuscle CD11b analyzes needs 2 cover test tubes:
The unicellular antibody (PE-CD45) that the phycoerythrin of the anti-people CD45 of unicellular antibody (FITC-CD11b)+1 μ l that the fluorescein isothiocyanate of the anti-people CD11b of (test tube B) 50 μ l PBS+5 μ l is puted together is puted together
(test tube B ') is identical with test tube B, adds 6 μ l phorbal12-myristate 13-acetate (PMA) solution (diluting in PBS with 1: 10).
2. adding 20 μ l blood carry out leukocyte analysis (being test tube B and B ') and add 5 μ l blood in each test tubes carrying out thrombocyte analysis (being test tube A) in each test tube.Blood to the middle adding 5 μ l SF-activation of test tube A ' sample.The EDTA that adds 6 μ l200mM in the blood sample of remaining about 300 μ l is used for cell counting.
Under room temperature with this test tube incubation 20 minutes.
4. only to the Paraformaldehyde 96 of test tube A and middle adding 200 each PBS of μ l of A ' and 2%, store down in 4 ℃ immediately, until analysis.
5. for leukocyte analysis (test tube B and B '), add 100 μ l Optilyse C RBC dissolved solution (5 times to treating the dissolved blood volume).Simple immediately vortex after the adding dissolved damping fluid in each test tube.
Under room temperature with this test tube incubation 10 minutes, (be transparent red solution, do not have muddy) fully until dissolving.
7. under room temperature, with the speed of 1300rpm centrifugal 2 minutes.
8. test tube is overturn fast, abandon dissolved solution.
9. if can be observed red bead, repeating step 5-7.
10. the Paraformaldehyde 96 that adds 100 each PBS of μ l and 2%.
11. store down in 4 ℃, until analysis.
To each blood sample, thrombocyte and leukocyte count are recorded in automatic CoulterAcT diff 2 blood analysers of multiparameter.
The transparent polycarbonate-polysiloxane copolymer that is used for comparing embodiment 9 and embodiment 8 comprises the polysiloxane of 6% weight, and wherein polydimethylsiloxane segmental chain length is about 50 unit.Employing is similar to embodiment 2 described method preparations in U.S. Patent Application Serial 10/797418 such as DeRudder.The composition representative of comparing embodiment 10 has the proprietary concentrate of improved blood compatibility.It comprises the methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS) (available from the TERLUX2802 of BASF) and 1% of 99 weight parts
H-Si6440P (available from Degussa Goldschmidt).Composition and performance are summarized in table 4.For each composition, the thrombocyte numerical value of representing with average deviation and standard deviation calculates based on 5 samples.The thrombocyte numerical value that does not wherein contain the control sample of any thermoplastic compounds incubation is (204 ± 29) * 10
6/ ml.For thermoplastic compounds, platelet count is high more required.The result shows that comparing embodiment 9, embodiment 8 and comparing embodiment 11 have undistinguishable platelet count on the statistics, and its platelet count is lower than the platelet count of (being not so good as) comparing embodiment 10.It is relevant with total content of siloxane of thermoplastic compounds that this thrombocyte numerical value can not be interpreted as.The active result of white corpuscle fluorescence intensity unit representation at random.Lower value is more wished.In this test, the white corpuscle activity value of control sample (no thermoplastic material) is 13 ± 6.The result shows, all comprises comparing embodiment 9 and the white corpuscle specific activity comparing embodiment 10 of embodiment 8 and 11 the white corpuscle activity low (excellence) of polycarbonate-polysiloxane block copolymers.
Table 4
| Comparing embodiment 9 | Embodiment 8 | Comparing embodiment 10 | Comparing embodiment 11 | |
| Composition | ||||
| Polycarbonate-polysiloxane | 57.91 | 57.91 | - | - |
| BPA-PC，21,800AMU | 27.96 | 27.96 | - | 35.0 |
| BPA-PC，30,000AMU | 13.98 | 13.98 | - | 65.0 |
| Phosphites stabilizers | 0.06 | 0.06 | - | 0.6 |
| Water | 1.00 | 1.00 | - | 0 |
| LSL | - | 1.01 | 1.01 | - |
| MABS | - | - | 100.00 | - |
| Performance | - | - | - | - |
| Platelet count (10 6/ml) | 78±14 | 87±24 | 115±20 | 68±19 |
| White corpuscle activity (random units) | 25±7 | 23±9 | 46±4 | 61±7 |
Embodiment 9, comparing embodiment 13 and 14
These embodiment illustrate and use the polycarbonate-polysiloxane block copolymers with shorter polysiloxane chain length can improve blood compatibility, cause the blood compatibility of composition suitable with the grouping of commodities thing with blood compatibility.These tests use above-mentioned thrombocyte to keep and the white corpuscle activity methods.Comparing embodiment 13 is identical with above-mentioned comparing embodiment 10, and representative has the proprietary concentrate of improved blood compatibility.Comparing embodiment 14 and embodiment 9 mainly are made up of polycarbonate-polysiloxane block copolymers, and the total polysiloxane level of this multipolymer is 3% weight, and polydimethylsiloxane segmental chain length is about 10 unit.Comparing embodiment 14 is made up of this multipolymer fully, and embodiment 9 also comprises the polycaprolactone-polysiloxane-polycaprolactone triblock copolymer of 1% weight.Composition and performance are summarized in table 5.The thrombocyte numerical value of platelet count control sample (no thermoplastic material) is (225 ± 50) * 10
6/ ml.The platelet count result shows that 3 kinds of all compositions have undistinguishable performance on the statistics.In other words, composition and comparing embodiment 13 compositions with polycarbonate-polysiloxane block copolymers of short siloxanes segment are represented the commodity thermoplastic blend with blood compatibility.In the white corpuscle activity test, the white corpuscle activity value of control sample is 12 ± 3.The active result of white corpuscle shows that the comparing embodiment 14 and embodiment 9 compositions that all comprise the polycarbonate-polysiloxane block copolymers of short siloxanes segment are better than comparing embodiment 13 compositions.Be that total siloxanes can not indicate blood compatibility unexpectedly.
Table 5
| Comparing embodiment 13 | Comparing embodiment 14 | Embodiment 9 | |
| Composition | |||
| Polycarbonate-polysiloxane | - | 100.00 | 100.00 |
| LSL | 1.01 | - | 1.01 |
| MABS | 100.00 | - | - |
| Performance | - | - | - |
| Platelet count (10 6/ml) | 121±30 | 101±26 | 97±34 |
| White corpuscle activity (random units) | 45±4 | 30±8 | 30±8 |
Embodiment 10 and 11, comparing embodiment 15 and 16
These test explanations add the blood compatibility that surface-modifying agent can improve composition in polycarbonate-polysiloxane copolymer.Employing is different from above-mentioned method and has tested 4 kinds of compositions.This method is carried out in two steps, at first with blood in test material, platelet count is decided in second pacing.Following blood is exposed to test material, will be collected in from people volunteer's blood in the anti-coagulant Citrate trianion phosphate-saline-glucose.Citrate trianion phosphate-saline-glucose solution comprises 0.299g Citric Acid, usp, Anhydrous Powder USP, 2.63g dehydration Trisodium Citrate USP, 0.222g one hypophosphite monohydrate disodium hydrogen USP, 2.90g glucose, 0.027g VITAMIN B4 USP and 100ml water.Use this damping fluid of 49ml to collect 350ml blood.The test material of preparation moulded parts is of a size of 50.8mm * 76.2mm * 3.175mm (2 inches * 3 inches * 0.125 inch), be placed on the hole of polystyrene Petri vessel, immerse subsequently in the phosphate buffer saline, before test material is exposed to blood, this damping fluid is removed.Add 25ml blood for each hole, collect the 0.5ml sample immediately and be used for cell counting.Use Environ shaker, constant temperature is exposed in the material 30 minutes under remaining 24.5ml blood stirred with 75 ± 5 rev/mins speed under 35 ± 2 ℃.To 3 samples of each testing of materials.The polystyrene flask of 3 skies is exposed in the blood as reference.Use COBAS MINOS Vet automatic hematology analyzer (Roche Diagnostics, France makes) to detect initial and after 30 minutes in the sample number of cell analyze the minimizing of number.(Bio-Rad USA) calibrates this equipment, measures subsequently to use three layers of contrast of traceable canonical reference contrast Liquichek16.Use following formula to calculate thrombocyte and keep (%): thrombocyte keeps (%)=(final hematoblastic concentration * 100)/(hematoblastic starting point concentration).
Comparing embodiment 15 adds that by the bisphenol-a polycarbonate homopolymer a small amount of releasing agent and phosphites stabilizers form.Comparing embodiment 16 comprises that containing 17.5% total siloxanes is about 50 unitary polycarbonate-polysiloxane copolymers, bisphenol-a polycarbonate homopolymer, phosphites stabilizers and water as segment and chain length.Repeat embodiment 10 and 11, the two all comprises a large amount of bisphenol-a polycarbonates, polycaprolactone-polysiloxane-polycaprolactone the triblock copolymer that adds transparent polycarbonate-polysiloxane copolymer, phosphites stabilizers and 1% weight (derives from Goldschmidt
H-Si 6440P).Composition and performance are summarized in table 6.The result shows, contains the embodiment 10 of polycarbonate-polysiloxane copolymer and polycaprolactone-polysiloxane-polycaprolactone triblock copolymer and 11 thrombocyte and keeps greater than (being better than) comparing embodiment 15 and 16.These results show, in the composition that comprises polycarbonate-polysiloxane copolymer, add surface-modifying agent for example polycaprolactone-polysiloxane-polycaprolactone triblock copolymer can improve the blood compatibility of said composition.
Table 6
| Comparing embodiment 15 | Comparing embodiment 16 | Embodiment 10 | Embodiment 11 | |
| Composition | ||||
| Polycarbonate-polysiloxane | - | 57.91 | 17.33 | 17.33 |
| BPA-PC，21,800AMU | 89.65 | 27.96 | 24.75 | 24.75 |
| BPA-PC，30,000AMU | 9.96 | 13.98 | 56.93 | 56.93 |
| Releasing agent | 0.27 | - | - | - |
| Phosphites stabilizers | 0.03 | 0.06 | 0.06 | 0.06 |
| Water | - | 0.10 | - | - |
| LSL | - | - | 0.99 | 0.99 |
| Performance | ||||
| Thrombocyte keeps (%) | 73.4±5.4 | 83.7±4.2 | 93.5±5.7 | 89.9±3.0 |
Embodiment 12-14, comparing embodiment 17 and 18
The variation of these test explanation surface-modifying agents.Contrast is polycarbonate homopolymer (comparing embodiment 17) and polycarbonate-polysiloxane copolymer (comparing embodiment 18).This polycarbonate homopolymer is that weight-average molecular weight is the bisphenol-a polycarbonate of 21,800 AMU.This polycarbonate-polysiloxane block copolymers contains the siloxanes of 6% weight, and the chain length of siloxanes segment is about 50 unit.Embodiment 12-14 all comprises the polycarbonate-polysiloxane block copolymers of 99% weight and the surface-modifying agent of 1% weight.In embodiment 12, surface-modifying agent is the polycaprolactone-polysiloxane-polycaprolactone triblock copolymer that derives from Goldschmidt
H-Si 6440P.In embodiment 13, surface-modifying agent is water-soluble poly oxyethane-polydimethylsiloxane-polyethylene oxide triblock copolymer, and total content of siloxane is 11% weight, and the number-average molecular weight of polyethylene oxide segment is 900 AMU.This surface-modifying agent derives from the SF1388 of GE Silicones.In embodiment 14, surface-modifying agent has following structure:
The median average of ethylene oxide unit in the 7.5 expression per molecules wherein.It derives from the Silwet of GESilicones
Tensio-active agent.Adopt the method for embodiment 10 and 11 to measure the reservation of % platelet count.Composition and the results are summarized in table 7.The result shows that the % thrombocyte that comprises each composition of polycarbonate-polysiloxane block copolymers and surface-modifying agent keeps all than independent polycarbonate-polysiloxane block copolymers or polycarbonate homopolymer height.
Table 7
| Comparing embodiment 17 | Comparing embodiment 18 | Embodiment 12 | Embodiment 13 | Embodiment 14 | |
| Composition | |||||
| Polycarbonate-polysiloxane | - | 100.0 | 99.0 | 99.0 | 99.0 |
| BPA-PC，21,800AMU | 100.0 | - | - | - | - |
| LSL | - | - | 1.0 | - | - |
| The polysiloxane that polyethers replaces | - | - | - | 1.0 | - |
| Polyether-polysiloxane-polyethers triblock copolymer | - | - | - | - | 1.0 |
| Performance | |||||
| Thrombocyte keeps (%) | 66.1±4.8 | 72.5±2.6 | 87.5±6.7 | 82.8±5.3 | 76.6±5.6 |
Though described the present invention with reference to embodiment preferred, what one skilled in the art should appreciate that is can carry out various variations and available equivalents replaces each key element under the situation that does not depart from the scope of the invention.In addition, under the situation that does not depart from base region of the present invention, can carry out many changes, make particular case or material adapt to instruction of the present invention.Therefore, mean that the present invention is not limited to as implementing the disclosed specific embodiments of best mode of the present invention, still present invention resides in all embodiments in additional claims scope.
The patent of all references, patent application and other references all are attached to herein by quoting in full.
Unless this paper illustrates in addition or context is obviously conflicting, otherwise has both comprised this concrete material itself when mentioning certain material among the present invention's (particularly at following claims), also comprises the affiliated class material of this material.In addition, it should be noted that term " first ", " second " etc. are not represented any order, amount or importance, but are used for each key element is distinguished mutually herein.
Claims (11)
1. composition, described composition comprises:
Comprise the polycarbonate-polysiloxane block copolymers of at least one polycarbonate block and at least one polysiloxane block and comprise that at least one polysiloxane segment and at least one are selected from the segmental surface-modifying agent of polyolefine, polyester, polyestercarbonate and polyethers, wherein said polycarbonate block comprises the repeating unit with following structure:
R wherein
160-100% is for replacing or unsubstituted divalent aromatic organic group in the group sum, and 0-40% is aliphatic divalent group or divalence alicyclic group; Wherein said polysiloxane block comprises the repeating unit with following structure:
R wherein
2Independent separately is C
1-C
12Alkyl.
2. the composition of claim 1, wherein said polycarbonate-polysiloxane block copolymers is made up of polycarbonate block and polysiloxane block substantially.
3. the composition of claim 1, the polysiloxane block of wherein said polycarbonate-polysiloxane block copolymers has following structure:
R wherein
2Independent separately is C
1-C
12Alkyl; R
3Independent separately is C
6-C
30Alkylene; X is 0 or 1; D is 5-120.
4. the composition of claim 3, wherein x is 0, R
3Independently have following structure separately:
R wherein
4Independent separately is halogen, C
1-C
8Alkyl or C
1-C
8-oxyl; M is 0-4; N is 2-12.
5. the composition of claim 1, wherein said polyester is a polyarylester.
6. the composition of claim 1, wherein said surface-modifying agent comprises the polyester-polysiloxane segmented copolymer.
7. the composition of claim 1, described composition also comprises polymkeric substance that is selected from polycarbonate, polyestercarbonate, polyester and composition thereof.
8. the composition of claim 7, wherein said polyester is a polyarylester.
9. the composition of claim 1, the polysiloxane block of wherein said polycarbonate-polysiloxane block copolymers has following structure:
R wherein
2Independent separately is C
1-C
12Alkyl; R
3Independent separately is C
6-C
30Alkylene; X is 0 or 1; D is 5-120;
Wherein said surface-modifying agent comprises the polyester-polysiloxane segmented copolymer; With
Wherein said composition also comprises aromatic polycarbonate.
10. the composition of claim 1, the polycarbonate block of wherein said polycarbonate-polysiloxane block copolymers comprises the repeating unit with following structure:
The polysiloxane block of wherein said polycarbonate-polysiloxane block copolymers comprises the repeating unit with following structure:
Wherein D is 5-100;
Wherein said composition comprises the polycarbonate-polysiloxane block copolymers of 5-99% weight;
Wherein said surface-modifying agent comprises polycaprolactone-poly-(dimethyl siloxane)-polycaprolactone triblock copolymer;
Wherein said composition comprises the described surface-modifying agent of 0.1-10% weight; With
Wherein said composition also comprises the bisphenol-a polycarbonate of 1-95% weight.
11. goods, described goods comprise among the claim 1-10 each composition.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US51937003P | 2003-11-12 | 2003-11-12 | |
| US60/519,370 | 2003-11-12 | ||
| US10/950,100 | 2004-09-24 |
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| CN100473695C true CN100473695C (en) | 2009-04-01 |
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| KR101340539B1 (en) * | 2010-11-23 | 2014-01-02 | 제일모직주식회사 | High gloss and high impact resistance polycarbonate resin composition having good surface property and molded article using the same |
| KR20120075076A (en) * | 2010-12-28 | 2012-07-06 | 제일모직주식회사 | Polycarbonate resin composition having good mold release property and appearance molded article using the same |
| KR101362875B1 (en) * | 2010-12-30 | 2014-02-14 | 제일모직주식회사 | Polycarbonate-polysiloxane copolymer and method for preparing the same |
| KR102367852B1 (en) * | 2015-04-30 | 2022-02-28 | 삼성전자주식회사 | Polymer composition and formed article and manufacturing method of the same |
| EP3464471B1 (en) * | 2016-06-03 | 2021-10-06 | Covestro Intellectual Property GmbH & Co. KG | Laminated sheet containing special siloxane block copolycarbonates as matrix material |
| CN108192488B (en) * | 2017-12-29 | 2021-03-02 | 广州立邦涂料有限公司 | Solvent-based bi-component high-smoothness varnish composition, preparation method and application |
| EP3569752B1 (en) * | 2018-05-15 | 2020-08-26 | SABIC Global Technologies B.V. | Nonwoven fabric and associated composite and methods of making |
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