DE2709389A1 - GLASS FIBER REINFORCED HALOGENBISPHENOLAETHYLENE POLYCARBONATE - Google Patents

Description

Glass fiber reinforced halogen-bisphenol-ethylene-Polycurhonnte.

The invention relates to thermoplastic compositions, the halobisphenoid thy len polycarbonate include which Fiber optic connector 1 included. This"; Compositions both show improved Izod impact properties as well as excellent flame retardant properties.

According to the prior art, only limited measurements were made with regard to the properties of chlorobispheno lü t hy len polycarbonates performed, such as the infrared spectroscopy data by Z.Wielgosz, Z.Boranowska and K.Janicka, the

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are reported in "Plaste und KautSdHiC ¹¹ IΓ, (12) '.Oi (li'72). Among the chlorobisphenolethylene polycarbonates which have been described by Z.Wielgosz et al., homopolymers of (1) 1,1- Dichloro-2,2-bis (1-hydroxyphenyl) ethylene, copolymers of 1, l-dichloro-2, 2-bis (l-hydroxyphenyl) iithylene and (2) bis (l-hydroxyphenyl) propane-2 , 2 and mixtures of homopolymers of (1) and (2).

Measurements enl; t Iten attempts at chlorobisphenolnthylene-T> to stabilize olycarbonate, as described by Z.Gobiczewski, Z.Wielgosz and K.Janicka in "Plastics and Rubber" IG (2) {; '. "· (IiGlO is reported to have the ineffectiveness commercially available hindered phenols, e.g. Parmanox, i.e. 2, e-di-t-butyl-1-methylphenol, Topanol C \, i.e. 2,2,1-tris ('^ -methy 1-1 -hydroxy-5-1-butylpheny 1) butaη, and Jonox : Π0, i.e. 1, '», 5-tris (1,5, -di-t-butyl-t-hydroxybenzyl) benzo I, as stabilizers for chlorobispheno 1 fi thy len-polycarbonate at elevated temperatures, e.g. from 1> 0 to 2ftO C. Further measurements concern the determination of the resistance to hydrolysis of chlorobispheno irithylene polycarbonates, as reported by Z.Boranowska and Z.Wielgosz, "Polimery" 15 (1), 12-11 (1ί · 7Ο).

Other well-known publications related to the manufacture of Ch lorbisphenolfithy len polycarbonates concern and the

State of the art show are the following:

The synthesis of ChlorbisphenolnIhylen-Polycarbonaten by the procedures described by S.Pore.jko et al. are described Polish patent I8.HU3, issued December 12th lüfvt,

called Method of Synthesizing self-extinguishing thermoplastics,

Z Dobkowski, B. Krajewski and Z.Wielgosz, "Polimery" 15

(8) Ί'Ϊ8 (1ί · 70), and Z.Wielgosz et al., "Polimery" 17, 7 (5

The applicant has no further publications regarding of the prior art known relating to

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the properties of halobisphenol ethylene polycarbonates or the processes for their preparation are of importance would be.

Unexpectedly, it has now been found that certain halogen bisphenol thirdylene polycarbonate compositions which Glass reinforcement agents contain, much improved Have impact properties. The improvement of the mechanical properties of the halobisphenolethylene polycarbonate compositions by means of glass fiber reinforcement is an essential contribution to the provision of Γ flame retardant or flame retardant mouth thermoplastic Materials as the glass fiber reinforced halobisphenolethylene polycarbonate is believed to be the best Impact properties and, the highest resistance to Surface flammability of any glass fiber reinforced polycarbonate compositions that Until today in accordance with the American standard methods ASTM El 62-67 (re-approved) 1973 Test method with the designation "Standard Method of Test" Tor Survace Flammability of Materials Using a Radiant Heat Energy Source " Surface flammability of materials is tested using a radiant heat exchanger (I le) have been.

The invention provides a thermoplastic composition, The halobisphenolrithylene polycarbonates and fiberglass reinforcing agents that have both improved notched Izod impact strength and toughness (notched Izod impact strength) as well as excellent flame resistance having.

The term "halobisphenolethylene polycarbonate" When used here and in the claims, includes any polycarbonate composition

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a, which in the Polyearboriathaupl ket 1 e "Halogenbis (phenyl) ethylene carbonate "units containing the following formula:

(I)

where, independently of one another, each R is hydrogen, chlorine, bromine or a C ₁ , _ir , - monovalent hydrocarbon or oxyhydrocarbon, each Y is hydrogen, chlorine or bromine with the proviso that at least one Y is chlorine or bromine, and m is an integer of at least 2 is. The monovalent hydrocarbon groups preferred in the present case are C. _} - alkyl or phenyl. Even more preferred polycarbonates contain units of the formula I in which each R is hydrogen and each Y is chlorine. Polycarbonates which contain only recurring components of the formula I are halogen bisphenols: i-thylenehomopolycarbonates, as defined here in the appended claims. Included within the scope of this invention are halobisphenol-ethylene-polycarbonates, which contain both Ha lögeηbis (phenyl ) ^H thy lenearhona t units of the formula I and "\ rencarbonat" units of the formula:

(II) .-

• Ar

-Ar '

0 - G

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contain, where R_ is an alkylene, alkylidene, cycloalkylene, Cycloalkylidene or arylene chain, or a mixture thereof, a chain selected from the group consisting of «'Ether, carbonyl, amine, a sulfur- or phosphorous-containing compound Chain; Ar and Ar * are arene radicals, Y is a substituent selected from the group consisting of organic, inorganic and organometallic radicals, X is a monovalent Carbon hydrogen group is selected from the class is, consisting of alkyl, \ ryl and cycloalkyl and mixtures thereof, a halogen, an ether group of Formula -OE, where E is a monovalent hydrocarbon radical is similar to X, a monovalent hydrocarbon group of the type represented by R-, ti represents an integer of at least 1, c represents an integer that is at least 0 or greater, is, a, b and c integers including Represent O, where a or c, but not both, can be O, and where η is an integer of at least 2 is.

V "!» Preferred copolycarbonates included in the scope of the invention are polycarbonates that contain both the halobis- (pheuyl ) ethylene carbonate units of the formula I a Is also Contain arene carbonate units of the following formula:

(III)

—Ι η

wherein, independently of one another .ledcs It is hydrogen, chlorine, bromine or a Cj_ _{} ()} - monovalent hydrocarbon group, independently of one another, R in d is hydrogen or

a h

a Cj_. _} q - are monovalent Koh lunwassorsfoffgruppe and

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η an integer of at least Ί is ». Tm νοι · lying! '. Ι lie hu νον' /. Ng * e einwert i ^ e KoIi ionwassers tof [groups are C ₁ Λ IkyI or phenyl. More preferred copolycarbonates contain bisphenyl carbonate units of the formula III, wherein each R is hydrogen and R and R are methyl.

g η

Ha loijenbispheno I ^; <t hy Icn polycarbonates can be produced by processes which are known to the person skilled in the art and as described, for example, by S.Porejko et al., Polish patent IF.Cf 5, issued on 1 * 2. December 1 '.- <Ή, with the name method for synthesizing self-.IHS-erasing thermoplastic ut of fen uikI ZV / iolgosz et al., Poliiicvy, 17, 7.> (1-72) are described. In general, the methods of S.Porejko et al. and Z.Wielgosz et al. Reactions of a chlorobispheno L- ^; t hy len, ie 1, 1-dich I or- "2 , '2-: jis (t-hydroxypheny I) · thy I en and bisphenol- ^, ie bis (1-liydroxypheny M-prop.in-li, 1 with a mixture ^{Carbonatvori;} mi fer, eg "hosgen, and a S'ureakzeptor, eg caustic soda, and a catalyst, such as triethylamine, wherein the reactions come under ago 1 Phosgeniei'unjisreakt ion are ions durchgef'ihrt conditions ie under Reaction conditions which are usually observed in the phosgenation of bisphenol \, as described in the Encyclopedia of Polymer Science and Technology IO under the title "Polycarbonate", pages 710-7 (51, Interseienee Publishers (Ιί) «1ί>) .

The following are examples of some halobisphenolrithylene compounds indicated in the manufacture of homo- and copolycarbonates in accordance with the phosgenation reaction conditions described by S.Porejko et al. and Z.Wielgosz et al. as well as those who are in the Encyclopedia of Polymer Science can be used:

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1,1-di bromo-2,2-bis (Ί -hydroxy phenyl) ithylene;

1, 1-dich 1or-2,2-bis (5-methyl-4-hydroxyphenyl) η thy le η;

Bromo-2,2-bis 1,1-di (n-di- η- hu ty 1-1 -hydroxyphenyl i) - a Thylen;

1, l-Diehlor-2, 2-bis (2-chloro-5-pthy l-4-) iydroxyphenyI) - :: t hylen;

1, 1-di-bromo-2, 2-bis (2, 5-di-bromo-1-hydroxyphenyl) ri thy len;

'-Bromo-2,2-bis (4-hydroxyphenyl) siamine;

1-chloro-2,2-bis (M, 5-diisopropyl-! -Hydroxyphenyl) ri thy le η; 1-ilroin-2,2-bis (2,6-di -1-but y 1-1 -hydroxy phenyl) fit hy len; 1-chloro-2,2-bis (2, β-dichloro-1-hydroxyphenyl) ethylene; 1-bromo-2,2-bis (2,3-dibromo-1-hydroxyphenyl) ethylene; 1, l-dichloro-2, 2-bis (1, i> -dich 1 or-1-hydroxyphenyl);) thy len; 1, 1-dichloro-2, 2-bis (3, 5-dibrom-4-hydroxyphenyl) fit hy len; 1,1-dibromo-2,2-bis (5-chloro-1-hydroxypheny 1) n thy len; 1-Ch 1 or-2,2-bis (\, 'l-dibromo-1-hydroxypheny 1) H thy len; Bi 2-s Hylen 1-bromo-2, (2-ch1or-4-hydroxypheny1) ät;

1,1-dichloro-2,2-bis (2,1,5-trichloro-1-hydroxyphenyl) ethylene;

1,1-di-bromo-2,2-bis ( Ί, 3,5, G-1e tvabrom-I-hydroxyphenyI) -fi thy len;

1-chloro-2, 2-bis (3-pheny l-Ί -liy droxypheny 1) 3 thy len; 1-bromo-2, 2-bis (1, 5-di pheny 1-1-hydroxypheny l) fithylenes;

1,1-1) 1 chloro-2, 2-bis (2, e-dipheny l-1-hydroxyphenyl) - * thy len;

1, l-dibromo-2. 2-bis (.1-bromo-f> -pheny 1-1 -hydroxyphenyl) -ethylene;

1-chloro-2,2-bis (3-methoxy-1-liy droxypheny 1) n thy len; 1-bromo-2,2-bis (.1, 5-dimethoxy-! -Hydroxy pheny I) a thy len; 1,1-dichloro-2, 2-> is (2- 'ithoxy-1-hydroxyphenyl) ethylene;

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1, lI) ibromo-2, 2-bis (2, ß-di * thoxy-4-hydroxyphenyl) nt hy len; 1-chloro-2,2-bis (5-phenyl-ether-4-hydroxyphenyl) ethylene; l-bromo-2, 2-bis ('i, 5-dipheny InI her- Λ -hydroxy phenyl) η thy len;

1, 1-dichloro-2, 2-bis (3-chloro-5-phenyla the r-4-hydroxyphenyl ) ethylene;

1,1-di bromo-2,2-bis (i-2-bromo-5-di phenyl ether-4-hydroxyphenyl) ethylene;

etc., among many others.

The following now follow examples of some arenedihydroxy compounds which are used in the production of halobisphenolethylene polycarbonates or mixtures of halobisphenolethylene polycarbonates with other polycarbonates which contain phenyl carbonate units of the forms II and III, in accordance with the phosgenation reaction conditions described by Z. Wielgosz et al. and S. ^D orejko et al. can be used with those described in the aforementioned Encyclopedia ot Polymer Science:

Resorcinol;

4,4'-dihydroxy diphenyl; 1, Π-dihydroxynaphthalene; 2, fi-dihydroxy-naphthalene; 4,4'-dihydroxydiphenylmethane; 4,4'-dihydroxy-1,1-η than; 4,4'-dihydroxy-diphenyl-1,1-butan; 4,4'-dihydroxy-diphenyl-1,1-isobutane; 4,4'-dihydroxy-dipheny1-1,1-cyclopentane; 4,4'-dihydroxy-dipheny1-1,1-cyclohexane; 4,1'-dihydroxy-diphenyl-phenylmethane;

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1,1'-dihydroxydiphenyl-2-chlorophenylmethane; 1,1'-dihydroxy-dipheny1-2,1-dichlorophenylmethane; 1,4 '-Uihydroxy-diphenyl-p-isopropylphenyl line than; 1,1 * -dihydroxy-diphenylnaphthylmethane; 1,1'-dihydroxydiphenyl-2,2-propane; • 1,4 '-dihydroxy -' {- methyl-diphenyl-2,2-propane; 1,4 * -dihydroxy-3-cyclohexy1-dipheny1-2,2-propane; 1,1'-dihydroxy-3-methoxy-dipheny 1-2,2-propane; 4,4'-dihydroxy-3-isopropyl-dipheny1-2,2-propane; 1,4 * -dihydroxy-3,3 * -dimethy1-dipheny 1-2,2-propane; 1,4'-dihydroxy-3,3 * -dichloro-dipheny1-2,2-propane; 4,4'-dihydroxydiphenyl-2,2-butane; 4,4'-dihydroxydiphenyl-2,2-pentane; 4,4'-dihydroxy-dipheny1-2,2 (4-methylpentane); 1,1'-dihydroxy-dipheny1-2,2-n-hexaη; 4,4'-dihydroxy-dipheny1-2,2-nonane; 4,4'-dihydroxy-diphenyl-1,4-heptane; 1,4'-dihydroxydiphenylphenylmethyl methane; 4,4 * -dihydroxy-dipheny1-4-chlorophenylmethyl methane; 1,1 * -dihydroxy-dipheny1-2,5-dichlorophenylmethyl methane; 4,4 * -dihydroxy-diphenyl-3,4-dichlorophenylmethyl methane; 4,4'-dihydroxy-diphenyl-4-fluorophenylmethyl methane; 4,4'-dihydroxy-diphenyl-2-naphthylmethyl methane; 1,1'-dihydroxy-tatraphenylmethane; 1,4'-dihydroxy-diphenylphenylcyanomethane; 4,4 * -dihydroxy-diphenyl-1,2- »than; 4,4'-dihydroxy-dijuenyl-l, 10-n-decane;

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4, 1 '-dihydroxy-diphenyl-l, ι-ϊ (1, β-dioxo-n-hexane); 1,4'-dihydroxy-diphenyl-l, 10 (1,10-dioxo-n-decane); Bis-p-hydroxy-phenyl ither ^i-'1, 1 'diphenyl;

oC _f oC, o ⁴ - ¹ , oL ' -Tetramethyl- oC, oC' - (di-p-hydroxyphenyl) p-xylylene;

OC , oC.oC ', oC'-tetramethyl-Oi, oC'-Cdi-p-hydroxypheny1) -mxylylene;

2,2'-IJihydroxy-.i,: J ', 5, 5'-tetramethy ldiphenylmet han;

1,4'-dihydroxy-Ί, 3'-dimethyl-diphenymethane; 1,4'-dihydroxy-2,2'-dimethyl-diphenylmethane;

4,4'-dihydroxy-. '}, 3', 5, 5 * -te trame thy l-dipheny lme t han;

1,4 '-dihydroxy-'}, 3'-dichloro-diphenyl methane; 4,1'-dihydroxy-1,3'-dimethoxy-diphenylmethane;

4,4'-dihydroxy-2,2 ', 5,5'-tetramethyl-diphenyl methane;

1,4'-dihydroxy-2,2 ', 3,3', 5,5 ', ·> , 6'-octamethyl-diphenylmethane;

1,4'-dihydroxy-2,2'-dimethy1-5,5'-diisopropyl-diphenylmethane;

4,4'-dihydroxy-2,2'-dimethyl-5,5-dipropyl-dipheny1-methane;

4,4'-dihydroxy-2,2'-dimethyl-5,5'-di-tert-butyldiphenylmethane;

4,4'-dihydroxydiphenyl-5,5-nonane; 4,4'-dihydroxy-diphenyl-e.ß-undecane; 4,4'-dihydroxy-diphenyi-3,3-butanone-2;

4,4'-dihydroxy-3,3'-dimethyl-dipheny1-3,3-butanone-2;

4,4'-dihydroxy-diphenyl-4,4-hexanone-3;

4,4'-dihydroxydiphenylmethyl-4-methoxyphenylmethan;

4, 4 '-dihydroxy-diphenyl ether; 4,4 * -dihydroxy-diphenyl sulfide;

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I, j '-dihydroxy - !, 3' -dime thy ldipheny lsul lid; 1,4'-dihydroxydiphenyl sulfoxide; 1, 1 '-dihydroxy-diphenyl sulfone; 1,1 '-dihydroxy-3, 3' -dich lordiplieny isulf one;

1,4'-dihydroxy-J, 'J *, 5,5'-1etramethyl-diphenyl methane;

4, 1'-dihydroxy-3,3 ', 5, S'-tetrachloro-diphenyl-l, 1-cyclohexane;

1,1 '-dihydroxy- !, V, Π, f>' - tetrachlorodiphenyl-2,2-propane;

1, 1'-I) ihydroxy-3,3 ', 5, 5'-tet ramel hy 1-2, 2', G, il'-tet rabromo-dipheny1-2,2-propane; and

1,4 '-diliydroxy-3, 3', 5, 5'-tet rabromo-diphenyl-2, 2-propane, etc., among many others.

The Halbisphenoliiii thylen-Polycarbonate preferred here

have a basic molar viscosity ^; itszahl (English: "intrinsic viscosity") of at least 0.3 and more preferable about O, ß deciliter per gram (dl'g) measured in either methylene chloride or chloroform, or similar Lösungsinittelsyst emen '25 at ⁰ C. The upper intrinsic Viscosity number is not critical, but it will usually be about 1.f>dl'g. Particularly useful halobisphenol ethylene polycarbonates usually have an intrinsic viscosity within the range of about 0.38 to about 0.7 dl g. Preferably, the Halogenbispl.enolnt hy len-Polycarbona te contain a sufficient number of repeating units of the formulas I or I and II or III, which were given above, in order to obtain a number-average average molecular weight of homo- or copolyrarbonates - including mixtures thereof with other polycarbonates - of at least about 5,000 and more preferably to provide a number average molecular weight of about 10,000 to about 100,000. Poly-

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can ften carbonate with such Molekulargewiehtseigenscha in the range of about 212.22 C ⁰ (4 ⁰ 1O F) and Ί Π, 3.'J ⁰ C (GSO ⁰ F) or even higher processed, and in the present case they are bevorzuijt clipboard
and 313.33 ⁰ C (6f> O ° F) processed.

Fall they are preferred between about 287.78 C (Γ35Ο F)

Mixtures of Ha logenbisphenolri ethylene polycarbonates and any other polycarbonate, the arene carbonate units containing formulas II or III as described above are also within the scope of the invention and can be prepared by any means known to those skilled in the art. Preferred blends are made by blends of halobisphenolrithylene polycarbonates and any other polycarbonate at a temperature above its softening point or their softening points are heated. Preferably the mixing or blending - if there is in the absence of one Solvent is carried out - at the elevated temperature specified above, i.e. above its softening point or the softening points, carried out while the mixture is subjected to mechanical working through will. Accordingly, mixtures can be made with devices such as extruders, including single and multiple screw presses, Banbury-JnnenmJ.schern (internal Banbury mixers), mixing rollers or other mechanical Devices are mixed by which the mixture is subjected to shear forces or shear stresses at elevated temperatures is subjected.

The term "fiberglass" when used here and in the appended claims is used, inter alia Cl) continuous fibers by the rapid weakening formed by streams of molten glass, and sir'ings formed when such glass frayed are gathered or bundled together as they are formed, and (2) discontinuous fibers passing through High pressure flow or air are formed, the or the

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at an angle downward on multiple forms of molten Glass is directed, which from the bottom of Glasschme Exit the tarpaulin.

In the present case preferred halogen bisphenolite hy len polycarbonate compositions of this invention contain reinforcing amounts of glass fibers such as milling dust, short glass lasers and glass strands, especially staple glass fibers (English: staple glass liber) and preferably Glass fibers with average fiber rings of approx 100 to βΟΟ pm and more preferably from 200 to 400 pm with the proviso that the glass fibers have a fiber finish that matches the polycarbonate resins used in this invention is compatible. When the electrical properties of the halobisphenol ethylene polycarbonate are important, there is a preferred glass reinforcement filler which is also defined here as fibrous glass thread, made of lime-aluminum-borosilicate glass, which is relatively soda free (commonly known as "E" glass), and these glass threads can be made by any standard method such as steam or Air bubbles, flame bubbles and mechanical pulling.

Any amount of an I Ia logenbinpheno 1 · 1 hy I enhoiro- or copolycarbonnts or mixtures of Ha 1 ogenbisphenol-tliy lcn-Polycarbonat with any other Tylyc.irljonat the 'Mrencarbona t "-units of the formulas II or III contains , can or can be used in combination with an amplifying amount of glass lasers. Preferred halo ^ en bisphenoIt ethylene polycarbonate compositions include polycarbonate compositions which are based on (! ewicli ι svevli ί 11 nisbas is - either in] { o; no- or copolymer form oJor in the form of fier mixtures - Ha logonbispheny 1 '^; t hy! ο near bo na I -unit (.mi der ^r or; \ u: l I zu \ rencaruonr »t -rinhei th of the form Ln II ocii; i * III i Diierha lij of the triangle from e I wa ^r : 'i to about

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BATH ORIGINAL

- / If

Γ ":") inn! sf ^:: vkor zu i; ovorzu ₍ {cii from w.) ^r ! O: ^c 'O bin et'vi' Ό:? ϋ o: it iia L ί <? n. .Our o.jen an ;; o ;; i? ^: .) eno Ijo vovzu ^ to umi insbesondciBZU; jevorzu, ', eT3eneroic! i g.iV glas "aservcr.s Γ irkt e Polycarbona I -Zusa.m.iense I z.ingen iiioser invention an, cue opt inn Lo mechanical '.'i' jcn.scln! "ten, inybesoiiilcve Ιζοι! - Korbscli la.'iz ¹ · liiifkei t oiJer -! 'es i igkei f", iS.iuc rs ho ff i ϋι! υ. \, tensile strength and F3ioge read t itfke possess it.

Any number of glass lasers on a weight basis can be used, for example 1 to 10, 10 to 10, 0 to 100 parts or even larger quantities of glass fibers per 100 parts of Halofienbisphenolnthylen-Polycarbonat. In the present case preferred compositions contain from about ^r 1 to about 50, and more preferably from about 7.5 to about 10 parts of glass lasers per 100 parts of halogen bisphe no-ethylene polycarbonate.

The glass fiber materials can be of any one of them Wise can be added to the polycarbonates, for example, the fibers can be added to polycarbonate solutions or melts, or they can be mixed with polycarbonate powder or mixtures thereof and are homogenized by subsequent melt extrusion in a way that is analogous to the process, which are also described elsewhere in relation to the preparation of mixtures of halobisphenolrithylene-polycarbonate 1 enes are. It is possible in the same course of the manufacturing process for the polycarbonate compositions other reinforcing and / or non-reinforcing fillers, flame retardant additives or others Additives such as pigments, mold release agents, stabilizers, Antioxidants, anti-drip agents, surface active agents To add funds etc.

The following examples illustrate the best mode to carry out the invention put into practice - but without restricting the invention. If the examples do not

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BATH ORIGINAL

As noted, the following general procedures are used in making and testing the resin blends Applied to this invention, departures from the general procedure are in the specific examples specified.

General procedure

A range of blends of Chlorbisphenolri thylen-Polycarbonaten and bisphenol-A polycarbonates were made accordingly made from non-commercially available material and from commercially available materials. The chlorobisphenol polycarbonate (in the examples as Bisphenol-E polycarbonate for short) was produced through the reaction of an aqueous alkaline solution of 1,1-dichloro-2,2-bis (4-hydroxypheny 1) fi1 hy len with Phosgene, with the reaction in the presence of triethylamine and methylene chloride in a temperature range of about 20 ° to about 40 ° C was carried out to chlorobisphenolethylene polycarbonates high molecular weight, which is an intrinsic viscosity, measured in methylene chloride at a temperature of 25.3 ° C, in the range of about 0.41 to 0.51. The 1,1-dichloro-2,2-bis (-1-hydroxyphenyl) n used is ethylene known and can be produced by the processes known for this.

The bisphenol-Λ-ΐ'οΙ carbonate, a commercial product from General Electric Company, was prepared by the reaction of an aqueous alkaline solution of Bis (1-hydroxyphenyl) propane-2,2 with phosgene, whereby the Reaction in the presence of triethylamine and methylene chloride in accordance with standard commercial reaction conditions was carried out to produce a bisphenol

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A high molecular weight polycarbonate to provide the an intrinsic viscosity within the range from about 0.16 to about 0.52 dl / g, measured in dioxane 25 ° C.

The resulting bisphenol E polycarbonate and the bisphenol A polycarbonate were mixed in powder form into a variety of compositions, extruded and cut into pellets. The pelletized materials were molded by injection molding or compression molding and tested accordingly:

Notched Izod Impact Strength (1'B "samples, ft.-lbs.per inch of notch) ASTM D2f> 6 method A;

Oxygen index ASTM ϋ2Β6Ί;

Yield Strength (kg'cm ² ; psi) ASTM I) 1822; L sample, 0.127 cm'min (0.05 "'min;

Bending limit (kg'cm "; psi) \ STM D 790.

Examples 1-7

A series of bisphenol E polycarbonate and bisphenol A polycarbonate blends containing various ratios of bisphenol E 'bisphenol components were prepared, the blends containing 10 parts by weight of glass fibers per 100 parts of polycarbonate. For control purposes, individual bisphenol E polycarbonate and bisphenol A polycarbonate compositions containing 10 parts by weight of glass fibers per 100 parts of the polycarbonates were also tested. The control samples and mixtures were tested according to the tests described in the general procedure. The results of the tests are compiled in Table I and also explained by FIGS. 1, 2, 'i and Ί.

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Table I.

Composition and mechanical properties of glass fiber reinforced mixtures of bisphenol-E and bisphenol- ^ polycarbonates.

Example no.

I. Polycarbonate Composition

(a) Bisphenol-E, phr (l)

(b) bisphenol-Λ, phr

(c) glass fiber, phr

II. Physical properties

(a) Notched Izod impact strength (2)

(b) Oxygen Index

(c) Yield strength kg-cm

(tensile yield stress;)

(d) flexural strength kg cm (flexural strength; (psi)

1 2 3 4th 5 r, 7th O 10 25th 50 75 90 100 100 90 75 50 25th 10 0 10 10 10 10 10 10 10

2.0 3.18 8.0 5.73 2.7 (3) 3, C.

2.6

33.5 32.3 53.0 d4, 5 54.2 Γ> 3, f. 54, Γ 363 650 64 5 655 660 715 722 C43O Γ 2 50 0185 C33 5 9466 10170 10270 13 5 1118 1100 1132 1137 1177 1218 614 6 15P3O 15660 16109 16190 16770 17320

(1) phr = parts per hundred of the polycarbonate resin

(2) Average of 5 or more test samples

(3) Experimental data error

O CO CO 00 CO

2 *.

Referring now to Figures 1, 2, 3 and 4, the data set forth in Table I is graphically presented. It is shown that (11 the notched Izod impact or strength properties of bisphenol-E 'bisphenol- ^ polycarbonate blends are unexpectedly improved compared to the impact properties found in glass fiber-reinforced polycarbonates, which only contain bisphenol-E- or contain bisphenol-A polycarbonates, (2) the values of the oxygen index of bisphenol-E ' bisphenol-Λ polycarbonate blends are exceptionally high, (3) the data for the yield strength and the flexural limit allow the conclusion that the observed values in FIG 1 is correct and that the impact resistance properties of BisphenolrE 'Bisphenol-A - polycarbonate blends are optimal depending on the proportions

. to arene carbonate / of halobisphenyl ^ ithylencarbonaty anrei len of halogen

bisphenolfit hy len-Pol year bonat -composition tongue η.

Although the above explanatory examples and the associated figures show the notched Izod impact strength, the oxygen index, the yield point and the bending limit of glass fiber reinforced polycarbonate blends of homopolymers of bisphenol-E - and ßisphenol-1-polycarboiiates describe, analogous results are obtained when copolymers of halobisphenol / ethylene polycarbonates containing comparable weight percentages of halobis (phenyl) ethylene carbonate units and have arene carbonate units.

The glass fiber reinforced halobisphenolthylene polycarbonates can be made into films, foils, sheet materials, fibers, laminates or other shaped objects conventional molding processes can be pressed or molded.

709841/0615

Those skilled in the art will recognize that other changes and modifications can be made in the particular embodiments of the invention described herein Modifications and embodiments also within the The scope of the invention is defined by the attached Claims is indicated.

709841/0615

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Claims (1)

Address a patent 1 . Halogen bisphenol olefin polycarbonate, thereby characterized in that the following leaves: (I) From (a) about 1 to 100 parts by weight of ilalogenbis- (pheny Dn thylene carbonate units of the formula (A): (A) If 0 - C wherein, independently of one another, each R is hydrogen,
Is chlorine, bromine or a C ₁ , ._ monovalent hydrocarbon or a hydrocarbon-based foxy group,
each Y is hydrogen, chlorine or bromine with the
Provided that at least one Y is chlorine or bromine,
and m is an integer from at least 2 to
(b) about '.)'. ' up to 0 parts by weight of carbonate units of the formula (B): 709841/0615 • ORIGINAL INSPECTED (B) (Y) ₁ -Ar R _f (γ) Ar ¹ .0 wherein U .. an alkylene, Λ Iky Ii de η-, Cycloal ky len-, Cycloa1kyliden- or arylene chain or a mixture thereof, a chain selected from the group consisting of ether, carbonyl, amine, a sulfur or phosphorus-containing chain; \ r and Ar 'are arene radicals, Y is a substituent selected from the group consisting of organic, inorganic and organometallic radicals, X is a monovalent hydrocarbon group selected from the class consisting of alkyl, aryl and cycloalkyl, and mixtures the same, a halogen, an ether group of the formula-OK, in which E is a monovalent hydrocarbon residue similar to X, a monovalent hydrocarbon group of the type represented by R .., d represents an integer of at least 1, c an integer Represents a number which is at least equal to 0 or greater, a, b and c: represent integers including 0, where a or c, but not both, can be “0”, and where η is an integer of at least 2, and (II) and an enhancing amount of one Glass fiber. Composition according to claim 1, characterized characterized that the arene carbona 1st-fin 1th have the following formula: 709841/0615 wherein R is as defined in claim 1 and Π and Are usually hydrogen or a C ₁ ~ hydrogen group. monovalent coals Composition according to claim 1, characterized characterized that the halogen bis- (PhenyDsthylencarbonat units have the following formula: (A) where R is hydrogen, chlorine, bromine, C- ₄ alkyl or phenyl , m is an integer of at least 2 and the arene carbonate units have the following formula: (B) 0 η 709841/0615 where R is as defined above and R and R. S h depending on each other hydrogen, C ₁ . Are alkyl or phenyl, η is an integer of at least 2. 4. Composition according to one of the preceding claims, characterized in that that the glass fibers are present in an amount of about 5 to 35% by weight. 5. Composition according to any one of the preceding claims ,characterized, that they are 20 to 80 parts by weight of the halobisphenylrithylene carbonate units and contains 80 to parts by weight of the arene carbonate units. 6. Composition according to claim 2, characterized in that R is hydrogen at least one Y is chlorine and the other Y is hydrogen and R and R ^ are methyl. 709841/0615