KR20070030919A - Methods of sterilizing polycarbonate articles - Google Patents

Abstract

The present invention relates to a method comprising treating a product with steam, the product comprising a composition comprising a polysiloxane-polycarbonate copolymer in an amount effective to provide thermal and hydrolytic stability to the product for at least 15 cycles. Each cycle, however, involves contact with steam for 20 minutes at a temperature of 100 ° C. and atmospheric pressure. The product can be used for a variety of purposes, such as food and medical devices.

Description

How to sterilize polycarbonate products {METHODS OF STERILIZING POLYCARBONATE ARTICLES}

The present invention relates to polycarbonate products, in particular polycarbonate products which can be repeatedly sterilized and methods for their preparation.

Polycarbonates are useful in the manufacture of products and components having a wide range of uses, from automotive parts to medical devices. Because of this wide range of uses, it is desirable to provide improved thermal and hydrolytic stability to polycarbonates. In particular, the medical device is preferably resistant to steam sterilization. Although some polycarbonate products can be steam sterilized at one time, many polycarbonate products generally have poor physical and / or mechanical properties of the polycarbonate due to repeated steam sterilization.

In general, resistance to steam sterilization has been attempted by using materials having higher glass transition temperatures and heat distortion temperatures. Some of these materials are polyetherimide, polysulfone, Bayer APEC (high thermal polycarbonate) and polyphthalyl carbonate (PPC, high thermal copolyester polycarbonate). In general, these materials have the drawback of preventing widespread use in steam sterilized products. For example, polyetherimides are colored, relatively expensive, and have low impact strength. Polysulfones are colored, fragile, viscous, and absorb water when exposed to light. Bayer's APEC is a stiff material that is difficult to process and sensitive to hydrolysis, and some copolyester polycarbonates are fragile colored materials. Thus, there is still a need in the art for polycarbonate products that do not significantly reduce their physical and / or mechanical properties despite repeated steam sterilization.

Summary of the Invention

  The above and other drawbacks in the art are the vaporization of products in which at least a portion of the product is formed with a composition comprising an amount of polysiloxane-polycarbonate copolymer effective to provide thermal and hydrolytic stability to the product for at least 15 cycles. Can be overcome by a process comprising treatment with each cycle, where each cycle includes contact with steam for 20 minutes at a temperature of at least 121 ° C. and a pressure of at least 1.5 atm.

In another embodiment, a method of making a thermally and hydrolytically resistant article is a product with a composition comprising a polysiloxane-polycarbonate copolymer in an amount effective to provide thermal and hydrolytic stability to the article for at least 15 cycles. Forming at least a portion of, wherein each cycle comprises contact with steam for 20 minutes at a temperature of 121 ° C. or higher and a pressure of 1.5 atm or higher.

In another embodiment, an article formed by the method described above is provided.

In another embodiment, an article having improved resistance to steam sterilization comprises an amount of polysiloxane-polycarbonate copolymer effective to provide thermal and hydrolytic stability to the article for at least 15 cycles, wherein each cycle is 121 ° C. Contact with steam for 20 minutes at the above temperature and pressure above 1.5 atm.

1 compares the Notch Izod impact retention for selected polycarbonate compositions after steam treatment.

2 compares Notch Izod impact retention for selected polycarbonate compositions after steam treatment.

FIG. 3 shows the instrumental impact retention values of selected polycarbonates after steam treatment.

4 shows the effect of steam treatment on hydrolytic stability in various polycarbonate compositions.

5 shows impact strength performance for selected polycarbonate compositions after steam treatment.

FIG. 6 shows the change in yellow index (“delta YI”) for selected polycarbonate compositions after steam treatment.

The inventors have unexpectedly learned that polysiloxane polycarbonate copolymers can be used to provide improved resistance to heat and hydrolysis to articles. In particular advantageous features, it has been found that the product can be repeatedly treated with steam (eg steam sterilization) without a significant reduction in one or more advantageous properties. In one embodiment, the product, despite repeated treatment with heat and / or steam, has no or little damage in terms of dimensional stability, ductility, impact strength, transparency and / or Vicat softening temperature. I found out.

In order to impart proper heat resistance during heat and / or steam treatment, eg steam sterilization, the products are formed from a composition comprising a polysiloxane-polycarbonate copolymer. Such copolymers include polysiloxane blocks and polycarbonate blocks. The polycarbonate block comprises a repeating structural carbonate unit of formula

Wherein at least 60% of the total number of R ¹ groups are aromatic organic radicals and the remainder are aliphatic, cycloaliphatic, or aromatic radicals. Each R ¹ may be an aromatic organic radical and may be a radical of the formula 2:

-A ¹ -Y ¹ -A ^2-

Wherein A ¹ and A ² are each monocyclic divalent aryl radicals and Y ¹ is a bridging radical having one or two atoms separating A ¹ and A ² . In an exemplary embodiment, A ¹ and A ² are separated by one atom. Exemplary non-limiting examples of radicals of this type include -O-, -S-, -S (O)-, -S (O ₂ )-, -C (O)-, methylene, cyclohexyl-methylene, 2- [2.2.1] -bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadedecidene, cyclododecylidene, and adamantylidene. The bridging radical Y ¹ may be a hydrocarbon group or a saturated hydrocarbon group such as methylene, cyclohexylidene, or isopropylidene.

The polycarbonate unit may be prepared by interfacial or melting reaction of a dihydroxy compound having a structure of formula HO-R ¹ -OH, including a dihydroxy compound of formula 3:

HO-A ¹ -Y ¹ -A ² -OH

Wherein Y ¹ , A ¹ and A ² are as defined above.

Also included are bisphenol compounds of formula (IV):

Where

R ^a and R ^b are each halogen atoms or monovalent hydrocarbon groups, which may be the same or different;

p and q are independently of each other an integer from 0 to 4;

X ^a represents one of the groups of formula (5):

Wherein R ^c and R ^d are independently a hydrogen atom or a monovalent linear or cyclic hydrocarbon group, and R ^e is a divalent hydrocarbon group.

Some illustrative non-limiting examples of suitable dihydroxy compounds include dihydroxy-substituted hydrocarbons whose names are specified in US Pat. No. 4,217,438 or described by the general formula (or general formula). Specific non-limiting examples of suitable dihydroxy compounds include: resorcinol, 4-bromoreresorcinol, hydroquinone, 4,4'-dihydroxybiphenyl, 1,6-dihydroxy Naphthalene, 2,6-dihydroxynaphthalene, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) -1-naphthylmethane, 1 , 2-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2- (4-hydroxyphenyl) -2- (3-hydroxyphenyl) Propane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 1,1-bis (hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) isobutene, 1,1-bis (4-hydroxyphenyl) cyclododecane, trans-2,3-bis (4 -Hydroxyphenyl) -2-butene, 2,2-bis (4-hydroxyfe Adamantine, (alpha, alpha'-bis (4-hydroxyphenyl) toluene, bis (4-hydroxyphenyl) acetonitrile, 2,2-bis (3-methyl-4-hydroxyphenyl) propane , 2,2-bis (3-ethyl-4-hydroxyphenyl) propane, 2,2-bis (3-n-propyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl- 4-hydroxyphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (3-methoxy-4- Hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-dichloro-2,2-bis (4-hydroxyphenyl) ethylene, 1,1-dibromo -2,2-bis (4-hydroxyphenyl) ethylene, 1,1-dichloro-2,2-bis (5-phenoxy-4-hydroxyphenyl) ethylene, 4,4'-dihydroxybenzo Phenone, 3,3-bis (4-lower Hydroxyphenyl) -2-butanone, l, 6-bis (4-hydroxyphenyl) -1,6-hexanedione, ethylene glycol bis (4-hydroxyphenyl) ether, bis (4-hydroxy Hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, 9,9-bis (4-hydroxyphenyl) fluor Lean, 2,7-dihydroxypyrene, 6,6'-dihydroxy-3,3,3 ', 3'-tetramethylspiro (bis) indane ("spirobiindane bisphenol"), 3,3- Bis (4-hydroxyphenyl) phthalide, 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7-dihydroxyphenoxatin, 2,7- Dihydroxy-9,10-dimethylphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole and the like, as well as tactical Mixture containing dihydroxy compound.

Specific non-limiting examples of types of bisphenol compounds represented by Formula 3 include 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis ( 4-hydroxyphenyl) propane (hereinafter referred to as "bisphenol A" or "BPA"), 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 1,1-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) n-butane, 2,2-bis (4-hydroxy-1-methylphenyl) propane, and 1, 1-bis (4-hydroxy tert-butylphenyl) propane is mentioned. Combinations comprising the aforementioned dihydroxy compounds can also be used. In addition to branched polysiloxane-polycarbonate copolymers, blends comprising linear polycarbonate units and branched polycarbonate units may also be useful. Branched polycarbonate units can be prepared by adding a branching agent during polymerization. Such branching agents include polyvalent organic compounds containing at least three functional groups selected from hydroxyl, carboxyl, carboxylic anhydride, haloformyl and mixtures of these functional groups. Specific examples include trimellitic acid, trimellitic anhydride, trimellitic acid trichloride, tris-p-hydroxy phenyl ethane, istin-bis-phenol, tris-phenol TC (1,3,5-tris ((p-hydroxyphenyl) isopropyl) benzene), tris-phenol PA (4 (4 (1,1-bis (p-hydroxyphenyl) -ethyl) alpha, alpha-dimethyl benzyl) phenol), 4-chloroformyl phthalic anhydride, trimesic acid, and benzophenone tetracarboxylic acid. Branching agents may be added at 0.05 to 2.0 wt% (wt.%). All types of polycarbonate end groups can be considered useful in polycarbonate compositions.

As used herein, “polycarbonate units” further includes copolymers comprising carbonate chain units and other chain units. Particular suitable copolymer units are polyester carbonate units (also known as copolyester polycarbonate units). Such copolymer units may further contain a repeating unit of formula 6 in addition to the carbonate chain repeating unit of formula 1:

Where

D is a divalent radical derived from a dihydroxy compound, such as a C _2-10 alkylene radical, a C _6-20 alicyclic radical, a C _6-20 aromatic radical or a polyoxyalkylene radical, wherein the alkylene group is 2 To 6 carbon atoms, specifically 2, 3 or 4 carbon atoms);

T is a divalent radical derived from a dicarboxylic acid, such as a C _2-10 alkylene radical, a C _6-20 alicyclic radical, a C _6-20 alkyl aromatic radical or a C _6-20 aromatic radical.

In one embodiment, D is a C _2-6 alkylene radical. In another embodiment, D is derived from an aromatic dihydroxy compound of formula

Where

R ^f is independently a halogen atom, a C _1-10 hydrocarbon group, or a C _1-10 halogen substituted hydrocarbon group, n is 0-4. Halogen may be bromine. Examples of compounds represented by Formula 7 include resorcinol, substituted resorcinol compounds such as 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol, 5-butyl resorcinol, 5-tert-butyl resorcinol, 5-phenyl resorcinol, 5-cumyl resorcinol, 2,4,5,6-tetrafluororesorcinol, 2,4,5,6-tetrabromo Resorcinol and the like; Catechol; Hydroquinone; Substituted hydroquinones such as 2-methyl hydroquinone, 2-ethyl hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone, 2-3-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone , 2,3,5,6-tetramethyl hydroquinone, 2,3,5,6-tetra-tert-butyl hydroquinone, 2,3,5,6-tetrafluorohydroquinone, 2,3, 5,6-tetrabromo hydroquinone and the like; Or combinations comprising one or more such compounds.

Examples of aromatic dicarboxylic acids that can be used to prepare polyesters are isophthalic acid or terephthalic acid, l, 2-di (p-carboxyphenyl) ethane, 4,4'-dicarboxydiphenyl ether, 4,4'-bisbenzoic acid And mixtures comprising one or more such acids. Acids containing condensed rings, such as 1,4-, 1,5-, or 2,6-naphthalenedicarboxylic acid, may also be present. Particular dicarboxylic acids are terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid, or combinations comprising one or more such dicarboxylic acids. Particular dicarboxylic acids include mixtures of isophthalic acid and terephthalic acid, wherein the weight ratio of terephthalic acid to isophthalic acid is from 10: 1 to 0.2: 9.8. In another embodiment, D is a C _2-6 alkylene radical and T is p-phenylene, m-phenylene, naphthalene, divalent cycloaliphatic radical or mixtures thereof. Polyesters of this type include poly (alkylene terephthalates).

In addition to the repeating structural carbonate units of Formula 1, the copolymer comprises a polydiorganosiloxane block comprising repeating structural units of Formula 8:

Wherein each R is the same or different and is a C _1-13 monovalent organic radical.

For example, R is a C ₁ -C ₁₃ alkyl group, a C ₁ -C ₁₃ alkoxy group, a C ₂ -C ₁₃ alkenyl group, a C ₂ -C ₁₃ alkenyloxy group, a C ₃ -C ₆ cycloalkyl group, C ₃ -C ₆ cycloalkoxy group, C ₆ -C ₁₀ aryl group, C ₆ -C ₁₀ aryloxy group, C ₇ -C ₁₃ aralkyl group, C ₇ -C ₁₃ aralkoxy group, C ₇ -C ₁₃ al Or a C ₇ -C ₁₃ alkaryloxy group. Combinations of the foregoing R groups can be used in the copolymer.

D in Formula 8 is selected to provide hydrolytic stability at an effective level during repeated steam treatments such as steam sterilization cycles. Thus, the value of D may vary depending on the type and relative amount of each component in the composition, such as the type and content of the polycarbonate block, the type and content of any polycarbonate resin, if any, described below, and the optional impact strength modifier (if any). Type and content, type of polysiloxane unit, and type and content of any other additives present in the composition. Suitable values of D can be measured by one skilled in the art without undue experimentation in accordance with the criteria disclosed herein. In general, D has an average value of 2 to 1000, specifically 10 to 100, more specifically 25 to 75. In one embodiment, D has an average value of 40 to 60, and in yet another embodiment D has an average value of 50. If D is less than this value, for example less than 40, it may be acceptable or advantageous to use relatively large amounts of polysiloxane-polycarbonate copolymers. In contrast, where D has a larger value, such as greater than 40, it is acceptable or advantageous to use relatively small amounts of polysiloxane-polycarbonate copolymers.

Certain polysiloxane-polycarbonate copolymers will be selected by those skilled in the art so as not to compromise the properties of the thermal and hydrolytic stability of the products made from the compositions. Particular types of suitable polysiloxane-polycarbonates have polydiorganosiloxane blocks comprising repeating structural units of formula (9):

Wherein D is as described above, each R is the same or different and is a C _1-13 monovalent organic radical.

For example, R is a C ₁ -C ₁₃ alkyl group, a C ₁ -C ₁₃ alkoxy group, a C ₂ -C ₁₃ alkenyl group, a C ₂ -C ₁₃ alkenyloxy group, a C ₃ -C ₆ cycloalkyl group, C ₃ -C ₆ cycloalkoxy group, C ₆ -C ₁₀ aryl group, C ₆ -C ₁₀ aryloxy group, C ₇ -C ₁₃ aralkyl group, C ₇ -C ₁₃ aralkoxy group, C ₇ -C ₁₃ al Or a C ₇ -C ₁₃ alkaryloxy group. Combinations of the foregoing R can be used in the copolymer. R ² in Formula 6 is a divalent C ₁ -C ₈ aliphatic group. In the formula (9), each M may be the same or different, as between a halogen, cyano, nitro, C ₁ -C ₈ alkylthio, C ₁ -C ₈ al Kiel, C ₁ -C ₈ alkoxy, C ₂ -C ₈ Alkenyl, C ₂ -C ₈ alkenyloxy groups, C ₃ -C ₈ cycloalkyl, C ₃ -C ₈ cycloalkoxy, C ₆ -C ₁₀ aryl, C ₆ -C ₁₀ aryloxy, C ₇ -C ₁₂ are Alkyl, C ₇ -C ₁₂ alkoxy, C ₇ -C ₁₂ alkaryl, or C ₇ -C ₁₂ alkaryloxy, wherein n is each independently 0, 1, 2, 3, or 4 .

In one embodiment, M is independently bromo or chloro, a C ₁ -C ₃ alkyl group (eg methyl, ethyl, or propyl), a C ₁ -C ₃ alkoxy group (eg methoxy, ethoxy, or pro Foxy), or a C ₆ -C ₇ aryl group (such as phenyl, chlorophenyl, or tolyl); R ² is a dimethylene, trimethylene or tetramethylene group; R is C _1-8 alkyl, haloalkyl (eg trifluoropropyl), cyanoalkyl, or aryl (eg phenyl, chlorophenyl or tolyl). In another embodiment, R is methyl, or a mixture of methyl and trifluoropropyl, or a mixture of methyl and phenyl. In another embodiment, M is methoxy, n is 1, R ² is a divalent C ₁ -C ₃ aliphatic group and R is methyl.

Such units may be derived from the corresponding dihydroxy polydiorganosiloxanes of formula

Wherein Y, R, D, M, R ² , and n are as described above.

The dihydroxy polysiloxane may be prepared by a platinum catalyzed addition reaction of a siloxane hydride of Formula 11 with an aliphatic unsaturated monohydric phenol:

Wherein R and D are as described above.

Suitable aliphatic unsaturated monophenols are for example eugenol, 2-alkylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2-bromophenol, 4- Allyl-2-tert-butoxyphenol, 4-phenyl-2-phenylphenol, 2-methyl-4-propylphenol, 2-allyl-4,6-dimethylphenol, 2-allyl-4-bromo- 6-methylphenol, 2-allyl-6-methoxy-4-methylphenol and 2-allyl-4,6-dimethylphenol. Mixtures comprising the aliphatic unsaturated monohydric phenols described above can also be used.

The polysiloxane-polycarbonate copolymer can be prepared by reacting the dihydroxy polysiloxane of formula 10 with the carbonate source and the dihydroxy aromatic compound of formula 3 by processes such as interfacial polymerization and melt polymerization. Although the reaction conditions for interfacial polymerization may vary, exemplary processes generally dissolve or disperse divalent reactants in aqueous caustic soda or caustic potassium and add the resulting mixture to a suitable water-immiscible solvent medium and control it. Contacting the reactant with a carbonate precursor in the presence of a suitable catalyst, such as triethylamine or a phase transfer catalyst, under a predetermined pH condition (eg, 8 to 10). In one embodiment, the copolymer may be prepared by phosgenation at a temperature of 0 ° C. to 100 ° C., and may also be prepared at a temperature of 25 ° C. to 50 ° C. The most commonly used water-immiscible solvents include methylene chloride, 1,2-dichloroethane, chlorobenzene, toluene and the like. Suitable carbonate precursors are for example carbonyl halides (eg carbonyl bromide or carbonyl chloride), or haloformates such as bishaloformates of dihydric phenols (eg bisphenol A, hydroquinone, etc.) Chloroformate or the like) or bishaloformate of glycol (eg, bishaloformate such as ethylene glycol, neopentyl glycol, polyethylene glycol). Combinations comprising one or more of these types of carbonate precursors may also be used. In one embodiment, monofunctional compounds such as phenol, tert-butyl phenol or para-cumylphenol can act as chain terminators to define the molecular weight of the polycarbonate.

Among the specific phase transfer catalysts that can be used are catalysts of formula (R ³ ) ₄ Q ⁺ X wherein R ³ is the same or different and is a C _1-10 alkyl group; Q is nitrogen or a person; X is halo Gen atom or C _1-8 alkoxy group or C _6-188 aryloxy group. Suitable phase transfer catalysts include, for example, [CH ₃ (CH ₂ ) ₃ ] ₄ NX, [CH ₃ (CH ₂ ) ₃ ] ₄ PX, [CH ₃ (CH ₂ ) ₅ ] ₄ NX, [CH ₃ (CH ₂₎ ) ₆ ] ₄ NX, [CH ₃ (CH ₂ ) ₄ ] ₄ NX, CH ₃ [CH ₃ (CH ₂ ) ₃ ] ₃ NX, CH ₃ [CH ₃ (CH ₂ )] ₃ NX, where X is Cl ^-, Br ^- are included, or a C _1-8 alkoxy group or C _6-188 aryloxy group). An effective amount of phase transfer catalyst may be 0.1 to 10% by weight based on the weight of the divalent reactant in the phosgenation mixture. In another embodiment, the effective amount of phase transition metal may be 0.5 to 2 weight percent based on the weight of bisphenol in the phosgenation mixture. One or two of the tubular reactor processes described in US Patent Application 2004/0039145 A1 can be used to synthesize polysiloxane polycarbonate copolymers.

Alternatively, a melting process can be used to prepare the copolymer. Generally, in the melt polymerization process, dihydroxy reactants and diaryl carbonate esters (eg, diphenyl carbonate) are co-reacted in the presence of a transesterification catalyst in a Banbury mixer, a twin screw extruder, etc. to form a uniform dispersion. The copolymer can be formed by doing so. Volatile monohydric phenol is removed from the molten reactant by distillation and the polymer is liberated from the molten residue.

Polycarbonate copolymers comprising polyester units can also be prepared by interfacial polymerization techniques, as described, for example, in US Pat. Nos. 3,169,121 and 4,487,896. Rather than using the dicarboxylic acid itself, it is possible and sometimes even preferred to use reactive derivatives of acids, such as the corresponding acid halides, in particular acid dichlorides and acid dibromide. Thus, for example, instead of using isophthalic acid, terephthalic acid or mixtures thereof, it is possible to use isophthaloyl dichloride, terephthaloyl dichloride and combinations comprising one or more thereof.

In the production of polysiloxane-polycarbonate copolymers, the content of dihydroxy polydiorganosiloxane is chosen to provide an effective level of hydrolysis resistance to the composition when repeatedly exposed to steam. Thus, the amount of dihydroxy polydiorganosiloxane will vary depending on the value of D and the relative content and type of each component (e.g., polycarbonate block, polysiloxane block, optional polycarbonate resin, optional impact modifier, and any other additives) in the composition. Can be. Suitable values for the dihydroxy polydiorganosiloxane can be determined by one skilled in the art without undue experimentation using the criteria indicated herein. Typically, the amount of dihydroxy polydiorganosiloxane is selected to produce a copolymer comprising 0.1 to 40 weight percent polydimethylsiloxane or an equivalent molar amount of another polydiorganosiloxane. Such copolymers may then be combined with other polymers to form blends, including blends comprising polysiloxane-polycarbonate copolymers having different polysiloxane contents. If the polydimethylsiloxane unit is less than 0.1% by weight, proper heat resistance is not achieved even if the copolymer in the composition is present in high content. If the polydimethylsiloxane unit exceeds 40% by weight, it may adversely affect the physical properties of the composition, such as two layers of the molded article, lower heat deformation temperature and difficulty in processing.

In typical embodiments, the amount of dihydroxy polydiorganosiloxane is selected to produce a copolymer comprising 0.5-12 wt.% Polydimethylsiloxane or an equivalent molar amount of another polydiorganosiloxane. In another embodiment, the dihydroxy polydiorganosiloxane is selected to produce a copolymer comprising 1 to 7 weight percent polydimethylsiloxane or an equivalent molar amount of another polydiorganosiloxane. Such copolymers can be used to prepare opaque or transparent products according to the method of synthesis of the copolymers as described in the art.

 The polysiloxane-polycarbonate copolymer may have a weight average molecular weight (measured by MW, for example gel permeation chromatography, ultracentrifugation or light scattering) of 10,000 to 200,000, in particular 20,000 to 100,000. In general, the polysiloxane-polycarbonate copolymer may have a weight average molecular weight of 15,000 to 100,000. Suitable polysiloxane-polycarbonate copolymers are commercially available from GE Plastics.

In addition to the polysiloxane-polycarbonate copolymers described above, the composition may include one or more additional components, such as additional thermoplastics and / or fillers and other additives. The additional components are chosen so as not to adversely affect the thermal and hydrolytic stability of the composition and thus may be high heat materials.

In one embodiment, the composition comprises a high temperature thermoplastic polymer that does not adversely affect the desired properties of the composition before or after treatment with steam, which is described in more detail below. In one embodiment, the high temperature thermoplastic polymer has a heat deflection temperature (HDT) of greater than 135 ° C. at 1.8 megapascals (MPa). In another embodiment, the high temperature thermoplastic polymer has a heat deflection temperature of greater than 150 ° C. at 0.45 MPa. Heat deflection temperature can be measured according to ASTM 648.

The high temperature thermoplastic polymers are polyoxymethylene, polyarylate, polyether ether ketones, polyethersulfones, poly (ethylene terephthalates), polyphenylene sulfides, polycarbonates, and combinations comprising one or more of these high temperature thermoplastic polymers. It may be selected from the group consisting of water.

In one embodiment, the high temperature thermoplastic polymer can be a high temperature polycarbonate comprising carbonate units of formula (1). Those skilled in the art can use and select a variety of high temperature polycarbonates so as not to compromise the above-described properties. In one embodiment, the hyperthermic polycarbonate is a copolymer comprising units derived from a dihydroxy compound of formula 3, preferably a bisphenol compound of formula 4, together with units derived from a high temperature monomer. Suitable high temperature monomers include, for example, bis (4-hydroxyphenyl) -p-mentane, 2-phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine, as described, for example, in US Pat. No. 5,344,999. (PPP), 4,4 '-(hexahydro-4,7-methano-indan-5-ylidene) diphenol (TCD, or tricyclodecane bisphenol), bisphenol TMC (1,3,5-trimethyl Cyclohexane) (APEC material of Bayer), 4- [1- [3- (4-hydroxyphenyl) -4-methylcyclohexyl] -1-methylethyl] phenol, 4,4 '-[1-methyl- 4- (1-methylethyl) -1,3-cyclohexanediyl] bisphenol, phenolphthalein, 2-methyl-3,3-bis (p-hydroxyphenyl) phthalimide, 2-butyl-3,3- Bis (p-hydroxyphenyl) phthalimide, 2-octyl-3,3-bis (p-hydroxyphenyl) phthalimide, and 1,3-bis (4-hydroxyphenyl) -1,3- Dialkylcyclohexanes, wherein the alkyl group has 1 to 4 carbon atoms. Specific examples of suitable high temperature polycarbonates include units derived from the high temperature monomers described above, including 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, bisphenol A, 2, 2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 1,1-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxy Phenyl) n-butane, 2,2-bis (4-hydroxy-1-methylphenyl) propane, and 1,1-bis (4-hydroxytert-butylphenyl) propane . Alternatively, high temperature polycarbonates are made from the polycarbonate monomers described above, which are then blended with high temperature monomers or other polymers that provide high heat resistance.

Another suitable high temperature polycarbonate is a copolyester polycarbonate comprising a unit of formula (1) together with a polyester unit of formula (6). In addition, the unit of formula 1 may be derived from a high temperature divalent compound such as bis (4-hydroxyphenyl) -p-mentane or a combination of such a high temperature divalent compound with another divalent compound such as bisphenol A. The ester unit is preferably aromatic. In one embodiment, the ester unit is derived from an aromatic dicarboxylic acid such as isophthalic acid or terephthalic acid.

The average molecular weight of the high temperature polycarbonate can be 5,000 to 100,000, more particularly 10,000 to 65,000, most particularly 15,000 to 45,000 as measured by gel permeation chromatography. Mixtures of different weights of polycarbonate can be used to achieve the desired viscosity and / or other physical properties.

High temperature polycarbonates can be prepared by processes such as interfacial polymerization and melt polymerization as described above. Suitable procedures for the preparation of high temperature copolyester polycarbonates are described, for example, in US Pat. No. 4,238,597. Suitable high temperature polycarbonates are the trade names LEXAN 4704, 4504, and 4404 available from GE Plastics, and APEC available from Bayer.

In addition to the high temperature polycarbonate resins described above, it is possible to use combinations of polycarbonate resins with other thermoplastic polymers, for example combinations of polycarbonates and / or polycarbonate copolymers with polyesters. “Combination” herein includes mixtures, blends, alloys, copolymers, and the like. Suitable polyesters include repeating units of formula (6) and may be, for example, poly (alkylene dicarboxylates), liquid crystalline polyesters, and polyester copolymers. It is also possible to use branched polyesters in which branching agents such as glycols having three or more hydroxyl groups or trivalent or polyvalent carboxylic acids are incorporated. Moreover, it is sometimes desirable to have various concentrations of acid and hydroxyl end groups on the polyester, depending on the end use desired for the composition.

In one embodiment, poly (alkylene terephthalate) is used. Specific examples of suitable poly (alkylene terephthalates) include poly (ethylene terephthalate) (PET), poly (l, 4-butylene terephthalate) (PBT), poly (ethylene naphthalanoate) (PEN), poly ( Butylene naphtanoate), (PBN), (polypropylene terephthalate) (PPT), polycyclohexanedimethanol terephthalate (PCT), and combinations comprising at least one of the foregoing polyesters. To prepare the copolyesters, such polyesters are also contemplated which have small amounts (eg 0.5 to 10% by weight) of units derived from aliphatic diacids and / or aliphatic polyols.

Blends of polycarbonates and polyesters comprise 10 to 90% by weight of polycarbonates and corresponding 90 to 10% by weight of polyesters, in particular poly (alkylene terephthalates). In one embodiment, the blend comprises 30 to 70 weight percent polycarbonate and the corresponding 70 to 30 weight percent polyester. The content is based on the total amount of polycarbonate resin and polyester resin.

The composition may further comprise an impact modifier composition comprising a specific combination of impact modifiers to increase impact resistance. Suitable impact modifiers include (i) elastomeric (ie rubber) polymeric substrates having a Tg of 0 ° C. or less (more particularly −40 ° C. to −80 ° C.), and (ii) a rigid polymerizable top grafted to the elastomer substrate. It may be an elastomer-modified graft copolymer comprising a substrate. As is known, elastomer-modified graft copolymers can be prepared by first providing an elastomeric polymer backbone. To prepare the graft copolymer, one or more (particularly two) grafting monomers are polymerized in the presence of the polymer backbone.

Depending on the content of the elastomer-modified polymer present, separate matrices or continuous phases of the grafted rigid polymer or copolymer may be obtained simultaneously with the elastomer-modified graft copolymer. Generally, such impact modifiers comprise 40 to 95 weight percent elastomer-modified graft copolymer and 5 to 60 weight percent graft (co) polymer based on the total weight of the impact modifier. In another embodiment, such impact modifiers range from 50 to 85 weight percent (more particularly with 15 to 50 weight percent (more particularly 15 to 25 weight percent) of the graft (co) polymer, based on the total weight of the impact modifier. 75 to 85 weight percent) of the rubber-modified graft copolymer. Ungrafted rigid polymers or copolymers may also be prepared separately, for example by radical polymerization, in particular emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization, and may be added to the impact modifier composition or the polycarbonate composition. Such ungrafted rigid polymers or copolymers may have a number average molecular weight of 20,000 to 200,000.

Suitable materials for use as the elastomeric polymer backbone include, for example, conjugated diene rubbers: copolymers of conjugated dienes with less than 50% by weight of copolymerizable monomers; C _1-8 alkyl (meth) acrylate elastomers; Olefin rubbers such as ethylene propylene copolymers (EPR) or ethylene-propylene-diene monomers (EPDM); Silicone rubber; Elastomeric C _1-8 alkyl (meth) acrylates; Elastomeric copolymers of C _1-8 alkyl (meth) acrylate with butadiene and / or styrene; Or combinations comprising at least one of the foregoing elastomers.

Suitable conjugated diene monomers for preparing the polymerizable backbone have the structure of Formula 12:

Wherein each X ^b is independently hydrogen, C ₁ -C ₅ alkyl, chlorine, bromine or the like.

Examples of conjugated diene monomers that may be used are butadiene, isoprene, 1,3-heptadiene, methyl-1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-pentadiene; 1,3- and 2,4-hexadiene, chloro- and bromo-substituted butadienes such as dichlorobutadiene, bromobutadiene, dibromobutadiene and the like, as well as such conjugated dienes And mixtures comprising at least one of the monomers. Particular conjugated diene copolymers are polybutadiene and polyisoprene.

Copolymers of conjugated diene rubbers, such as those prepared by aqueous radical emulsion polymerization of conjugated dienes and one or more monomers copolymerizable therewith, can also be used. Suitable monomers for copolymerizing with conjugated dienes include monovinylaromatic monomers containing a condensed aromatic ring structure such as vinyl naphthalene, vinyl anthracene, and the like, or monomers of Formula 13:

Wherein X ^c is independently hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₆ -C ₁₂ aryl, C ₇ -C ₁₂ aralkyl, C ₇ -C ₁₂ alkaryl, C ₁ -C ₁₂ alkoxy, C ₃ -C ₁₂ cycloalkoxy, C ₆ -C ₁₂ aryloxy, chloro, bromo, or hydroxy and R is hydrogen, C ₁ -C ₅ alkyl, bromo, or chloro. Examples of suitable monovinylaromatic monomers that can be used are styrene, 3-methylstyrene, 3,5-diethylstyrene, 4-n-propylstyrene, alpha-methylstyrene, alpha-methyl vinyltoluene, alpha -Chlorostyrene, alpha-bromosstyrene, dichlorostyrene, dibromosstyrene, tetra-chlorostyrene, combinations containing one or more of these compounds, and the like. Styrene and / or alpha-methylstyrene are commonly used as monomers that can be copolymerized with conjugated diene monomers. Mixtures of the foregoing monovinyl monomers and monovinylaromatic monomers can also be used.

Other monomers that can be copolymerized with conjugated dienes are monovinyl monomers such as itaconic acid, acrylamide, N-substituted acrylamide or methacrylamide, maleic anhydride, maleimide, N-alkyl, aryl or haloaryl substituted Maleimide, glycidyl (meth) acrylate, and monomers of Formula 14:

Wherein R is as defined above and X ^c is cyano, C ₁ -C ₁₂ alkoxycarbonyl, C ₁ -C ₁₂ aryloxycarbonyl and the like.

Examples of the monomer of formula 14 are acrylonitrile, ethacrylonitrile, methacrylonitrile, alpha-chloroacrylonitrile, beta-chloroacrylonitrile, alpha-bromoacrylonitrile, methyl Acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, propyl acrylate, isopropyl acrylate, 2-ethylhexyl acrylate, combinations comprising one or more of these monomers Water and the like. Monomers such as n-butyl acrylate, ethyl acrylate, and 2-ethylhexyl acrylate are commonly used as monomers capable of copolymerizing with conjugated diene monomers.

(Meth) acrylate rubbers suitable for use as elastomeric polymer backbones optionally contain up to 15% by weight of comonomers (e.g., styrene, methyl methacrylate, butadiene, isoprene, vinyl methyl ether or acrylonitrile). And a crosslinked particulate emulsified homopolymer or copolymer of C _1-8 alkyl (meth) acrylates (particularly C _4-6 alkyl acrylates) mixed with a mixture comprising one or more of these comonomers). . Optionally, up to 5% by weight of polyvalent crosslinkable comonomers such as divinylbenzene, alkylenediol di (meth) acrylates such as glycol bisacrylate, alkylenetriol tri (meth) acrylates , Polyester di (meth) acrylate, bisacrylamide, triallyl cyanurate, triallyl isocyanurate, allyl (meth) acrylate, diallyl maleate, diallyl fumarate, diallyl adipate, citric acid Trialyl esters of phosphoric acid, triallyl esters of phosphoric acid, and the like, as well as combinations comprising one or more of these crosslinkers may be present.

Elastomeric polymer substrates may be in the form of blocks or random copolymers. The particle size of the substrate is not of great importance, for example, the average particle diameter of the particles of the substrate may be 0.05 to 1.2 micrometers, 0.2 to 0.8 micrometers, or graft in an emulsion-based polymerizable rubber latex. It may be from 0.5 to 10 micrometers, and even from 0.6 to 1.5 micrometers, in mass polymerized rubber substrates incorporating incorporated monomeric aggregates. Particle diameters can be measured by simple lightcasting methods or capillary hydrodynamic chromatography (CHDF). The rubber substrate may be a moderately crosslinked conjugated diene or C _4-6 alkyl acrylate rubber particulates and may have a gel content of greater than 70%. Also suitable are mixtures of conjugated dienes and C _4-6 alkyl acrylate rubbers.

In preparing the elastomeric graft copolymers, the elastomeric polymer backbone may comprise 40 to 95 weight percent total graft copolymer, or may comprise 50 to 85 weight percent, and still 75 to 85 weight percent Elastomer-modified graft copolymers, with the remainder being rigid graft phases.

In one embodiment, the elastomer-modified graft polymer can be obtained by graft copolymerization reaction of a mixture comprising monovinylaromatic monomers and optionally one or more co-units in the presence of one or more elastomeric substrates. Monovinylaromatic monomers described above, such as styrene, alpha-methyl styrene, halosstyrene (eg dibromosstyrene), vinyltoluene, vinyl xylene, butyl styrene, para-hydroxy styrene, methoxy styrene Ren, or combinations comprising one or more of these monovinylaromatic monomers, may be used on rigid grafts. Monovinylaromatic monomers may be used in combination with one or more comonomers, for example monovinyl monomers and / or monomers of formula (14). In one particular embodiment, the monovinylaromatic monomer is styrene or alpha-methyl styrene and the comonomer is acrylonitrile, ethyl acrylate, and / or methyl methacrylate. In another specific embodiment, the rigid graft phase is a copolymer of styrene and acrylonitrile, a copolymer of alpha-methylstyrene and acrylonitrile, or a methyl methacrylate homopolymer or copolymer.

Specific examples of such elastomer-modified graft copolymers include acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene-butyl acrylate (ASA), methyl methacrylate-acrylonitrile Reel-butadiene-styrene (MABS), methyl methacrylate-butadiene-styrene (MBS), and acrylonitrile-ethylene-propylene-diene-styrene (AES) It is not limited to this.

In another embodiment, the elastomer-modified graft polymer is to be obtained by emulsion graft polymerization of a mixture comprising at least one of the aforementioned monovinylic monomers and / or monomers of Formula 14 in the presence of at least one elastomeric polymer substrate. Can be. In one particular embodiment, the monovinyllic monomer is acrylonitrile, methacrylonitrile, ethyl acrylate, methyl acrylate, and / or methyl methacrylate.

Elastomer-modified graft polymers can be prepared using a continuous, semi-batch or batch process by mass, emulsifying, suspending, solution and combined processes such as bulk-suspending, emulsifying-bulk, bulk-solution or other techniques. Can be polymerized. As mentioned above, the use of particular combinations of specific impact modifiers surprisingly results in excellent results.

In particular, the first impact modifier is prepared by emulsion polymerization, alkali metal salts of C _6-30 fatty acids (eg sodium stearate, lithium stearate, sodium oleate, potassium oleate, etc.), and alkali metal carbonates, It does not include basic materials such as amines (eg, dodecyl dimethyl amine, dodecyl amine, etc.) and ammonium of amines. Such basic materials can be used primarily as surfactants in emulsion polymerization to promote transesterification and / or degradation of polycarbonates. Instead, ionic sulfate, sulfonate or phosphate surfactants may be used to prepare the impact modifiers, especially the elastomeric base portion of the impact modifier. Suitable surfactants are for example C _1-22 alkyl or C _7-25 alkylaryl sulfonate, C _1-22 alkyl or C _7-25 alkylaryl sulfate, C _1-22 alkyl or C _7-25 alkylaryl phosphate, Substituted silicates and combinations comprising one or more of these surfactants. Particular surfactants may be C _6-16 and additionally C _8-12 alkyl sulfonates.

The emulsion polymerization process for the preparation of the impact modifiers of the present invention is not critical and is described and described in several patent documents and in the literature of companies such as Rohm & Haas and General Electric Company. have. Indeed, many of the impact modifiers described above may be used under the condition that alkali metal salts, alkali metal carbonates and other basic materials of fatty acids are absent. However, in one embodiment, the impact modifier has a core-shell modified structure wherein the core is an elastomeric polymer substrate and the shell is a rigid thermoplastic polymer that is easily wetted by a PC. The shell may only physically surround the core, or the shell may be partially or essentially completely grafted to the core. The shell may comprise a polymerization product of monovinylaromatic compounds and / or monovinyl monomers or alkyl (meth) acrylates. Particular impact modifiers of this type are MBS impact modifiers, wherein the butadiene substrate is prepared using the sulfonates, sulfates or phosphates described above as surfactants. It is also preferred that the impact modifier has a pH of 3 to 8 (more preferably 4 to 7).

Acrylonitrile-butadiene-styrene graft copolymers are well known in the art and many are from BLENDEX® grades 131, 336, 338, 360, and 415 from General Electric Company. Commercially available, including high rubber content acrylonitrile-butadiene-styrene resins available from.

In addition to polycarbonate-polysiloxane copolymers, additional thermoplastic polymers, and optional impact modifiers (hereinafter referred to as "resin compositions"), the compositions may include various additives commonly incorporated in compositions of this type, wherein the additives It is provided that after repeated treatment with steam it does not adversely affect the desired properties of the composition, in particular the hydrolytic and / or thermal stability. Thus, additives which produce a decomposition catalyst in the presence of moisture, such as hydrolyzable labile phosphates, are not preferred. Mixtures of additives may be used. Such additives may be added at a suitable time during mixing of the components forming the composition or may be added in the form of a masterbatch.

Suitable fillers or reinforcing agents are for example TiO ₂ ; Fibers such as asbestos, carbon fiber and the like; Silicate and silica powders such as aluminum silicate (mullite), synthetic calcium silicate, zirconium silicate, fumed silica, crystalline silica graphite, natural silica sand, and the like; Boron powders such as boron-nitride powder, boron-silicate powders and the like; Alumina; Magnesium oxide (magnesia); Calcium sulfate (as its anhydride, dihydrate and trihydrate); Calcium carbonates such as chalk, limestone, marble, synthetic precipitated calcium carbonates and the like; Talc, such as fibrous, modular, acicular, lamellar talc, and the like; Wollastonite; Surface treated wollastonite; Glass spheres such as hollow and solid glass spheres, silicate spheres, cenospheres, aluminosilicates (armoshere) and the like; Kaolin, such as kaolin, soft kaolin, calcined kaolin, kaolin, including various coatings known in the art to facilitate compatibility with polymeric matrix resins, and the like; Single crystal fibers, or “whiskers” such as silicon carbide, alumina, boron carbide, iron, nickel, copper, and the like; Glass fibers (including continuous and choppered fibers) such as E, A, C, ECR, R, S, D, and NE glass and quartz, and the like; Sulfides such as molybdenum sulfide, zinc sulfide and the like; Barium compounds such as barium titanate, barium ferrite, barium sulfate, heavy spar, and the like; Metals and metal oxides such as particulate or fibrous aluminum, bronze, zinc, copper and nickel and the like; Flaked fillers such as glass flakes, flake silicon carbide, aluminum diboride, aluminum flakes, steel flakes and the like; Fibrous fillers such as short inorganic fibers such as those derived from blends comprising at least one of aluminum silicate, aluminum oxide, magnesium oxide and calcium sulfate hemihydrate; Natural fillers and reinforcing agents such as wood flour, cellulose, cotton, sisal, jute, starch, coke flour, lignin, ground nut shells, maize, fibrous products such as chopped, etc. obtained by grinding wood; Poly (ether ketone), polyimide, polybenzoxazole, poly (phenylene sulfide), polyester, polyethylene, aromatic polyamide, aromatic polyimide, polyetherimide, polytetrafluoroethylene, acrylic resin, poly (vinyl Reinforcing organic fibrous fibers formed from organic polymers capable of forming fibers such as alcohol); As well as additional fillers and reinforcing agents such as mica, clay, feldspar, flue dust, fillite, quartz, quartzite, perlite, tripoly, diatomaceous earth, carbon black, and the like, or combinations comprising one or more such fillers or reinforcing agents. .

Fillers and reinforcements may be coated with a layer of metallic material that facilitates conduction or may be surface treated with silane to improve adhesion and dispersibility with the polymeric matrix resin. Reinforcing fillers may also be provided in the form of monofilament or multifilament fibers and may be used alone or for example co-weaving or core / sheath, side-by-side, orange ( orange) or can be used in combination with other types of fibers via matrix and fibril configurations or by other methods known to those skilled in the art of fiber making. Suitable coweaving structures include, for example, glass fiber-carbon fibers, carbon fiber-aromatic polyimide (aramid) fibers, aromatic polyimide glass fibers, and the like. Fibrous fillers include, for example, rovings, woven fibrous reinforcements such as 0 to 90 degree fabrics, and the like; Nonwoven reinforcements such as continuous strand mats, choppered strand mats, tissues, paper and felt, and the like; Or in the form of a three-dimensional reinforcing agent such as a braid. Fillers may generally be used in amounts of 1 to 50 parts by weight, based on 100 parts by weight of the resin composition.

Suitable heat stabilizer additives include, for example, organic phosphites such as triphenyl phosphite, tris- (2,6-dimethylphenyl) phosphite, tris- (mixed mono- and di-nonylphenyl) phosphite, and the like; Phosphonates such as dimethylbenzene phosphonate and the like; Phosphates such as trimethyl phosphate and the like or combinations comprising one or more of these thermal stabilizers. Thermal stabilizers are generally used in amounts of 0.01 to 1.0 parts by weight, based on 100 parts by weight of polycarbonate resin and any impact modifier. In one embodiment, the heat stabilizer additive is present in an amount of 0.03 to 0.09 parts by weight based on 100 parts by weight of the resin composition.

Suitable antioxidant additives include, for example, organic phosphites such as tris (nonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert) -Butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite and the like; Alkylated monophenols or polyphenols; Alkylated reaction products of polyphenols and dienes such as tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrosuccinate)] methane and the like; Butylation reaction products of paracresol or dicyclopentadiene; Alkylated hydroquinones; Hydroxylated thiodiphenyl ether; Alkylidene-bisphenols; Benzyl compounds; Esters of beta- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with mono or polyhydric alcohols; Esters of beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with mono or polyhydric alcohols; Esters of thioalkyl or thioaryl compounds such as distearylthioopionate, dilaurylthioopionate, ditridecylthiodipropionate, octadecyl-3- (3,5-di Tert-butyl-4-hydroxyphenyl) propionate, pentaerythryl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and the like; Amides of beta- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid, and the like, or combinations comprising one or more of these antioxidants. Antioxidants are generally used in amounts of 0.001 to 1.0 parts by weight based on 100 parts by weight of the resin composition.

Suitable light stabilizer additives include, for example, benzotriazoles such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -benzotriazole and 2-hydroxy-4-n-octoxy benzophenone and the like, or combinations comprising at least one of these light stabilizers. Light stabilizers are generally used in amounts of 0.001 to 3.0 parts by weight based on 100 parts by weight of the resin composition.

Suitable UV absorber additives include, for example, hydroxybenzophenones; Hydroxybenzotriazole; Hydroxybenzotriazine; Cyanoacrylate; Oxanilides; Benzoxazinone; 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) -phenol (CYASORB 5411); 2-hydroxy-4-n-octyloxybenzophenone (CYASORB 531); 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) -phenol (CYASORB 1164); 2,2 '-(l, 4-phenylene) bis (4H-3,1-benzoxazin-4-one) (CYASORB UV-3638); 1,3-bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenylacryloyl) oxy] methyl] Propane (UVINUL 3030); 2,2 '-(l, 4-phenylene) bis (4H-3,1-benzoxazin-4-one); l, 3-bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenylacryloyl) oxy] methyl] Propane; Nano-sized inorganic materials such as titanium oxide, cerium oxide and zinc oxide, all of which have a size of less than 100 nanometers; Or combinations comprising at least one of these UV absorbers. UV absorbers are generally used in amounts of 0.001 to 3.0 parts by weight based on 100 parts by weight of the resin composition.

Suitable plasticizer additives include, for example, phthalic acid esters such as dioctyl-4,5-epoxy-hexahydrophthalate, tris- (octoxycarbonylethyl) isocyanurate, tristearin, epoxidized soybean oil and the like or such plasticizers And combinations comprising one or more of them. The plasticizer may generally be used in an amount of 1 to 50 parts by weight based on 100 parts by weight of the resin composition.

Suitable antistatic additives include, for example, glycerol monostearate, sodium stearyl sulfonate, sodium dodecylbenzenesulfonate, and the like or combinations of such antistatic agents. In one embodiment, carbon fibers, carbon nanofibers, carbon nanotubes, carbon black, or combinations thereof may be used in polymer resins containing chemical antistatic agents to impart electrostatic dissipation to the composition. The antistatic agent is generally used in an amount of 0.001 to 5.0 parts by weight based on 100 parts by weight of the resin composition.

Suitable release additives include, for example, stearyl stearate, pentaerythritol tetrastearate, 1-decene (ethylflu), beeswax, montan wax, paraffin wax, or the like or combinations comprising one or more of these release agents. The mold release agent is used in an amount of 0.10 to 3.0 parts by weight based on 100 parts by weight of the resin composition.

Suitable lubricant additives include, for example, fatty acid esters such as alkyl stearyl esters (eg methyl stearate) and the like; Mixtures of hydrophilic and hydrophobic surfactants and methyl stearate, such as methyl stearate and polyethylene-polypropylene glycol copolymers, including polyethylene glycol polymers, polypropylene glycol polymers and copolymers thereof in suitable solvents; Or combinations comprising one or more of these lubricants. Lubricants are generally used in amounts of 0.01 to 5.0 parts by weight, based on 100 parts by weight of the resin composition.

Suitable pigment additives include, for example, inorganic pigments such as metal oxides and mixed metal oxides (eg, zinc oxide, titanium dioxide, iron oxide, etc.); Sulfides (eg, zinc sulfide, etc.); Aluminate; Sodium sulfo-silicates; Sulfates and chromates; Carbon black; Zinc ferrides; Ultramarine blue; Pigment brown 24; Pigment red 101; Pigment yellow 119; Organic pigments such as azo, diazo, quinacridone, perylene, naphthalene tetracarboxylic acid, flabanthrone, isoindolinone, tetrachloroisoindolinone, anthraquinone, anthrone, dioxazine, phthalocsai Non- and azo lakes; Pigment Blue 60, Pigment Red 122, Pigment Red 149, Pigment Red 177, Pigment Red 179, Pigment Red 202, Pigment Violet 29, Pigment Blue 15, Pigment Green 7, Pigment Yellow 147 and Pigment yellow 150, or a combination comprising one or more of these pigments. Pigments are generally used in amounts of 0.00001 to 20 parts by weight based on 100 parts by weight of the resin composition.

Suitable dyes include, for example, organic dyes such as coumarin 460 (blue), coumarin 6 (green), neil red and the like; Lanthanide complexes; Hydrocarbon and substituted hydrocarbon dyes; Polycyclic aromatic hydrocarbons; Scintillation dyes (eg, oxazoles and oxadiazoles); Carbocyanine dyes; Phthalocyanine dyes; Oxazine dyes; Carbostyryl dyes; Porphyrin dyes; Acridine dyes; Anthraquinone dyes; Arylmethane dyes; Azo dyes; Diazonium dyes; Nitro dyes; Quinone imine dyes; Tetraazolium dyes; Thiazole dyes; Perylene dyes; Perinone dyes; Bis-benzoxazolylthiophene (BBOT); Xanthene dyes; Fluorescent materials such as anti-stokes shift dyes that absorb at near infrared wavelengths and emit visible wavelengths; Luminescent dyes such as 7-amino-4-methylcoumarin; 3- (2'-benzothiazolyl) -7-diethylaminocoumarin; 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole; 2,5-bis- (4-biphenylyl) -oxazole; 2,2'-dimethyl-p-quaterphenyl; 2,2-dimethyl-p-terphenyl; 3,5,3 "", 5 ""-tetra-tert-butyl-p-quinkephenyl; 2,5-diphenylfuran; 2,5-diphenyloxazole; 4,4'-diphenylstilbene; 4-Dicyanomethylene-2-methyl-6- (p-dimethylaminostyryl) -4H-pyran; 1,1'-diethyl-2,2'-carbocyanine iodide; 3,3'-diethyl-4,4 ', 5,5'-dibenzothiatricarbocyanine iodide; 7-dimethylamino-1-methyl-4-methoxy-8-azaquinolone-2; 7-dimethylamino-4-methylquinolone-2; 2- (4- (4-dimethylaminophenyl) -1,3-butadienyl) -3-ethylbenzothiazolium perchlorate; 3-diethylamino-7-diethyliminophenoxazonium perchlorate; 2- (l-naphthyl) -5-phenyloxazole; 2,2'-p-phenylene-bis (5-phenyloxazole); Rhodamine 700; Rhodamine 800; Pyrene; Chrysene; Rubrene; Coronene and the like, or combinations comprising one or more such dyes. The dye is generally used in an amount of 0.0001 to 20 parts by weight based on 100 parts by weight of the resin composition.

In cases where foaming is desired, suitable foaming agents include, for example, halohydrocarbons that generate low boiling halohydrocarbons and carbon dioxide; Blowing agents which are solid at room temperature and which produce nitrogen, carbon dioxide and ammonia gas when heated at temperatures above the decomposition temperature such as azodicarbonamides, metal salts of azodicarbonamides, 4,4'-oxybis (benzenesulfonyl Hydrazide), sodium bicarbonate, ammonium carbonate, and the like, or combinations comprising one or more such blowing agents. Blowing agents are generally used in molar ratios of 2.0 to 10 based on the total moles of carbonate structural units in the polycarbonate as described in US Pat. No. 5,597,887.

Suitable flame retardants that may be added may be organic compounds comprising phosphorus, bromine and / or chlorine. Non-bromine and non-chlorine phosphorus-containing flame retardants, such as organic phosphates and organic compounds containing phosphorus-nitrogen bonds, are sometimes preferred for regulatory reasons.

One type of exemplary organic phosphate is (GO) ₃ P = 0, wherein each G independently is an alkyl, cycloalkyl, aryl, alkaryl, or aralkyl group, provided that at least one G is an aromatic group Aromatic phosphate). Two of the G groups may be joined together to form a ring group, an example of which is the diphenyl pentaerythritol diphosphate described in US Pat. No. 4,154,775 to Axelrod. Other suitable aromatic phosphates include, for example, phenyl bis (dodecyl) phosphate, phenyl bis (neopentyl) phosphate, phenyl bis (3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di (p-tolyl) phosphate, bis (2-ethylhexyl) p-tolyl phosphate, tritolyl phosphate, bis (2-ethylhexyl) phenyl phosphate, tri (nonylphenyl) phosphate, bis (dodecyl) p-tolyl phosphate, Dibutyl phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis (2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate and the like. Particular aromatic phosphates are compounds in which each G is aromatic, such as triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate and the like.

Also useful are divalent or polyvalent aromatic phosphorus-containing compounds, for example compounds having the structure:

Wherein each G ¹ is independently a hydrocarbon having 1 to 30 carbon atoms; Each G ² is independently hydrocarbon or hydrocarbonoxy having 1 to 30 carbon atoms; Each X is independently bromine or chlorine; m is 0-4; n is 1 to 30.

Examples of suitable divalent or polyvalent aromatic phosphorus-containing compounds are resorcinol tetraphenyl diphosphate (RDP), bis (diphenyl) phosphate of hydroquinone and bis (diphenyl) phosphate of bisphenol A (the oligomeric and Polymerizable counterparts). The process for preparing the divalent or polyvalent aromatic compounds described above is described in British Patent No. 2,043,083.

Examples of suitable flame retardants containing phosphorus-nitrogen bonds include phosphonite chloride, phosphorus ester amide, phosphate amide, phosphonic acid amide, phosphinic acid amide, tris (aziridinyl) phosphine oxide. When present, the phosphorus-containing flame retardant is generally present in an amount of 0.001 to 10 parts by weight, or may be present in an amount of 0.01 to 5 parts by weight, based on 100 parts by weight of the resin composition.

Halogenated materials are also used as a useful class of flame retardants. Such materials are aromatic halogen compounds and resins of Formula 15:

Wherein R is an alkylene, alkylidene or cycloaliphatic bond such as methylene, ethylene, propylene, isopropylene, isopropylidene, butylene, isobutylene, amylene, cyclohexylene, cyclopentylidene and the like; A bond selected from the group consisting of oxygen ethers; Carbonyl; Amines; Or sulfur containing bonds such as sulfides, sulfoxides, sulfones and the like. R may also consist of two or more alkylene or alkylidene bonds connected by groups such as aromatic, amino, ether, carbonyl, sulfide, sulfoxide, sulfone and the like.

Ar and Ar 'of Formula 15 are each independently mono- or polycarbocyclic aromatic groups such as phenylene, biphenylene, terphenylene, naphthylene and the like. Ar and Ar 'may be the same or different.

Y is a substituent selected from the group consisting of organic, inorganic or organometallic radicals. Substituents represented by Y are either (1) halogen such as chlorine, bromine, iodine, fluorine, or (2) ether groups of the formula OE, where E is a monovalent hydrocarbon radical similar to X, or (3) to R Monovalent hydrocarbon groups of the type indicated by, or (4) other substituents such as nitro, cyano and the like, wherein the substituents are essentially inert under the condition that they may be one or more, such as two halogen atoms, per aryl nucleus.

When present, each X is independently a monovalent hydrocarbon group, such as an alkyl group (eg, methyl, ethyl, propyl, isopropyl, butyl, decyl, etc.); Aryl groups (eg, phenyl, naphthyl, biphenyl, xylyl, tolyl, etc.); Aralkyl groups (eg, benzyl, ethylphenyl, etc.); Cycloaliphatic groups (eg, cyclopentyl, cyclohexyl, etc.). The monovalent hydrocarbon group itself may contain inert substituents.

each d is independently the maximum number equal to the number of substitutable hydrogens on the aromatic ring comprising 1 to Ar or Ar '. each of e is independently a maximum number equal to the number of substitutable hydrogens on 0 to R. a, b, and c are each independently an integer comprising 0. If b is not 0, a is not 0 and c is not 0. Alternatively, a or c (but not both) may be zero. When b is zero, the aromatic group is bonded by a direct carbon-carbon bond.

The hydroxyl and Y substituents on the aromatic groups Ar and Ar 'may vary in ortho, meta or para positions on the aromatic ring, and the groups may have any possible geometric relationship to each other.

Within the scope of the above formulas include bisphenols of the following representative compounds: 2,2-bis- (3,5-dichlorophenyl) propane; Bis- (2-chlorophenyl) -methane; Bis (2,6-dibromophenyl) methane; 1,1-bis- (4-iodophenyl) ethane; 1,2-bis- (2,6-dichlorophenyl) ethane; 1,1-bis- (2-chloro-4-iodophenyl) ethane; 1,1-bis- (2-chloro-4-methylphenyl) ethane; 1,1-bis- (3,5-dichlorophenyl) ethane; 2,2-bis- (3-phenyl-4-bromophenyl) ethane; 2,6-bis- (4,6-dichloronaphthyl) propane; 2,2-bis- (2,6-dichlorophenyl) -pentane; 2,2-bis- (3,5-dibromophenyl) hexane; Bis- (4-chlorophenyl) phenylmethane; Bis- (3,5-dichlorophenyl) cyclohexylmethane; Bis- (3-nitro-4-bromophenyl) methane; Bis- (4-hydroxy-2,6-dichloro-3-methoxyphenyl) methane; 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) propane; And 2,2-bis- (3-bromo-4-hydroxyphenyl) propane. Within the formula, 1,3-dichlorobenzene, 1,4-dibromobenzene, l, 3-dichloro-4-hydroxybenzene, and biphenyls such as 2,2'-dichlorobiphenyl, polybrominated 1,4-diphenoxybenzene, 2,4'-dibromobiphenyl, and 2,4'-dichlorobiphenyl, as well as decabromo diphenyl oxide and the like.

Also useful are oligomeric and polymerizable halogenated aromatic compounds such as copolycarbonates of bisphenol A and tetrabromobisphenol A and carbonate precursors such as phosgene. Metal synergists such as antimony oxide can also be used with flame retardants. When present, the halogen-containing flame retardant may be present in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the resin composition, or may be present in an amount of 0.01 to 5 parts by weight.

Inorganic flame retardants such as potassium perfluorobutane sulfonate (limar salt) and potassium diphenylsulfone sulfonate as well as sulfonates such as perfluoroalkane sulfonate described in US Pat. No. 3,775,367; Salts formed by reacting alkali or alkaline earth metals (which may be lithium, sodium, potassium, magnesium, calcium and barium salts) and inorganic acid complex salts (eg oxo-anions), such as alkali and alkaline earth metals of carboxylic acids Salts (eg, Na ₂ CO ₃ , K ₂ CO ₃ , MgCO ₃ , CaCO ₃ , BaCO ₃ , and BaCO ₃ ) or fluoro-anionic complexes (eg, Li ₃ AlF ₆ , BaSiF ₆ , KBF ₄ , K ₃ AlF ₆ , KAlF ₄ , K ₂ SiF ₆ , and / or Na ₃ AlF ₆ ) and the like may also be used. When present, the inorganic flame retardant salt may generally be present in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the resin composition, and may also be present in an amount of 0.01 to 5 parts by weight.

Antidrip agents, such as fibril forming or non-fibrill forming fluoropolymers (eg polytetrafluoroethylene (PTFE)), may also be used. The antidrip agent may be encapsulated by the above-mentioned rigid copolymer, for example, SAN. PTFE encapsulated in SAN is known as TSAN. Encapsulated fluoropolymers can be prepared by polymerizing the encapsulating polymer in the presence of a fluoropolymer, such as an aqueous dispersion. TSAN is very advantageous over PTFE in that TSAN is more easily dispersed in the composition. Suitable TSANs may include, for example, 50 weight percent PTFE and 50 weight percent SAN, based on the total weight of the encapsulated fluoropolymer. The SAN may include, for example, 75 weight percent styrene and 25 weight percent acrylonitrile based on the total weight of the copolymer. Alternatively, the fluoropolymer can be premixed in any way with an aromatic polycarbonate resin or a second polymer such as SAN to form agglomerated materials useful as antidrip agents. Either method can be used to prepare encapsulated fluoropolymers. The antidripping agent is generally used in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the resin composition.

The relative content of each component of the composition depends on the desired properties, the particular component used, and the like, and can be readily determined by one skilled in the art according to the following criteria. In one embodiment, the resin composition comprises 4 to 100 weight percent polysiloxane-polycarbonate copolymer, 0 to 15 weight percent impact modifier, and 0 to 96 weight percent additional polymer. In another embodiment, the resin composition comprises 25 to 90 weight percent polysiloxane-polycarbonate copolymer, 0 to 12 weight percent impact modifier, and 10 to 75 weight percent additional polymer, preferably high temperature thermoplastics. . In another embodiment, the resin composition comprises 30 to 85 weight percent polysiloxane-polycarbonate copolymer, 0 to 10 weight percent impact modifier; And 15-70% by weight of optional additional polymer. The values for the aforementioned weight percentages are all based on the combined weight of the resin composition, ie the combined weight of the polysiloxane-polycarbonate, any impact modifier and any optional additional polymer.

The abovementioned mixtures are considered to be optimal for the performance requirements of thermally and hydrolytically stable products, in particular products intended for steaming, for example dishwashers or autoclaves. Mixtures using lower amounts of polysiloxane-polycarbonate copolymers have lower retention of ductility during steaming, especially steam sterilization, while mixtures using higher amounts of polysiloxane-polycarbonate copolymers have repeated steaming. The resistance to heat-induced deformations leading to softening of the syrup can be lowered or have higher releasability.

The compositions may optionally be choppered in a Henschel high speed mixer, such as in one embodiment a polysiloxane-polycarbonate copolymer, an optional impact modifier, any additional polymer and any optional additives. It can be prepared by first mixing with glass strand or other filler. Other low shear processes, including but not limited to passive mixing, can also achieve such mixing. It is most effective when the polysiloxane-polycarbonate copolymer is well dispersed throughout the composition. In some situations, slight heating can help disperse the polysiloxane-polycarbonate copolymer during the mixing operation. Solvents may be used to aid in the dispersion of the polysiloxane-polycarbonate copolymer.

The blend may then be injected through the hopper into the throat of the twin screw extruder. Alternatively, one or more components may be incorporated into the composition by feeding downstream from the throat directly into the extruder and / or via a sidestuffer. Such additives may also be combined in the masterbatch with the desired polymer resin and fed into the extruder. Optionally, a redistribution catalyst may be included to control the molecular weight of the polymer in the blend and / or redistribute the polysiloxane blocks to the blend. Redistribution catalysts include, for example, catalysts produced by reacting a branched site production rate polyvalent phenolic branching agent and a basic transesterification catalyst together in the presence of an inert organic solvent. Suitable polyhydric phenolic or carboxylic acid branching agents useful for reaction with transesterification catalysts are aromatic and contain three or more functional groups which are carboxyl, carboxylic anhydride, phenol, haloformyl or mixtures thereof. Non-limiting examples of such polyvalent aromatic compounds include 1,1,1-tri (4-hydroxyphenyl) ethane, 2,2 ', 5,5'-tetra (4-hydroxyphenyl) hexane, trimellitic anhydride , Trimellitic acid, trimellitoyl trichloride, 4-chloroformyl phthalic anhydride, pyromellitic acid, pyromellitic dihydrate, melitric acid, melitric anhydride, trimes, benzophenone tetracarboxylic acid, benzophenone tetracarboxylic anhydride, and the like. Can be mentioned. Preferred polyhydric phenolic or carboxylic acid compounds are 1,1,1-tri (4-hydroxyphenyl) ethane, trimellitic anhydride, trimellitic acid or haloformyl derivatives thereof. Suitable transesterification catalysts are, for example, oxides, hydrides, hydroxides, carbonates, carboxylates, alkoxides, or amides of ammonium, alkyl ammonium, alkali or alkaline earth metals, as well as basic metal oxides such as zinc oxide, lithium stearate And salts of weak acids such as organotitanium, organoaluminum and organotin (eg tetraoctyl titanate). Other catalysts include, for example, polyacrylates and polymethacrylates; Divinylbenzene; Triallyl isocyanurate; Trimethylolpropane trimethylacrylate; Ethoxylated bisphenol A diacrylate; Trimethylolpropane triacrylate; Pentaerythritol triacrylate; Pentaerythritol tetraacrylate.

Extruders generally operate at temperatures higher than the temperature required to flow the composition. The extrudate is immediately quenched in a batch of water and pelleted. The pellets produced can be 1/4 inch (6.35 mm) long or short as desired when cutting the extrudate. Such pellets can be used for subsequent molding, shaping or forming.

The composition may be extruded into a film, sheet, tate, web, tube (both cylinder and non-cylindrical), or the like, or may be shaped, formed or molded into a product by commercially available and conventional procedures (eg, Injection molding, extrusion molding, etc.).

Suitable products can be wide range. In one embodiment, the product is steamed as its regular maintenance and / or use part. As used herein, “steam treatment” and “contact with steam” should be understood to include contact with steam alone or with steam and water under the conditions indicated. In another embodiment, the product is steamed ("steam autoclave sterilization") in a steam autoclave as its regular maintenance and / or use part, for example a medical device. Some examples of medical devices include syringes, blood filter housings, blood bags, solution bags, venous connectors, dialysis machines, catheters, medical storage trays, medical devices, medical tubes, heart pacemakers and defibrillators, cannulas, implants Prostheses, heart assist devices, heart valves, vascular grafts, extra-corporeal devices, artificial organs, pacemaker leads, defibrillator leads, blood pumps, balloon pumps, AV shunts, biosensors, cells Capsule membranes, wound dressings, artificial joints, orthopedic implants, and syringes.

Examples of non-medical devices that can be steamed as regular maintenance and use parts include food trays, animal cages, cable sheathings, varnish and coating equipment, pumps and structural parts of vehicles, ore mining screens and Conveyor belts, laminating compounders, aviation equipment, chocolate molds, watercooker components, washing machine components, dishwasher components, dishwasher safety components, and the like. In some applications, the products may be treated with both steam treatment (eg dishwasher) and steam autoclave sterilization treatment under less stringent conditions.

In one particular embodiment, a method is provided that includes treating a product with steam, wherein at least a portion of the product is an amount of polysiloxane effective to provide thermal and hydrolytic stability to the product for at least 15 cycles. Formed from a composition comprising a polycarbonate copolymer, each cycle comprising contacting the steam for 20 minutes at a temperature of at least 100 ° C. and at least 1.0 atmosphere. In another embodiment, at least a portion of the article is formed from a composition comprising a polysiloxane-polycarbonate copolymer in an amount effective to provide thermal and hydrolytic stability to the article for at least 15 cycles, wherein each cycle is Contacting the steam for 20 minutes at a temperature of < RTI ID = 0.0 > 121 C < / RTI >

Another embodiment includes treating the product with steam, comprising exposing the product to steam for at least 15 cycles at 100 ° C. and atmospheric pressure, wherein the product provides thermal and hydrolytic stability to the product. Effective amounts of the following polysiloxane-polycarbonate copolymers are included. Another embodiment includes treating the product with steam, comprising exposing the product to steam for at least 15 cycles at a temperature of 121 ° C. and 1.5 atmospheres, wherein the product is thermal and hydrolytically stable to the product. And an amount of polysiloxane-polycarbonate copolymer effective to provide.

Another embodiment includes steam autoclaving a medical device, wherein at least a portion of the medical device comprises an amount of polysiloxane-polycarbonate copolymer effective to provide autoclave resistance to the product for at least 15 cycles. It is formed from a composition comprising, each cycle comprising contacting the steam for 20 minutes at a temperature of 121 ° C. or higher and at least 1.5 atmospheres.

In another specific embodiment, a method of steam sterilizing a product is provided, comprising exposing the product to steam at a temperature of 121 ° C. and 1.5 atmospheres for at least 15 cycles, wherein the product is vapor autoclave resistant to the product. And an amount of polysiloxane-polycarbonate copolymer effective to provide.

Steam sterilization is frequently used for medical purposes because of its convenience and reliability. Steam sterilization may involve autoclaving the product for one or more effective cycles. One effective cycle depends greatly on the pressure, temperature, and cycle length, as well as the autoclave used, the user of the autoclave, and the product being sterilized. The autoclave cycle can also be carried out in the presence of various steam boiler additives. Typical boiler additives for reducing corrosion in steam generators are amino compounds such as morpholine, hydrazine, N, N-diethylaminoethanol ("NALCO 359" or "BETZ NA-9"), and octadecylamine. Steam sterilization is a trade name such as "Castle 7900" (acoustic detergent), "Chem Crest 14" (ultrasound detergent), "Tergitol Min Foam 2X" (nonionic surfactant), etc. It is also possible in the presence of hospital detergents and cleaners such as those sold as.

In another embodiment, the polysiloxane-polycarbonate copolymer is present in an amount sufficient to provide thermal and hydrolytic stability to the product when steaming for at least 15 cycles (100 minutes each cycle) at 100 ° C. under atmospheric pressure. do.

In another embodiment, the polysiloxane-polycarbonate copolymer is sufficient to provide thermal and hydrolytic stability to the product upon steam autoclave treatment for at least 15 cycles at 121 ° C. under 1.5 atmospheres (each cycle is 20 minutes). Present in quantities. In another embodiment, the polysiloxane-polycarbonate copolymer is sufficient to provide thermal and hydrolytic stability to the product when subjected to steam autoglide treatment for at least 15 cycles (121 minutes each) at 121 ° C. under 2.0 atmospheres. Present in quantities. In another embodiment, the polysiloxane-polycarbonate copolymer is sufficient to provide thermal and hydrolytic stability to the article when steam autoclaves for at least 15 cycles at 135 ° C. under 1.5 atmospheres (each cycle is 20 minutes). Present in quantities. In another embodiment, the polysiloxane-polycarbonate copolymer provides thermal and hydrolytic stability to the article when subjected to vapor autoclave treatment for at least 15 cycles (135 minutes at 20 ° C.) under 2 atmospheres, each cycle being 20 minutes. Present in sufficient quantities.

As used herein, a product having "thermal and hydrolytic stability" refers to an article comprising a composition of the present invention after steaming, including autoclaving treatment under the above conditions, that impact strength, tensile strength, ductility, dimensional stability, It means that there is no significant reduction in one or more of the physical or mechanical properties such as vicat softening temperature, transparency and the like. Steam treatment can be carried out at 100 to 200 ° C. under 1 to 30 atmospheres. As used herein, "significant reduction" means that certain physical or mechanical properties are reduced to such an extent that the product is unsuitable for future use. Those skilled in the art will understand that the reduction in physical properties that make a product unsuitable for future use will vary greatly depending on factors such as the particular product and / or its intended use. In the embodiments described below, various physical and / or mechanical properties of articles with improved thermal and hydrolytic stability are described. A criterion for determining whether a product to be steamed should be deemed unsuitable for future use is to determine whether the syringe, for example after repeated steam sterilization, does not meet the characteristics of impact resistance described below. The criteria for suitability for such future use may be applied in a similar manner to any or all of the physical and / or mechanical properties described below. The steam treatment criteria used herein to determine suitability for future use are only one example of thermal and hydrolytic stability, and parameters of specific mechanical and / or physical properties of the product after sterilization described by those skilled in the art are described below. If it can be preserved, equivalent alternative standards for it may be measured.

For example, a product with thermal and hydrolytic stability may be able to withstand 15 or more treatment cycles while maintaining the original tensile strength of at least 50%, specifically 75%, wherein each cycle is Contact with steam for 20 minutes at 100 ° C. under atmospheric pressure. In another embodiment, a product having thermal and hydrolytic stability is such that the product is capable of withstanding at least 15 autoclave cycles while maintaining at least 50% of initial tensile strength, specifically 75% of initial tensile strength. Each cycle involves contacting the steam for 20 minutes at 121 ° C. or 135 ° C. under 1.5 or 2.0 atmospheres (gauge).

In another embodiment, a product having thermal and hydrolytic stability is characterized in that the product has a ductility of 50% to 99%, specifically a ductility of 60% to 99%, more specifically a ductility of 75% to 99% Capable of withstanding 15 or more steam cycles, maintaining contact with steam for 20 minutes at temperatures of 100 ° C. or higher under atmospheric pressure. In another embodiment, a product having thermal and hydrolytic stability is characterized in that the product has a ductility of 50% to 99%, specifically a ductility of 60% to 99%, more specifically a ductility of 75% to 99% Capable of withstanding 15 or more autoclave cycles, maintaining contact with steam for 20 minutes at 121 ° C. or 135 ° C. under 1.5 or 2.0 atmospheres. The ductility herein can be measured by using five to ten 1/8 inch (3.12 mm) ASTM or ISO bars of the compositions of the present invention, each of which being impact tested by ASTM D 256 or ISO 180 / 1A. . In general, stress whitening or tensile failure indicates a mode of soft failure, while lack of stress whitening or brittle fracture indicates a brittle failure mode. Elongation is expressed as a percentage of the ductile failure mode.

In another embodiment, the significant reduction in dimensional stability is such that any dimension of the product exceeds 10% after at least 15 autoclave cycles, each cycle including contact with steam for 20 minutes at 100 ° C. under atmospheric pressure. It means to change. In another embodiment, the significant reduction in dimensional stability is that any dimension of the product is contacted with steam for 20 minutes at 121 ° C. or 135 ° C. under 15 or 2.0 atmospheres (gauge) of at least 15 autoclave cycles. After the change). For example, when measuring the diameter of an unfilled glass tube before and after autoclave treatment, the dimension of the diameter at any point of the tube exceeds 10% after being treated with steam at 100 ° C. under atmospheric pressure. Not to be changed can be considered that the product is dimensional stability. In another embodiment, the dimension of the tube at any point of the tube should not change more than 5% after autoclave treatment at 121 ° C. or 135 ° C. under 1.5 or 2.0 atmosphere after 15 cycles. Can be considered to be.

In another embodiment, a product having thermal and hydrolytic stability may be subjected to 121 ° C. to 400 ° C., in particular after 15 or more autoclave cycles, each cycle comprising contacting steam for 20 minutes at 100 ° C. under atmospheric pressure. Can have a vicat softening temperature (temperature measured when the softening of the product is first observed, as measured by ASTM D-1525) of 125 ° C to 300 ° C, more specifically 130 ° C to 220 ° C. In another embodiment, the article with thermal and hydrolytic stability is 121 after 15 or more cycles (each cycle comprising contacting steam for 20 minutes at 121 ° C. or 135 ° C. under 1.5 or 2.0 atmosphere (gauge)). It may have a vicat softening temperature of ℃ to 400 ℃, specifically 125 ℃ to 300 ℃, more specifically 130 ℃ to 220 ℃.

In another embodiment, a product having thermal and hydrolytic stability is 1/8 inch (3.12) according to ASTM D256 after at least 15 cycles (each cycle comprising contacting steam for 20 minutes at 100 ° C. under atmospheric pressure). mm) can have a notched Izod impact (NII) of 3 to 18 ft-lb / inch (feet-lb / inch), or 3 to 14 ft-lb / inch when measured at room temperature. In another embodiment, a product having thermal and hydrolytic stability comprises at least 15 autoclave cycles, each cycle contacting steam for 20 minutes at 121 ° C. or 135 ° C. under 1.5 or 2.0 atmospheres (gauge). Notched Izod of 3 to 18 ft-lb / inch (feet-lb / inch), or 3 to 14 ft-lb / inch, as measured later at room temperature using a 1/8 inch (3.12 mm) bar according to ASTM D256 May have an impact.

In another embodiment, the product comprises from 15% to 100 as measured according to ASTM D256 after treatment with steam for at least 15 cycles (each cycle comprising contacting steam for 20 minutes at 100 ° C. under atmospheric pressure). %, Specifically 40% to 100%, more specifically 60% to 100% retention of NII. In another embodiment, when measured according to ASTM D256 after at least 15 autoclave cycles, each cycle comprising contacting steam for 20 minutes at 121 ° C or 135 ° C under 1.5 or 2.0 atmospheres (gauge) The product may have an NII retention of 15% to 100%, specifically 40% to 100%, more specifically 60% to 100%.

The thermoplastic composition may have significantly improved hydrolytic aging stability as indicated by the reduction in the weight average molecular weight and / or the rate of change of melt flow after exposure to high humidity conditions. Melt flow is the ratio of extrusion of the thermoplastic material through the pores at the specified temperature and load. This provides a means to measure the flow of molten material and can be used to measure the degree of degradation of the plastic as a result of exposure to heat and / or moisture. The degraded material generally flows more due to the reduced molecular weight and may exhibit reduced physical properties. Typically, the melt flow rate is measured both before and after storage under conditions of high humidity and then calculated as the difference in the rates.

As measured according to ISO 1133 at 300 ° C./1.2 kg (after 6 minutes of preheating), the rate of change of the melt flow is less than about 20% after 15 cycles of 20 minutes at 100 ° C. under atmospheric pressure, specifically Is less than 1 to 15%, and more specifically less than about 10%, a composition suitable for the formation of a product may have improved hydrolytic aging stability. Melt after 15 autoclave cycles for 20 minutes at 121 ° C or 135 ° C under 1.5 or 2.0 atmospheres (gauge) as measured according to ISO 1133 at 300 ° C / 1.2 kg (Kg) (after 6 minutes of preheating) Compositions suitable for the formation of autoclave products may also have improved hydrolytic aging stability in that the rate of change of flow is less than about 20%, specifically less than 1-15%, and more specifically less than about 10%. have.

When measured by gel permeation chromatography in dichloromethane using polystyrene standards, the rate of change in the weight average molecular weight is 1-10%, or 1-8% after 15 cycles for 20 minutes at 100 ° C. under atmospheric pressure. Or, moreover, from 1 to 5%, a composition suitable for the formation of a product may have improved hydrolytic aging stability. As measured by gel permeation chromatography in dichloromethane using polystyrene standards, the rate of change in the weight average molecular weight after 15 autoclave cycles for 20 minutes at 121 ° C or 135 ° C under 1.5 or 2.0 atmospheres (gauge) Compositions suitable for the formation of autoclave products may have improved hydrolytic aging stability in that from 1 to 10%, or 1 to 8%, or even 1 to 5%.

In one embodiment, transparent compositions can be used, for example when visualizing through or inside a product is important. For example, in medical applications such as blood and secretion handling devices, it may be important to be able to see bubbles, blood clots, foreign bodies, etc., for example in blood and drainage. The compositions described herein can produce devices with wall thicknesses of 1/4 inch (6.35 mm) or less without adversely affecting their transparency. Furthermore, after steaming for at least 15 cycles (each cycle comprising contacting steam for 20 minutes at 100 ° C. or higher above atmospheric pressure), the product has a turbidity of less than 30% and 40 as measured according to ASTM D1003. Permeability greater than%, specifically less than 20% haze and greater than 50%, more specifically less than 15% haze and greater than 60%. Furthermore, after autoclave treatment for 15 or more autoclave cycles (each cycle comprising contacting steam for 20 minutes at 121 ° C or 135 ° C under 1.5 or 2.0 atmospheres (gauge)), measured according to ASTM D1003 The product may have less than 30% turbidity and more than 40% transmittance, specifically less than 20% turbidity and more than 50% transmittance, more specifically less than 15% turbidity and more than 60% transmittance. have.

In one embodiment, the steamed or steam sterilized products described herein can have increased resistance to steam as compared to polycarbonate compositions that do not contain a polysiloxane-polycarbonate copolymer. In one embodiment, an autoclave resistant article made from a composition comprising a polysiloxane-polycarbonate copolymer is prepared after 1 to 5000 autoclave cycles at 100 ° C. to 300 ° C. under 1 to 3 atmospheres, specifically 1 After 5 to 1000 autoclave cycles at 110 ° C. to 250 ° C. under 2 atmospheres, more specifically after 10 to 100 autoclave cycles at 120 ° C. to 200 ° C. under 1 to 1.8 atmospheres, as described above. There is stability. For example, an autoclave resistant article made from a polysiloxane-polycarbonate copolymer can be used for 1 to 5000 autoclave cycles at 100 ° C. to 300 ° C. under 1 to 3 atmospheres, further from 110 ° C. to 1 to 2 atmospheres. There is dimensional stability for 5 to 1000 autoclave cycles at 250 ° C. and even more for 10 to 100 autoclave cycles at 120 ° C. to 200 ° C. under 1 to 1.8 atmospheres.

The invention is further illustrated by the following non-limiting examples.

In the following examples, the following materials are used.

A: polycarbonate-polysiloxane copolymer; 3.5 weight percent polydimethylsiloxane, where D is 45 to 50

B: polycarbonate-polysiloxane copolymer; 5.0 weight percent polydimethylsiloxane, wherein D is 45 to 50

Bl: polysiloxane-polycarbonates tested with ISO-10993; 3.5 wt% polysiloxane, wherein D is 45 to 50

LEXAN 141: versatile, medium viscosity BPA polycarbonate

LEXAN 164H: polycarbonate product with improved hydrolytic stability

HPS6: high viscosity, high molecular weight polycarbonate

4704: High Temperature Polyphthalyl-BPA Carbonate Copolymer

Example 1

Samples of the above polymers were molded into 0.125 inch (3.2 mm) thick ASTM bars. The original notched Izod impact strength was measured according to ASTM D256. The sample was then placed in a saturated vapor autoclave and the autoclave was held at 121 ° C. (250 ° F.) for the indicated time. The sample was taken out and notched, and the notched Izod impact strength of the autoclaved sample was measured. Data was recorded as retention of the original Notched Izod impact strength. In all cases, 5 bars were measured for each sample.

A comparison of Notch Izod impact retention of Bl (3.5% polysiloxane product) and selected polycarbonate products is shown in FIG. 1 and Table 1. Table 1 shows the effect of the autoclave at extended 121 ° C. on the notched Izod impact strength (ft-lb / inch) of the selected products. Ductility indicates what percentage of the sample is destroyed in a flexible manner. "Std dev" used in all examples is the standard deviation.

Although the Bl product had lower viscosity and lower heat distortion temperature values than 4704 and HPS6, its impact property retention was better after autoclaving at 121 ° C. for an extended time. Surprisingly, Bl showed much greater ductility than other comparative samples over a much longer average autoclave duration.

Example 2

Samples were molded and notched by ISO Izod bars. Initial notched Izod impact strength was measured. The sample was then placed in a saturated steam autoclave and the autoclave was held at 100 ° C. (212 ° F.) for the indicated time. The sample was taken out and the notched Izod impact strength of the autoclaved sample was measured. Data was recorded as retention of the original Notched Izod impact strength. In all cases, 5 bars were measured for each sample.

Table 2 shows the retention of Notched Izod impact strength of polysiloxane-polycarbonate product to polycarbonate product in kilojoules per square meter (kJ / m 2). The MVR used in all examples is expressed in cm 3/10 min as melt viscosity measured according to ISO 1133. Notched Izod impact strength was given in kJ / m 2 according to ISO 180 / 1A.

Polysiloxane-containing polycarbonate products also showed improved property retention and increased pressure at 100 ° C. (212 ° F.). Polysiloxane-containing products A and B showed better Notch Izod impact and instrumentation impact retention than 164H, a polycarbonate product optimized for improved hydrolytic stability as shown in Tables 2 and 3 and FIGS. 2 and 3 .

The content of Si (PDMS) indicates the content of silicon in polydimethylsiloxane. As shown, samples A and B were shown to maintain ductility over an extended period of time as opposed to 164H without ductility after 25 hours of autoclave treatment.

Table 3 shows the retention of instrumentation impact energy (J) of polysiloxane-polycarbonate products versus polycarbonate products. Over 800 hours, both A and B retained about 85% of their original energy maximum, while 164H maintained only about 56% of their original energy maximum. Puncture energy and energy at maximum are expressed in Joules according to the ISO 6603 method. Ductility is the ductility measured by the number of samples broken in a ductile manner.

Example 3

In Example 3 the samples were molded into 0.125 inch (3.2 mm) thick ASTM Izod bars. Initial notched Izod impact strength was measured. The sample was then placed in a saturated vapor autoclave and the autoclave was held at 121 ° C. (250 ° F.) for the indicated time. The sample was taken out and notched, and the notched Izod impact strength of the autoclaved sample was measured. Data was recorded as retention of the original Notched Izod impact strength. In all cases, 5 bars were measured for each sample.

Table 4 shows that when the polysiloxane-polycarbonate content was increased, the notch Izod impact (ft-lb / inch) retention rate was improved after autoclave treatment at 121 ° C. and 1.5 atm.

Blends of BPA-PPC (polyphthalyl carbonate) copolymers, polycarbonates, and polysiloxane-polycarbonate copolymers were autoclaved for an extended time at 121 ° C. to impart increased hydrolytic stability. As shown in Table 4 and FIG. 4, the heat deflection temperature was reduced due to the presence of polysiloxane, but the inclusion of polysiloxane-polycarbonate copolymers increased the initial ductility and retention of Izod impact properties compared to PPC-PC blends. .

Example 4

In this example, 100% to 0% by weight of polysiloxane containing 6% by weight of polydimethylsiloxane containing 0 to 100% by weight of a specific high temperature polycarbonate comprising BHPM and BPA units in a weight ratio of 52 to 48, respectively. Used in blends with polycarbonate copolymers. The autoclave conditions used in this example are a temperature of 135 ° C. and a pressure of 2 bar. The "cycle number" in the table is the number of equivalent cycles that autoclave for 20 minutes at 135 ° C. under a pressure of 2 bars. Notched Izod impact strength of the sample is presented in the table below.

This example demonstrates that the Notch Izod impact strength of a product made from a mixture of polysiloxane polycarbonate copolymers and BHPM-polycarbonate copolymers, while products made from 100% polysiloxane polycarbonate copolymers cannot tolerate even three autoclave cycles. Showed that it was maintained over six autoclave cycles. As can be seen in Table 5 and FIG. 5, the impact strength performance of the products made with 80% polysiloxane polycarbonate copolymer and 20% BHPM-polycarbonate copolymer was the best.

As shown in Table 5 and Figure 5, samples with lower amounts of polysiloxane polycarbonate copolymers and higher amounts of BHPM-polycarbonate copolymers showed reduced impact strength after only three autoclave cycles. Moreover, as can be seen in Table 5 and Figure 5, when 100% BHPM-polycarbonate copolymer was used, impact strength was lost after only three autoclave cycles.

Example 5

In this example, and as can be seen in Table 6 and FIG. 6, the yellow index (“delta YI” of the copolymers of the polysiloxane polycarbonate copolymers and BHPM-polycarbonate copolymers described above (detailed need for this) The change in ") was acceptable after 12 autoclave cycles. In this example, the acceptable level of delta YI rate was less than 20%. The autoclave cycle used in this example is a treatment in the autoclave for 20 minutes at a temperature of 135 ° C. and a pressure of 2 bar.

As can be seen in Table 6 and FIG. 6, a sample of 100% polysiloxane polycarbonate copolymer was shown to have an unacceptable level of turbidity after six autoclave cycles. Furthermore, as can be seen in Table 6 and FIG. 6, when 100% of the BHPM-polycarbonate copolymer was used, good turbidity could be maintained at acceptable levels after 12 autoclave cycles.

Products comprising polysiloxane-polycarbonate copolymers could be steam sterilized for extended periods of time without loss of hydrolysis and / or dimensional stability. In addition, despite prolonged steam sterilization, the product hardly damages or damages all of the beneficial physical properties of the polycarbonate, such as ductility, impact strength, impact retention, moisture resistance, transparency, and / or softening temperature. Did not do it.

Unless the context clearly indicates otherwise, the singular indefinite articles "a", "an" and "the" include plural referents. All ranges of end values describing the same feature are combinable and include cited end values. All references are incorporated herein by reference.

While the present invention has been described with respect to specific embodiments, those skilled in the art will understand that various changes may be made and equivalents thereof may be substituted without departing from the scope of the present disclosure. In addition, various modifications may be made to adapt a particular situation or material to the teachings of the present disclosure without departing from the essential scope thereof. Therefore, it is to be understood that the invention is not limited to the specific embodiments disclosed in the best mode contemplated for carrying out the invention, but includes all embodiments falling within the scope of the appended claims.

Claims (26)

Treating the article with a vapor comprising a composition comprising a composition containing a polysiloxane-polycarbonate copolymer in an amount effective to provide thermal and hydrolytic stability to the article for at least 15 cycles, each cycle comprising a temperature of 100 ° C and A process comprising contacting the steam for 20 minutes at atmospheric pressure. The method of claim 1, The article comprises a composition containing an amount of polysiloxane-polycarbonate copolymer effective to provide thermal and hydrolytic stability to the article for at least 15 cycles, each cycle at a temperature of 121 ° C. and a pressure of 1.5 atmospheres. 20 minutes of contact with steam. The method of claim 1, The article comprises a composition containing an amount of polysiloxane-polycarbonate copolymer effective to provide thermal and hydrolytic stability to the article for at least 15 cycles, each cycle at a temperature of 135 ° C. and a pressure of 2.0 atm. 20 minutes of contact with steam. The method of claim 1, Wherein the polysiloxane-polycarbonate copolymer comprises 0.1 to 40 weight percent polydimethylsiloxane or an equivalent molar amount of another polydiorganosiloxane. The method of claim 1, Wherein said composition comprises from 4 to 100 weight percent polysiloxane-polycarbonate copolymer based on the total amount of resin composition. The method of claim 1, The composition further comprises 1 to 96% by weight of a high temperature thermoplastic polymer, wherein the high temperature thermoplastic polymer has a heat deflection temperature of greater than 135 ° C. at 1.8 Mpa as measured according to ASTM D648. The method of claim 6, Wherein said high temperature thermoplastic polymer is a high temperature polycarbonate. The method of claim 7, wherein Hyperthermic polycarbonate is bis (4-hydroxyphenyl) -p-mentane, 2-phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine, 4,4 '-(hexahydro-4,7- Meta-indan-5-ylidene) diphenol, bisphenol (1,3,5-trimethylcyclohexane), 4- [1- [3- (4-hydroxyphenyl) -4-methylcyclohexyl]- 1-methylethyl] phenol, 4,4 '-[1-methyl-4- (1-methylethyl) -1,3-cyclohexanediyl] bisphenol, phenolphthalein, 2-methyl-3,3-bis (4 -Hydroxyphenyl) phthalimide, 2-butyl-3,3-bis (4-hydroxyphenyl) phthalimide, 2-octyl-3,3-bis (p-hydroxyphenyl) phthalimide, or A method comprising units derived from combinations comprising at least one of these compounds. The method of claim 5, Wherein the high temperature polycarbonate is a copolyester polycarbonate. The method of claim 9, High Temperature Copolyester Polycarbonates Bis (4-hydroxyphenyl) -p-mentane, 2-phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine, 4,4 '-(hexahydro-4 , 7-methano-indane-5-ylidene) diphenol, bisphenol (1,3,5-trimethylcyclohexane), 4- [1- [3- (4-hydroxyphenyl) -4-methylcyclo Hexyl] -1-methylethyl] phenol, 4,4 '-[1-methyl-4- (1-methylethyl) -1,3-cyclohexanediyl] bisphenol, phenolphthalein, 2-methyl-3,3- Bis (p-hydroxyphenyl) phthalimide, 2-butyl-3,3-bis (p-hydroxyphenyl) phthalimide, 2-octyl-3,3-bis (p-hydroxyphenyl) phthalimide Or a unit derived from an aromatic dicarboxylic acid and a unit derived from a combination comprising at least one of these compounds. The method of claim 1, Method of treating the product with steam sufficient to achieve sterilization. The method of claim 11, How the product is treated with steam in an autoclave. The method of claim 1, Wherein the content of said polysiloxane-polycarbonate copolymer is an amount sufficient to provide 50 to 99% ductility to the product after 15 cycles. The method of claim 1, Wherein the content of the polysiloxane-polycarbonate copolymer is an amount sufficient to provide a vicat softening temperature of 121 ° C. to 400 ° C. to the product after 15 cycles. The method of claim 1, Wherein the content of the polysiloxane-polycarbonate copolymer is an amount sufficient to provide a notched Izod impact strength of 3 to 18 ft-lb / inch as measured by ASTM D256 after 15 autoclave cycles. The method of claim 1, Wherein the content of the polysiloxane-polycarbonate copolymer is sufficient to provide 15-100% Notched Izod impact retention after 15 autoclave cycles, wherein the Notched Izod impact strength is measured by ASTM D256. The method of claim 1, Wherein the content of said polysiloxane-polycarbonate copolymer is an amount sufficient to provide a yellow index change of less than 20% in the product after 15 autoclave cycles. The method of claim 1, Wherein the content of the polysiloxane-polycarbonate copolymer is an amount effective to provide 0% to 20% haze and 60% to 100% transmittance to the product after 15 autoclave cycles. The method of claim 1, Wherein the content of the polysiloxane-polycarbonate copolymer is an amount effective to provide a change of any single dimension of less than 10% to the product after 15 autoclave cycles. The method of claim 1, The product is a medical device. The method of claim 20, Medical devices include syringes, blood filter housings, blood bags, solution bags, venous connectors, dialysis machines, catheters, medical storage trays, medical devices, medical tubes, heart pacemakers and defibrillators, cannulas, implantable prostheses Cardiac aids, heart valves, vascular grafts, extra-corporeal devices, artificial organs, pacemaker leads, defibrillator leads, blood pumps, balloon pumps, AV shunts, biosensors, cell capsule membranes , Wound dressings, artificial joints, orthopedic implants, and syringes. The method of claim 1, The product is a non-medical device. The method of claim 22, Non-medical devices consist of food trays, animal cages, cable sheathings, varnish and coating equipment, pumps and structural parts of vehicles, ore mining screens and conveyor belts, laminating compounders, aviation instruments and chocolate forming molds. Selected from the group consisting of: Vaporizing a product comprising a composition comprising a composition comprising a polysiloxane-polycarbonate copolymer in an amount sufficient to provide 15-100% Notch Izod impact retention after 15 autoclave cycles, Strength is measured by ASTM D256, each cycle comprising contact with steam for 20 minutes at a temperature of 100 ° C. and atmospheric pressure. Forming a product comprising a composition comprising a composition containing an amount of polysiloxane-polycarbonate copolymer effective to provide thermal and hydrolytic stability to the product for at least 15 autoclave cycles, each cycle comprising a temperature of 100 ° C. and A method of making a product comprising contacting steam for 20 minutes at atmospheric pressure. An article formed by the method of claim 25.

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