Method for accelerated degradation of thermoplastics

Abstract

A method of determining degradation of a thermoplastic when exposed to light and heat includes illuminating the thermoplastic with a desired wavelength of light at a desired irradiance while maintaining the thermoplastic at a desired temperature. The method is useful to measure the discoloration rate of transparent, translucent and opaque thermoplastics such as polycarbonates, the discoloration rate being determined by transmission or reflectance spectra of transmitted or reflected white light through or from the thermoplastic.

Claims

1. A method for determining degradation of a thermoplastic, the method comprising: illuminating a plurality of samples of thermoplastic, for a period of time, with light having a peak intensity centered at a wavelength from about 400 nm to about 500 nm and an irradiance from about 400 W/m.sup.2 to about 150,000 W/m.sup.2; measuring the temperatures of the plurality of samples of the thermoplastic, wherein the temperature of each of the at least two samples of the thermoplastic is measured by a separate thermocouple associated with that sample; calculating an average temperature of the thermoplastic using the temperatures of the plurality of samples of the thermoplastic; maintaining the average temperature of the thermoplastic at a temperature from about 23 C. to about 175 C. during the period of time; and repeating the illuminating and maintaining steps for a plurality of successive periods of time.

2. The method of claim 1, further comprising repeating the illuminating and maintaining steps for a plurality of successive time periods for a plurality of different thermoplastic formulations; and evaluating the degradation of the plurality of different thermoplastic formulations.

3. The method of claim 2, wherein evaluating the degradation comprises visually inspecting the thermoplastic, measuring a degree of discoloration of the thermoplastic, or both.

4. The method of claim 1, wherein the average temperature of the thermoplastic is maintained at a temperature from about 90 C. to about 130 C.

5. The method of claim 3, wherein measuring the degree of discoloration of the thermoplastic comprises: (1) illuminating the thermoplastic with white light, a portion of the white light being transmitted through the thermoplastic; and generating a transmission spectrum from the portion of the white light transmitted through the thermoplastic; or (2) illuminating the thermoplastic with white light, a portion of the white light being reflected from the thermoplastic; and generating a reflectance spectrum of the portion of the white light reflected from the thermoplastic; or (1) and (2).

6. The method of claim 3, further comprising comparing the degrees of discoloration measured after successive periods of time with one another.

7. A method for determining a discoloration rate of a plurality of polycarbonate samples, the method comprising: illuminating the plurality of polycarbonate samples with light having a peak intensity centered at a wavelength from about 400 nm to about 500 nm and an irradiance from about 400 W/m.sup.2 to about 150,000 W/m.sup.2 for a first period of time; measuring the temperatures of each of at least some of the polycarbonate samples by a separate thermocouple associated with that sample and calculating an average temperature of the thermoplastic using the temperatures of the at least some of the polycarbonate samples; and maintaining the average temperature at a temperature from about 23 C. to about 175 C. during the first period of time.

8. The method of claim 7, further comprising evaluating a degree of discoloration of the polycarbonate after the first period of time has elapsed.

9. The method of claim 7, further comprising: repeating said illuminating, maintaining and measuring steps for a plurality of polycarbonate samples of different formulations; and comparing the discoloration of said plurality of different polycarbonate formulations with one another.

10. The method of claim 7, wherein evaluating said degradation comprises visually inspecting the polycarbonate.

11. The method of claim 7, wherein evaluating the degradation comprises measuring a degree of discoloration of the polycarbonate.

12. The method of claim 11, wherein measuring the degree of discoloration of the polycarbonate comprises: (1) illuminating the polycarbonate with white light, a portion of the white light being transmitted through the polycarbonate; and generating a transmission spectrum from the portion of the white light transmitted through the polycarbonate; or (2) illuminating the transparent polycarbonate with white light, a portion of the white light being reflected from the transparent polycarbonate; and generating a reflectance spectrum of the portion of the white light reflected from the transparent polycarbonate; or (1) and (2).

13. The method of claim 7, further comprising: repeating the illuminating and maintaining steps for a second period of time; after the second period of time has elapsed, measuring a degree of discoloration of the transparent polycarbonate.

14. The method of claim 13, further comprising comparing the degree of discoloration measured after the first period of time with the degree of discoloration after the second period of time.

15. A method for determining a discoloration rate of a plurality of samples of transparent polycarbonate, the method comprising: illuminating the plurality of samples of transparent polycarbonate with light having a peak intensity centered at a wavelength from about 400 nm to about 500 nm and an irradiance from about 50,000 W/m.sup.2 to about 150,000 W/m.sup.2 for a period of time; measuring the temperatures of at least some of the plurality of samples of transparent polycarbonate by a separate thermocouple associated with that sample and calculating an average temperature of the thermoplastic using the temperatures of the at least some of the samples of the transparent polycarbonate; maintaining the average temperature at a temperature from about 23 C. to about 175 C. during the first period of time; repeating the illuminating and maintaining steps for a plurality of successive periods of time; and after each the successive period of time, measuring a degree of discoloration of the transparent polycarbonate.

16. The method of claim 15, further comprising measuring temperatures of at least two samples of the transparent polycarbonate; and calculating an average temperature of the transparent polycarbonate using the temperatures of the at least two samples of the transparent polycarbonate.

17. The method of claim 15, further comprising: repeating the illuminating, maintaining and measuring steps for a plurality of successive time periods for a plurality of different transparent polycarbonate formulations; and comparing the discoloration of the plurality of different transparent polycarbonate formulations with one another.

18. The method of claim 1, further comprising selecting a thermoplastic sample.

19. The method of claim 7, further comprising selecting a polycarbonate formulation sample.

20. The method of claim 15, further comprising selecting a transparent polycarbonate sample.

21. A method for determining degradation of a thermoplastic, the method consisting essentially of: illuminating a plurality of thermoplastics, for a period of time, with light having a peak intensity centered at a wavelength from about 410 nm to about 480 nm and an irradiance from about 400 W/m.sup.2 to about 150,000 W/m.sup.2; maintaining the average temperature of the thermoplastic at a temperature from about 23 C. to about 175 C. during the period of time; and repeating the illuminating and maintaining steps for a plurality of successive periods of time.

22. The method of claim 21, further comprising selecting a thermoplastic sample.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1a is an illustrative, schematic diagram illustrating an example device for executing a method for determining degradation of a thermoplastic, such as an opaque, translucent or transparent polycarbonate;

(2) FIG. 1b is an illustrative, schematic diagram illustrating an example device for executing a method for determining degradation of a thermoplastic, such as an opaque, translucent or transparent polycarbonate;

(3) FIG. 2 is a flow chart illustrating an example method for determining degradation of thermoplastic according to the invention; and

(4) FIGS. 3 and 4 are flow charts that illustrate exemplary methods for measuring a degree of discoloration of thermoplastic samples.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

(5) The present invention may be understood more readily by reference to the following detailed description taken in connection with the accompanying figures and examples, which form a part of this disclosure. It is to be understood that this invention is not limited to the specific devices, methods, applications, conditions or parameters described and/or shown herein, and that the terminology used herein is for the purpose of describing particular embodiments by way of example only and is not intended to be limiting of the claimed invention. Also, as used in the specification including the appended claims, the singular forms a, an, and the include the plural, and reference to a particular numerical value includes at least that particular value, unless the context clearly dictates otherwise. The term plurality, as used herein, means more than one. When a range of values is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent about, it will be understood that the particular value forms another embodiment. All ranges are inclusive and combinable.

(6) It is to be appreciated that certain features of the invention which are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. Further, reference to values stated in ranges include each and every value within that range.

(7) The summary, as well as the following detailed description, is further understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, there are shown in the drawings exemplary embodiments of the invention; however, the invention is not limited to the specific methods, compositions, and devices disclosed. In addition, the drawings are not necessarily drawn to scale. In the drawings:

(8) FIG. 1a shows an exemplary apparatus 10 which is useful for determining degradation of thermoplastics, in particular, for characterizing and comparing the rate of discoloration of opaque, translucent and transparent polycarbonates. Apparatus 10 comprises an oven chamber 12 (a chamber may be open or closed to the exterior environment during operation) in which a plurality of thermoplastic samples are positioned for testing. Three samples, 14, 16 and 18, each formed of a sample pair, each sample pair comprising two sample elements (14a, 14b, 16a, 16b, and 18a, 18b respectively), are shown by way of example, it being understood that more or fewer samples can be tested by the method according to the invention.

(9) Each sample pair 14a and 14b, 16a and 16b, 18a and 18b is illuminated by a respective light source 20, 22, 24 comprising, for example, LEDs 26 whose light emissions 28 are transmitted using silica glass waveguides 30. The LEDs and the waveguides work together so as to illuminate the samples with light spread over a desired range of wavelengths and intensities according to the parameters of the method described below. Each sample is instrumented with a respective thermometric transducer 32, for example, a thermocouple, for measuring the temperature of each sample. Transducers 32 generate electrical signals, for example, in the form of voltages, which are indicative of the temperature of each sample. Each sample pair may be heated by a respective heating element 34, 36 and 38 for example, an electrical resistance heater.

(10) The light sources 20, 22 and 24, and heating elements 34, 36 and 38 are independently controlled by a controller 40. Controller 40 may be, for example, a programmable logic controller or a computer with resident software and firmware. Controller 40 receives, manipulates and interprets temperature signals from the thermometric transducers 32 and, using this information in a feedback loop, controls the operation of the light sources 20, 22 and 24 (LEDs 26) and the heating elements 34, 36 and 38 according to the algorithms provided by its resident software. Controller 40 may also record and log data from the test. Communication between the various components and the controller 40 is effected in this example over dedicated communication lines 42.

(11) In the example method according to the invention, the samples are divided into sample pairs 14a, 14b, 16a, 16b and 18a, 18b, each having a respective illumination source 20, 22 and 24 and a respective heater 34, 36 and 38 because the method uses the average temperature derived from at least two sample elements comprising the sample pair to control operation of the respective heating elements 34, 36 and 38 for each sample pair so as to maintain the samples at a desired temperature as specified for a particular test protocol. Optionally, each sample pair may be tested at a different temperature and irradiance from a neighboring sample. Apparatus 10 can thus test samples of different materials, wherein each sample element in a sample pair is comprised of the same material, i.e., sample elements 14a and 14b are the same material, sample elements 16a and 16b are the same material (but not necessarily the same as sample elements 14a and 14b). Controller 40 calculates the average temperatures of the sample pairs and uses this information to control the heating elements 34, 36 and 38. The samples are cooled by natural circulation of air within the oven chamber 12. Fans or may also be used for a forced circulation regime if necessary.

(12) FIG. 1b shows an alternative example apparatus 10 which is useful for determining degradation of thermoplastics, in particular, for characterizing and comparing the rate of discoloration of opaque, translucent and transparent polycarbonates. Apparatus 10 comprises an oven chamber 12 in which a heating element 14 is positioned. The heating element 14 establishes and maintains the ambient air within the chamber 12 at a desired temperature appropriate for a particular test protocol (e.g., the temperature necessary to heat the sample to desired temperature). In a practical example, the heating element 14 may be an electrical resistance heater. At least one light source 16 is also positioned within chamber 12, the light source 16 being selected to emit light over a desired frequency range appropriate to the test requirements. In a particular example, the light source 16 may comprise one or more LEDs 18 whose light is channeled by a silica glass waveguide 20 so as to impinge upon a thermoplastic sample 22 positioned within the chamber 12 for testing.

(13) Temperature of the ambient air within the chamber 12 is monitored by a temperature measuring device 24 positioned within the chamber, for example, a thermometer or a thermocouple, which generates electrical signals indicative of the air temperature within the chamber. Another temperature measuring device 26 (e.g., a thermocouple) is mounted on the thermoplastic sample 22 and used to monitor the sample temperature, which may be in some cases be higher than the air temperature due to the light impinging on the sample from the light source 16. Signals from the temperature measuring devices 24 and 26 are supplied to a controller 28, which uses the temperature information to control the heating element 14 and the light source 16 during testing of the sample 22. Controller 28 may be, for example, a programmable logic controller or a computer with resident software, which, in addition to receiving and interpreting the temperature signals and controlling the operation of the light source 16 and the heating element 14, may also record and log data from the test. Communication between the various components and the controller 28 is effected in this example over dedicated communication lines 30.

(14) FIG. 2 is a flow chart that outlines an example method of determining degradation of opaque, translucent and transparent thermoplastics according to the invention. In this example, each thermoplastic sample, such as a transparent polycarbonate of a first formulation, may be a single sample or even be provided as multiple samplese.g., a sample paircomprising two or more sample elements. (Herein, the terms sample, sample pair and sample elements refer to a sample material being tested.) A sample or sample pair may be illuminated with light for a desired period of time as noted at box 44. When determining discoloration of a transparent polycarbonate for use with LED lamps for example, it has been found advantageous to use illuminating light having its peak intensity centered at a wavelength from about 400 nm to about 500 nm and having an irradiance from about 400 W/m.sup.2 to about 150,000 W/m.sup.2 (calibration for all irradiance values via a power meter such as the Model UP 55N 40S-H9 marketed by GENTEC-EO USA Inc. of Lake Oswego, Oreg.).

(15) As noted in box 46, during illumination, the temperature of each sample or sample pair may be maintained at a respective desired temperature, for example, from about 23 C. to about 175 C. for the desired period of time. (The maximum sample temperature is generally limited by the glass transition temperature or the melting point of the material being tested.) The temperature is maintained by measuring the temperatures of one or more sample elements (e.g., two elements), calculating the average temperature, and using that average temperature to control heating and cooling. The data derived from this test can be used to determine a rate of degradation of the samples, as well as for comparative purposes with other samples having different formulations. For transparent materials, irradiance from about 50,000 W/m.sup.2 to about 150,000 W/m.sup.2, as well as 50,000 W/m.sup.2 to about 110,000 W/m.sup.2 is also believed to be useful, as is an irradiance of about 75,000 W/m.sup.2. Sample temperatures from about 90 C. to about 130 C. are also believed to be useful, as are sample temperatures of about 120 C. as well as 130 C. For opaque materials, irradiance from about 400 W/m.sup.2 to about 50,000 W/m.sup.2 are considered useful, as is an irradiance of about 3,500 W/m.sup.2. Sample temperatures from about 23 C. to about 130 C. are also believed to be useful, as are sample temperatures of about 90 C. Additionally, illuminating light wavelengths wherein the peak intensity of the light is centered from about 410 nm to about 480 nm (measured radiometrically) are considered useful, as is illuminating light having its peak intensity centered at about 447 nm (measured radiometrically). These parameters are expected to allow for an illumination time period of as much as 100 hours, resulting in a measurable discoloration of the transparent polycarbonate without destroying the samples. It is further expected that illuminating light having its peak intensity centered at about 459 nm (measured radiometrically) will be useful as well as illuminating light emitted from an LED source and centered at about 470 nm dominant wavelength (measured photometrically) and about 550 nm measured radiometrically.

(16) It may in some cases be desirable to prevent heat build-up in the samples. Heat build-up may be avoided by cooling the samples during illumination. Cooling of each sample, as noted in box 48, may be accomplished, for example, by providing a separation distance between the sample and the light source sufficient to permit circulation of the ambient air around the sample and thereby allow convective cooling. Other methods of cooling, such as forced air cooling using a fan or even using refrigeration methods (with or without a fan) are also suitable.

(17) The step of evaluating the degradation of the sample is noted in box 50. This evaluation step may be accomplished, for example, by a simple visual observation of the samples, or photographs of the samples. Measurement techniques are also useful, as explained in detail below with reference to FIGS. 3 and 4.

(18) As described in box 52, the illuminating, maintaining and evaluating steps may be repeated for a plurality of successive time periods to provide, for example, the rate of discoloration of a polycarbonate sample as a function of time over which it is illuminated. This may show, for example, whether the rate of discoloration increases, decreases, or remains the same over time as it is exposed to the light. The successive time periods may be equal to one another.

(19) As noted in boxes 54 and 56, the method comprising the illuminating, maintaining and evaluating steps may be repeated for a plurality of successive time periods for a plurality of different thermoplastic samples having different formulations. This permits comparative evaluation between different polycarbonate formulations to determine their relative suitability for various applications, such as for use with LED lamps and luminaries (full lighting fixtures) as noted below.

(20) As shown in boxes 58 and 60 of FIG. 3, measurement of the transparent thermoplastic degradation, in this example discoloration of the transparent polycarbonate, is effected by illuminating the samples with white light after the desired time period has elapsed, and generating a transmission spectrum from a portion of the white light transmitted through the sample. In an alternate method outlined in boxes 62 and 64 of FIG. 4, the samples are illuminated with white light after the desired time period has elapsed and a reflectance spectrum is generated from the portion of the white light reflected from the sample. Either spectrum is expected to provide a useful measure of the discoloration of a transparent thermoplastic such as polycarbonate. The measurement method shown in FIG. 4 could also be effectively applied to opaque and translucent thermoplastics.

(21) A quantitative evaluation of the discoloration may be determined using either the Yellowness Index or the CIE L*a*b color system. The Yellowness Index is governed by two standards, ASTM E313 (2010) for opaque materials, and ASTM D1925 (1995), for transparent materials. For opaque materials, the Yellowness Index YI is calculated according to the formula:

(22) $\mathrm{YI}=100\left(\frac{0.847Z}{Y}\right)$

(23) and for transparent materials the Yellowness index is calculated according to the formula:

(24) $\mathrm{YI}=100.Math.\left(\frac{1.28.Math.X-1.06.Math.Z}{Y}\right)$
wherein X, Y and Z are tristimulus values for CIE illuminant C and the 1931 CIE 2 standard observer. Numerical values for a particular sample are obtained using a commercially available spectrophotometer, such as the X-Rite i7 Spectrophotometer marketed by X-Rite of Grand Rapids Mich.

(25) The example method outlined in FIGS. 2-4 may be used to gather data on a plurality of different polycarbonate formulations and then compare the discoloration rates of the various different formulations to determine which might be suitable for use in LED lighting, those sample polycarbonate formulations having the slowest discoloration rate being advantageous. Testing methods using the parameters outlined herein have permitted illumination time periods of 100 hours for transparent materials and have been used to evaluate numerous different samples to determine and compare their discoloration rates.

(26) Various polycarbonate formulations to which the example method may be applied are described below.

Definitions

(27) Ranges articulated within this disclosure, e.g. numerics/values, shall include disclosure for possession purposes and claim purposes of the individual points within the range, sub-ranges, and combinations thereof.

(28) Various combinations of elements of this disclosure are encompassed by this invention, e.g. combinations of elements from dependent claims that depend upon the same independent claim.

(29) The word about should be given its ordinary and accustomed meaning and should be relative to the word or phrase(s) that it modifies. In the context of pKa, the word about as it pertains to pKa can equal the value of the numeric or can equal in the range of +/0.1 of the pKa unit, e.g. pKa of about 8.3 can include 8.2, and the word about as it pertains to branching level can equal the value of the numeric or can equal in the range +/0.05% of the branching level, e.g. about 1% can encompass 0.95%. The delineation of the word about in the context pKa and branching level should not in any way limit the ordinary and accustomed meaning of the word about for other language/numerics that the word about modifies.

(30) The pKa values used in the model for the end-capping agents are listed in Table 1 below:

(31) TABLE-US-00001 TABLE 1 End-capping agent pKa* p-cyanophenol 8.2 p-methyl-hydroxy benzoate 8.4 Phenol 9.9 p-t-butylphenol 10.2 p-methoxyphenol 10.4 p-cumylphenol 10.5 *pKa values for all of the end-capping agents but p-t-butyl phenol and p-cumylphenol were obtained from the following reference: J. AM. CHEM. SOC. 2002, 6424. The values chosen in the reference were listed in the S7 category in Table 3 of the reference. The pKa value for p-t-butylphenol was obtained from the following reference: Journal of Molecular Structure: THEOCHEM 805, 2006, 31. The pKa for methyl-p-hydroxybenzoate was obtained from the following reference: Chromatographia Vol. 39, No. 5/6, September 1994. The pKa value for p-cumylphenol was approximated based on the values of similar structures.
Polycarbonate Material/Structural Backbone of the Composition

(32) In one embodiment, the plastic material of the plastic composition can comprise a polycarbonate. Descriptions of the various types of polycarbonates are articulated below, but should not be construed as limiting.

(33) Various types of polycarbonates that have a repeating structural background of the following formula:

(34) ##STR00001##
can be utilized.

(35) The selection of a polycarbonate backbone of choice depends on many factors such as end use and other factors understood by one of ordinary skill the art.

(36) In one embodiment, the polycarbonates have repeating structural carbonate units of the formula (1):

(37) ##STR00002##

(38) wherein greater than or equal to 60 percent of the total number of R.sup.1 groups contain aromatic organic groups and the balance thereof are aliphatic, alicyclic, or aromatic groups.

(39) In another embodiment, the polycarbonate is derived from bisphenol-A.

(40) In another embodiment, each R.sup.1 group is a divalent aromatic group, for example derived from an aromatic dihydroxy compound of the formula (2):
HO-A.sup.1-Y.sup.1-A.sup.2-OH(2)

(41) wherein each of A.sup.1 and A.sup.2 is a monocyclic divalent arylene group, and Y1 is a single bond or a bridging group having one or two atoms that separate A.sup.1 from A.sup.2. In an exemplary embodiment, one atom separates A.sup.1 from A.sup.2. In another embodiment, when each of A.sup.1 and A.sup.2 is phenylene, Y.sup.1 is para to each of the hydroxyl groups on the phenylenes. Illustrative non-limiting examples of groups of this type are O, S, S(O), S(O).sub.2, C(O), methylene, cyclohexyl-methylene, 2-[2.2.1]-bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene, and adamantylidene. The bridging group Y.sup.1 can be a hydrocarbon group or a saturated hydrocarbon group such as methylene, cyclohexylidene, or isopropylidene.

(42) Included within the scope of formula (2) are bisphenol compounds of general formula (3):

(43) ##STR00003##
wherein R.sup.a and R.sup.b each represent a halogen atom or a monovalent hydrocarbon group and can be the same or different; p and q are each independently integers of 0 to 4; and X.sup.a represents a single bond or one of the groups of formulas (4) or (5):

(44) ##STR00004##
wherein R.sup.c and R.sup.d are each independently hydrogen, C.sub.1-12 alkyl, C.sub.1-12 cycloalkyl, C.sub.7-12 arylalkyl, C.sub.1-12 heteroalkyl, or cyclic C.sub.7-12 heteroarylalkyl, and R.sup.e is a divalent C.sub.1-12 hydrocarbon group. In particular, R.sup.c and R.sup.d are each the same hydrogen or C.sub.1-4 alkyl group, specifically the same C.sub.1-3 alkyl group, even more specifically, methyl.

(45) In an embodiment, R.sup.c and R.sup.d taken together represent a C.sub.3-20 cyclic alkylene group or a heteroatom-containing C.sub.3-20 cyclic alkylene group comprising carbon atoms and heteroatoms with a valency of two or greater. These groups can be in the form of a single saturated or unsaturated ring, or a fused polycyclic ring system wherein the fused rings are saturated, unsaturated, or aromatic. A specific heteroatom-containing cyclic alkylene group comprises at least one heteroatom with a valency of 2 or greater, and at least two carbon atoms. Exemplary heteroatoms in the heteroatom-containing cyclic alkylene group include O, S, and N(Z), where Z is a substituent group selected from hydrogen, hydroxy, C.sub.1-12 alkyl, C.sub.1-12 alkoxy, or C.sub.1-12 acyl.

(46) In a specific exemplary embodiment, X.sup.a is a substituted C.sub.3-18 cycloalkylidene of the formula (6):

(47) ##STR00005##
wherein each R.sup.r, R.sup.p, R.sup.q, and R.sup.t is independently hydrogen, halogen, oxygen, or C.sub.1-12 organic group; I is a direct bond, a carbon, or a divalent oxygen, sulfur, or N(Z) wherein Z is hydrogen, halogen, hydroxy, C.sub.1-12 alkyl, C.sub.1-12 alkoxy, or C.sub.1-12 acyl; h is 0 to 2, j is 1 or 2, i is an integer of 0 or 1, and k is an integer of 0 to 3, with the proviso that at least two of R.sup.r, R.sup.p, R.sup.q, and R.sup.t taken together are a fused cycloaliphatic, aromatic, or heteroaromatic ring. It will be understood that where the fused ring is aromatic, the ring as shown in formula (6) will have an unsaturated carbon-carbon linkage where the ring is fused. When k is 1 and i is 0, the ring as shown in formula (6) contains 4 carbon atoms, when k is 2, the ring as shown contains 5 carbon atoms, and when k is 3, the ring contains 6 carbon atoms. In one embodiment, two adjacent groups (e.g., R.sup.q and R.sup.t taken together) form an aromatic group, and in another embodiment, R.sup.q and R.sup.t taken together form one aromatic group and R.sup.r and R.sup.p taken together form a second aromatic group.

(48) Non-limiting examples of dihydroxy compounds that can provide polycarbonates with Tgs greater than 170 C. include 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one (PPPBP), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane) (Bisphenol TMC), 4,4-(1-phenylethane-1,1-diyl)diphenol (bisphenol AP) as well as adamantyl containing aromatic dihydroxy compounds and flourene containing aromatic dihydroxy compounds.

(49) Specific example of dihydroxy compounds of formula (2) can be the following formula (7):

(50) ##STR00006##
(also known as 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one (PPPBP)) also known as 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine.

(51) Alternatively, the dihydroxy compounds of formula (2) may be the following formula (8):

(52) ##STR00007##
(also known as 4,4-(1-phenylethane-1,1-diyl)diphenol (bisphenol AP) also known as 1,1-bis(4-hydroxyphenyl)-1-phenyl-ethane).

(53) Alternatively, the dihydroxy compounds of formula (2) may be the following formula (9):

(54) ##STR00008##
(bisphenol TMC) also known as 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane). Examples of adamantyl containing aromatic dihydroxy compounds and flourene containing aromatic dihydroxy compounds are set forth in Formulas (A) and (B) respectively.

(55) ##STR00009##

(56) Another possible polycarbonate with high Tg is set forth in formula (C):

(57) ##STR00010##

(58) A polycarbonate can have a bisphenol of formula (D) as a repeating monomer unit therein:

(59) ##STR00011##

(60) When k is 3 and i is 0, bisphenols containing substituted or unsubstituted cyclohexane units are used, for example bisphenols of formula (10):

(61) ##STR00012##
wherein each R.sup.f is independently hydrogen, C.sub.1-12 alkyl, or halogen; and each R.sup.g is independently hydrogen or C.sub.1-12 alkyl. The substituents can be aliphatic or aromatic, straight chain, cyclic, bicyclic, branched, saturated, or unsaturated. Such cyclohexane-containing bisphenols, for example the reaction product of two moles of a phenol with one mole of a hydrogenated isophorone, are useful for making polycarbonate polymers with high glass transition temperatures and high heat distortion temperatures. Cyclohexyl bisphenol containing polycarbonates, or a combination comprising at least one of the foregoing with other bisphenol polycarbonates, are supplied by Bayer Co. under the APEC trade name.

(62) Other useful dihydroxy compounds having the formula HOR.sup.1OH include aromatic dihydroxy compounds of formula (11):

(63) ##STR00013##
wherein each R.sup.h is independently a halogen atom, a C.sub.1-10 hydrocarbyl such as a C.sub.1-10 alkyl group, a halogen substituted C.sub.1-10 hydrocarbyl such as a halogen-substituted C.sub.1-10 alkyl group, and n is 0 to 4. The halogen is usually bromine.

(64) Some illustrative examples of dihydroxy compounds include the following: 4,4-dihydroxybiphenyl, 1,6-dihydroxynaphthalene, 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-hydroxyphenyl)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-sec-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-t-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-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone, 1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, ethylene glycol bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, 9,9-bis(4-hydroxyphenyl)fluorine, 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-dihydroxyphenoxathin, 2,7-dihydroxy-9,10-dimethylphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole, resorcinol, substituted resorcinol compounds such as 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol, 5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenyl resorcinol, 5-cumyl resorcinol, 2,4,5,6-tetrafluoro resorcinol, 2,4,5,6-tetrabromo resorcinol, or the like; catechol; hydroquinone; substituted hydroquinones such as 2-methyl hydroquinone, 2-ethyl hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone, 2,3,5,6-tetramethyl hydroquinone, 2,3,5,6-tetra-t-butyl hydroquinone, 2,3,5,6-tetrafluoro hydroquinone, 2,3,5,6-tetrabromo hydroquinone, and the like, as well as combinations comprising at least one of the foregoing dihydroxy compounds.

(65) Specific examples of bisphenol compounds that can be represented by formula (2) include 1,1-bis(4-hydroxyphenyl) methane, 1,1-bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane (hereinafter 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, 1,1-bis(4-hydroxy-t-butylphenyl) propane, 3,3-bis(4-hydroxyphenyl) phthalimidine, 2-phenyl-3,3-bis(4-hydroxyphenyl) phthalimidine (PPPBP), and 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (DMBPC). Combinations comprising at least one of the foregoing dihydroxy compounds can also be used.

(66) Polycarbonate as used herein includes homopolycarbonates, copolymers comprising different R.sup.1 moieties in the carbonate (also referred to herein as copolycarbonates), and copolymers comprising carbonate units and other types of polymer units, such as ester units. In one specific embodiment, the polycarbonate is a linear homopolymer or copolymer comprising units derived from bisphenol A, in which each of A.sup.1 and A.sup.2 is p-phenylene and Y.sup.1 is isopropylidene in formula (2). More specifically, greater than or equal to 60%, particularly greater than or equal to 80% of the R.sup.1 groups in the polycarbonate are derived from bisphenol A.

(67) Another specific type of copolymer is a polyester carbonate, also known as a polyester-polycarbonate. Such copolymers further contain, in addition to recurring carbonate chain units of the formula (1), repeating units of formula (9):

(68) ##STR00014##
wherein D is a divalent group derived from a dihydroxy compound, and can be, for example, a C.sub.2-C.sub.10 alkylene group, a C.sub.6-C.sub.20 alicyclic group, a C.sub.6-C.sub.20 aromatic group or a polyoxyalkylene group in which the alkylene groups contain 2 to 6 carbon atoms, specifically 2, 3, or 4 carbon atoms; and T divalent group derived from a dicarboxylic acid, and can be, for example, a C.sub.2-C.sub.10 alkylene group, a C.sub.6-C.sub.20 alicyclic group, a C.sub.6-C.sub.20 alkyl aromatic group, or a C.sub.6-C.sub.20 aromatic group.

(69) In one embodiment, D is a C.sub.2 to C.sub.30 alkylene group having a straight chain, branched chain, or cyclic (including polycyclic) structure. In another embodiment, D is derived from an aromatic dihydroxy compound of formula (3) above. In another embodiment, D is derived from an aromatic dihydroxy compound of formula (8) above.

(70) Examples of aromatic dicarboxylic acids that can be used to prepare the polyester units include isophthalic or terephthalic acid, 1,2-di(p-carboxyphenyl)ethane, 4,4-dicarboxydiphenyl ether, 4,4-bisbenzoic acid, and combinations comprising at least one of the foregoing acids. Acids containing fused rings can also be present, such as in 1,4-, 1,5-, or 2,6-naphthalenedicarboxylic acids. Specific dicarboxylic acids are terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid, or combinations thereof. A specific dicarboxylic acid comprises a combination of isophthalic acid and terephthalic acid wherein the weight ratio of isophthalic acid to terephthalic acid is 91:9 to 2:98. In another specific embodiment, D is a C.sub.2-6 alkylene group and T is p-phenylene, m-phenylene, naphthalene, a divalent cycloaliphatic group, or a combination thereof. This class of polyester includes the poly(alkylene terephthalates).

(71) The molar ratio of ester units to carbonate units in the copolymers can vary broadly, for example 1:99 to 99:1, specifically 10:90 to 90:10, more specifically 25:75 to 75:25, depending on the desired properties of the final composition.

(72) In a specific embodiment, the polyester unit of a polyester-polycarbonate can be derived from the reaction of a combination of isophthalic and terephthalic diacids (or derivatives thereof) with resorcinol. In another specific embodiment, the polyester unit of a polyester-polycarbonate is derived from the reaction of a combination of isophthalic acid and terephthalic acid with bisphenol-A. In a specific embodiment, the polycarbonate units are derived from bisphenol A. In another specific embodiment, the polycarbonate units are derived from resorcinol and bisphenol A in a molar ratio of resorcinol carbonate units to bisphenol A carbonate units of 1:99 to 99:1.

(73) A specific example of a polycarbonate-polyester is a copolycarbonate-polyester-polysiloxane terpolymer comprising carbonate units of formula (1), ester units of formula (9), and polysiloxane (also referred to herein as polydiorganosiloxane) units of formula (10):

(74) ##STR00015##
wherein each occurrence of R is same or different, and is a C.sub.1-13 monovalent organic group. For example, R may independently be a C.sub.1-13 alkyl group, C.sub.1-13 alkoxy group, C.sub.2-13 alkenyl group, C.sub.2-13 alkenyloxy group, C.sub.3-6 cycloalkyl group, C.sub.3-6 cycloalkoxy group, C.sub.6-14 aryl group, C.sub.6-10 aryloxy group, C.sub.7-13 arylalkyl group, C.sub.7-13 arylalkoxy group, C.sub.7-13 alkylaryl group, or C.sub.7-13 alkylaryloxy group. The foregoing groups may be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof. Combinations of the foregoing R groups may be used in the same copolymer. In an embodiment, the polysiloxane comprises R groups that have a minimum hydrocarbon content. In a specific embodiment, an R group with a minimum hydrocarbon content is a methyl group.

(75) The value of E in formula (10) may vary widely depending on the type and relative amount of each component in the plastic (e.g., thermoplastic) composition, the desired properties of the composition, and like considerations. Herein, E has an average value of 5 to 200, with the specific amount chosen so that a 1.0 mm thick plaque of the plastic composition (i.e., plastic material, coated conversion material(s), any additive(s)) has a transparency (% T) of greater than or equal to 30%. It is readily understood by an artisan that the E value is chosen (e.g., adjusted such as when the amount of siloxane in the material and when the siloxane is introduced to form the material and/or the process for making the material) to achieve a balance between transparency, flame retardancy, and impact. In an embodiment, E has an average value of 16 to 50, specifically 20 to 45, and more specifically 25 to 45. In another embodiment, E has an average value of 4 to 15, specifically 5 to 15, more specifically 6 to 15, and still more specifically 7 to 12.

(76) In an embodiment, polydiorganosiloxane units are derived from dihydroxy aromatic compound of formula (11):

(77) ##STR00016##

(78) wherein E is as defined above; each R may independently be the same or different, and is as defined above; and each Ar may independently be the same or different, and is a substituted or unsubstituted C.sub.6-30 arylene group, wherein the bonds are directly connected to an aromatic moiety. Suitable Ar groups in formula (11) may be derived from a C.sub.6-30 dihydroxy aromatic compound, for example a dihydroxy aromatic compound of formula (2), (3), (7), or (8) above. Combinations comprising at least one of the foregoing dihydroxy aromatic compounds may also be used. Examples of dihydroxy aromatic compounds include resorcinol (i.e., 1,3-dihydroxybenzene), 4-methyl-1,3-dihydroxybenzene, 5-methyl-1,3-dihydroxybenzene, 4,6-dimethyl-1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 1,1-bis(4-hydroxyphenyl) methane, 1,1-bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane, 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, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl sulfide), and 1,1-bis(4-hydroxy-t-butylphenyl) propane. Combinations comprising at least one of the foregoing dihydroxy compounds may also be used. In an embodiment, the dihydroxy aromatic compound is unsubstituted, or is not substituted with non-aromatic hydrocarbon-containing substituents such as, for example, alkyl, alkoxy, or alkylene substituents.

(79) In a specific embodiment, where Ar is derived from resorcinol, the polydiorganosiloxane repeating units are derived from dihydroxy aromatic compounds of formula (12):

(80) ##STR00017##
or, where Ar is derived from bisphenol-A, from dihydroxy aromatic compounds of formula (13):

(81) ##STR00018##
wherein E is as defined above.

(82) In another embodiment, polydiorganosiloxane units are derived from dihydroxy aromatic compound of formula (14):

(83) ##STR00019##
wherein R and E are as described above, and each occurrence of R.sup.2 is independently a divalent C.sub.1-30 alkylene or C.sub.7-30 arylene-alkylene, and wherein the polymerized polysiloxane unit is the reaction residue of its corresponding dihydroxy aromatic compound. In a specific embodiment, where R.sup.2 is C.sub.7-30 arylene-alkylene, the polydiorganosiloxane units are derived from dihydroxy aromatic compound of formula (15):

(84) ##STR00020##
wherein R and E are as defined above. Each R.sup.3 is independently a divalent C.sub.2-8 aliphatic group. Each M may be the same or different, and may be a halogen, cyano, nitro, C.sub.1-8 alkylthio, C.sub.1-8 alkyl, C.sub.1-8 alkoxy, C.sub.2-8 alkenyl, C.sub.2-8 alkenyloxy group, C.sub.3-8 cycloalkyl, C.sub.3-8 cycloalkoxy, C.sub.6-10 aryl, C.sub.6-10 aryloxy, C.sub.7-12 arylalkyl, C.sub.7-12 arylalkoxy, C.sub.7-12 alkylaryl, or C.sub.7-12 alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4.

(85) In an embodiment, M is bromo or chloro, an alkyl group such as methyl, ethyl, or propyl, an alkoxy group such as methoxy, ethoxy, or propoxy, or an aryl group such as phenyl, chlorophenyl, or tolyl; R.sup.3 is a dimethylene, trimethylene or tetramethylene group; and R is a C.sub.1-8 alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such as phenyl, chlorophenyl or tolyl. In another embodiment, R is methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl. In still another embodiment, M is methoxy, n is 0 or 1, R.sup.3 is a divalent C.sub.1-3 aliphatic group, and R is methyl.

(86) In a specific embodiment, the polydiorganosiloxane units are derived from a dihydroxy aromatic compound of formula (16):

(87) ##STR00021##
wherein E is as described above.

(88) In another specific embodiment, the polydiorganosiloxane units are derived from dihydroxy aromatic compound of formula (17):

(89) ##STR00022##
wherein E is as defined above.

(90) Dihydroxy polysiloxanes typically can be made by functionalizing a substituted siloxane oligomer of formula (18):

(91) ##STR00023##
wherein R and E are as previously defined, and Z is H, halogen (Cl, Br, I), or carboxylate. Examples of carboxylates include acetate, formate, benzoate, and the like. In an exemplary embodiment, where Z is H, compounds of formula (18) may be prepared by platinum catalyzed addition with an aliphatically unsaturated monohydric phenol. Examples of aliphatically unsaturated monohydric phenols include eugenol, 2-allylphenol, 4-allylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2-bromophenol, 4-allyl-2-t-butoxyphenol, 4-phenyl-2-allylphenol, 2-methyl-4-propenylphenol, 2-allyl-4,6-dimethylphenol, 2-allyl-4-bromo-6-methylphenol, 2-allyl-6-methoxy-4-methylphenol, and 2-allyl-4,6-dimethylphenol. Combinations comprising at least one of the foregoing may also be used. Where Z is halogen or carboxylate, functionalization may be accomplished by reaction with a dihydroxy aromatic compound of formulas (2), (3), (7), (8), or a combination comprising at least one of the foregoing dihydroxy aromatic compounds. In an embodiment, compounds of formula (12) may be formed from an alpha, omega-bisacetoxypolydiorangonosiloxane and a dihydroxy aromatic compound under phase transfer conditions.

(92) In some embodiments a copolycarbonate terpolymer can be used. Specific copolycarbonate terpolymers include those with polycarbonate units of formula (1) wherein R.sup.1 is a C.sub.6-30 arylene group, polysiloxane units derived from siloxane diols of formula (13), (16) or (17), and polyester units wherein T is a C.sub.6-30 arylene group. In an embodiment, T is derived from isophthalic and/or terephthalic acid, or reactive chemical equivalents thereof. In another embodiment, R.sup.1 is derived from the carbonate reaction product of a resorcinol of formula (8), or a combination of a resorcinol of formula (8) and a bisphenol of formula (4).

(93) The relative amount of each type of unit in the foregoing terpolymer will depend on the desired properties of the terpolymer, and are readily determined by one of ordinary skill in the art without undue experimentation, using the guidelines provided herein. For example, the polycarbonate-polyester-polysiloxane terpolymer can comprise siloxane units in an amount of 0.1 to 25 weight percent (wt %), specifically 0.2 to 10 wt %, more specifically 0.2 to 6 wt %, even more specifically 0.2 to 5 wt %, and still more specifically 0.25 to 2 wt %, based on the total weight of the polycarbonate-polyester-polysiloxane terpolymer, with the proviso that the siloxane units are provided by polysiloxane units covalently bonded in the polymer backbone of the polycarbonate-polyester-polysiloxane terpolymer. The polycarbonate-polyester-polysiloxane terpolymer can further comprise 0.1 to 49.85 wt % carbonate units, 50 to 99.7 wt % ester units, and 0.2 to 6 wt % polysiloxane units, based on the total weight of the polysiloxane units, ester units, and carbonate units. Alternatively, the polycarbonate-polyester-polysiloxane terpolymer comprises 0.25 to 2 wt % polysiloxane units, 60 to 96.75 wt % ester units, and 3.25 to 39.75 wt % carbonate units, based on the total weight of the polysiloxane units, ester units, and carbonate units. The specific amount of terpolymer and the composition of the terpolymer will be chosen so that a 1.0 mm thick plaque of the composition transparency (% T) of greater than or equal to 30%.

(94) In a further embodiment, a method of making an article of manufacture that has a V0 94 rating at a thickness of 2.0 mm (specifically at a thickness of 1.5 mm) comprises: (a) providing a polycarbonate, wherein the polycarbonate has a repeating structural background of the following formula

(95) ##STR00024##
wherein greater than or equal to 60 percent of the total number of R.sup.1 groups contain aromatic organic groups and the balance thereof are aliphatic, alicyclic, or aromatic groups; an end capping agent; a branching agent; (b) selecting the end-capping agent based upon the molecular weight of the polycarbonate and the branching level imparted by the branching agent, wherein the MVR of the polycarbonate is 1 to 15 cubic centimeter per 10 minutes (cm.sup.3/10 min) and wherein the pKa of the end-capping agent is 8.3 to 11; (c) forming a polycarbonate containing the end-capping agent and the branching that has a peak melt viscosity of greater than or equal to 8,000 poise when measured using a parallel plate melt rheology test at a heating rate of 10 C./min at a temperature of 350 C. to 450 C.; and (d) blending a conversion material and a flame retardant with the formed polycarbonate.

(96) The peak melt viscosity can be greater than or equal to 25,000 poise when measured using a parallel plate melt rheology test at a heating rate of 10 C./min at a temperature of 350 C. to 450 C.

(97) In another embodiment, the composition comprises: a flame retardant; a conversion material; a polycarbonate, wherein the polycarbonate has a repeating structural background of the following formula

(98) ##STR00025##
wherein greater than or equal to 60 percent of the total number of R.sup.1 groups contain aromatic organic groups and the balance thereof are aliphatic, alicyclic, or aromatic groups and wherein the polycarbonate contains one or more bisphenols; wherein the polycarbonate comprises an end-capping agent; wherein the polycarbonate comprises a branching agent; and wherein the polycarbonate containing the branching agent and the end-capping agent has a peak melt viscosity of greater than or equal to 7,000 poise when calculated from the equation of wherein the peak melt viscosity equals: 57135.91+36961.39*BL+14001.13*MW.sup.1/346944.24*pKa322.51*BL*MW.sup.1/32669.19*BL*pKa+215.83*MW.sup.1/3*pKa+1125.63*BL.sup.2200.11*MW.sup.2/3+2231.15*pKa.sup.2, wherein BL is the mole ratio of the branching agent in the formulation determined by dividing the number of moles of branching agent by the total number of moles of bisphenol or bisphenols in the composition, the MW is the weight-averaged molecular weight of the polycarbonate containing the branching agent and the end-capping agent as determined by gel permeation chromatography using polycarbonate standards, and the pKa is the pKa of the end capping agent; and wherein a molded article of the composition has a UL 94 V0 rating at a thickness of 2.0 mm, specifically at 1.5 mm, and more specifically at 1.0 mm.

(99) In a further embodiment, the peak melt viscosity is greater than or equal to 25,000 as calculated by the above equation.

(100) In another embodiment, a method of making an article of manufacture that has a V0 94 rating at a thickness 1.5 mm comprises: (a) providing a polycarbonate, wherein the polycarbonate has a repeating structural background of the following formula

(101) ##STR00026##
wherein greater than or equal to 60 percent of the total number of R.sup.1 groups contain aromatic organic groups and the balance thereof are aliphatic, alicyclic, or aromatic groups and wherein the polycarbonate contains one or more bisphenols; an end capping agent that is not cyanophenol; a branching agent; (b) selecting the end-capping agent based upon the molecular weight of the polycarbonate and the branching level imparted by the branching agent, wherein the MVR of the polycarbonate is 1 to 15 cm.sup.3/10 min and wherein the pKa of the end-capping agent is 8 to 11; (c) forming a polycarbonate containing the end-capping agent and the branching agent that has a peak melt viscosity that is greater than or equal to 7,000 poise when calculated from the equation of wherein the peak melt viscosity equals: 57135.91+36961.39*BL+14001.13*MW.sup.1/346944.24*pKa322.51*BL*MW.sup.1/32669.19*BL*pKa+215.83*MW.sup.1/3*pKa+1125.63*BL.sup.2200.11*MW.sup.2/3+2231.15*pKa.sup.2; and wherein BL is the mole ratio of the branching agent in the formulation determined by dividing the number of moles of branching agent by the total number of moles of bisphenol or bisphenols in the composition, the MW is the weight-averaged molecular weight of the formed polycarbonate as determined by gel permeation chromatography using polycarbonate standards, and the pKa is the pKa of the end capping agent; and (d) blending a flame retardant and a conversion material with the formed polycarbonate.

(102) In a further embodiment, the peak melt viscosity is greater than or equal to 25,000 poise calculated from the above equation.

(103) Branching Agents for Polycarbonate Containing Compositions

(104) The polycarbonates herein may include branched polycarbonate(s). Various types of branching agents can be utilized for the embodiments encompassed by this disclosure.

(105) Branched polycarbonate blocks can be prepared by adding a branching agent during polymerization. These branching agents include polyfunctional organic compounds containing at least three functional groups selected from hydroxyl, carboxyl, carboxylic anhydride, haloformyl, and mixtures of the foregoing functional groups. Specific examples include trimellitic acid, trimellitic anhydride, trimellitic trichloride (TMTC), tris-p-hydroxy phenyl ethane (THPE), 3,3-bis-(4-hydroxyphenyl)-oxindole (also known as isatin-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. The branching agents can be added at a level of 0.05 to 2.0 wt %. Mixtures comprising linear polycarbonates and branched polycarbonates can be used.

(106) In some embodiments, a particular type of branching agent is used to create branched polycarbonate materials. These branched polycarbonate materials have statistically more than two end groups. The branching agent is added in an amount (relative to the bisphenol monomer) that is sufficient to achieve the desired branching content, that is, more than two end groups. The molecular weight of the polymer may become very high upon addition of the branching agent and may lead to viscosity problems during phosgenation. Therefore, in some embodiments, an increase in the amount of the chain termination agent is used in the polymerization. The amount of chain termination agent used when the particular branching agent is used is generally higher than the instance when only a chain termination agent is used. The amount of chain termination agent used is generally above 5 mole percent and less than 20 mole percent compared to the bisphenol monomer.

(107) In some embodiments, the branching agent is a structure derived from a triacid trichloride of the formula (19):

(108) ##STR00027##
wherein, in this formula (19), Z is hydrogen, a halogen, C.sub.1-3 alkyl group, C.sub.1-3 alkoxy group, C.sub.7-12 arylalkyl, alkylaryl, or nitro group, and z is 0 to 3; or a branching agent derived from a reaction with a tri-substituted phenol of the formula (20):

(109) ##STR00028##
wherein, in this formula (20), T is a C.sub.1-20 alkyl group, C.sub.1-20 alkyleneoxy group, C.sub.7-12 arylalkyl, or alkylaryl group, S is hydrogen, a halogen, C.sub.1-3 alkyl group, C.sub.1-3 alkoxy group, C.sub.7-12 arylalkyl, alkylaryl, or nitro group, s is 0 to 4.

(110) In another embodiment, the branching agent is a structure having formula (21):

(111) ##STR00029##

(112) Examples of specific branching agents that are particularly effective in the compositions include trimellitic trichloride (TMTC), tris-p-hydroxy phenyl ethane (THPE) and isatin-bis-phenol. In one embodiment, in formula (19), Z is hydrogen and z is 3. In another embodiment, in formula (20), S is hydrogen, T is methyl, and s is 4.

(113) The relative amount of branching agents used in the manufacture of the polymer will depend on a number of considerations, for example the type of R.sup.1 groups, the amount of cyanophenol, and the desired molecular weight of the polycarbonate. In general, the amount of branching agent is effective to provide about 0.1 to 10 branching units per 100 R.sup.1 units, specifically about 0.5 to 8 branching units per 100 R.sup.1 units, and more specifically about 0.75 to 5 branching units per 100 R.sup.1 units. For branching agents having formula (20), the amount of branching agent tri-ester groups are present in an amount of about 0.1 to 10 branching units per 100 R.sup.1 units, specifically about 0.5 to 8 branching units per 100 R.sup.1 units, and more specifically about 0.75 to 5 tri-ester units per 100 R.sup.1 units. For branching agents having formula (21), the amount of branching agent tricarbonate groups are present in an amount of about 0.1 to 10 branching units per 100 R.sup.1 units, specifically about 0.5 to 8 branching units per 100 R.sup.1 units, and more specifically about 0.75 to 5 tri-phenylcarbonate units per 100 R.sup.1 units. In some embodiments, a combination of two or more branching agents may be used.

(114) In one embodiment, the polycarbonate of the composition has a branching level of greater than or equal to 1%, or greater than or equal to 2%, or greater than or equal to 3%, or 1% to 3%.

(115) End-Capping Agents for Polycarbonate Containing Compositions

(116) Various types of end-capping agents can be utilized herein provided that such agents do not significantly adversely affect the desired properties of the compositions, such as transparency, ductility, fire retardants, and the like.

(117) Examples of endcapping agents (also referred to as chain stoppers) include certain mono-phenolic compound(s), and/or mono-carboxylic acid chloride(s), and/or mono-chloroformate(s). Mono-phenolic chain stoppers are exemplified by monocyclic phenols such as phenol and C.sub.1-C.sub.22 alkyl-substituted phenols such as p-cumyl-phenol, and p-t-butyl phenol; and monoethers of diphenols, such as p-methoxyphenol, phenols with phenols with cyano-substitution such as p-cyanophenol, or with halogen substitution such as p-flurophenol, or with nitro-substitution such as 4-nitrophenol. Alkyl-substituted phenols with branched chain alkyl substituents having 8 to 9 carbon atoms can be specifically mentioned. Certain mono-phenolic UV absorbers can also be used as an endcapping agent, for example 4-substituted-2-hydroxybenzophenones and their derivatives, aryl salicylates, monoesters of diphenols such as resorcinol monobenzoate, 2-(2-hydroxyaryl)-benzotriazoles and their derivatives, 2-(2-hydroxyaryl)-1,3,5-triazines and their derivatives, and the like. For example, the polycarbonate can have an end-cap comprising phenol, such as alkyl-substituted phenols, ether-substituted phenols, ester-substituted phenols, cyano-substituted phenols, and halogen substituted phenols, as well as combinations comprising at least one of the foregoing. Optionally, the end-capping agents can be selected from: cyanophenol and a phenol containing substitution(s) with aliphatic groups, olefinic groups, aromatic groups, halogens, ester groups, ether groups, and combinations comprising at least one of the foregoing.

(118) Of particular usefulness commercially, the end-capping agents can be phenol, e.g., specifically, can be selected from: cyanophenol, para-t-butylphenol, para-cumylphenol, and combinations comprising at least one of the foregoing.

(119) Additional thermoplastic material to which the method may be applied include polyethylene terephthalates (PET) and polybutylene terephthalate (PBT), polyethylene napthalate (PEN), polymethyl methacrylate (PMMA), polystyrene (PS), cyclic olefinic polymers (COP) and cyclic olefinic copolymers (COC), polyetherimide as well as polycarbonate/polyester blends. In addition to thermoplastics, the method may also be used to test silicone based compounds as provided by Dow Corning.

(120) The method is further illustrated by the following non-limiting examples.

Example 1Transparent Polycarbonate Test

(121) Testing using the method according to the invention was conducted on four different transparent polycarbonate formulations. The polycarbonate samples for each formulation comprised square plates approximately 3030 mm and 1.5 mm thick. Sample transparent polycarbonate formulations were illuminated with light having a peak intensity centered on 447 nm (measured radiometrically) at an irradiance of 50,000 W/m.sup.2 (calibration via a power meter). The illumination of the samples was performed in an oven within which the sample temperature (in this example, an average of two samples) was maintained at a temperature of 120 C. Illumination was provided over a series of 6 (unequal) intervals for a total of 1,729 hours or until failure of the sample. Samples that experienced catastrophic failure (i.e., melting, charring) were removed from the oven between successive periods of illumination. At the end of each interval, the samples were allowed to cool and their % transmittance ratio and degree of discoloration, as determined using the Yellowness Index, was measured using a spectrophotometer. The % transmittance ratio was calculated by measuring an initial % transmittance value for each sample before exposure of the samples and then measuring the % transmittance of each sample after each exposure interval and then calculating the ratio of the % transmittance after each exposure interval to the initial % transmittance. The % transmittance measurements were determined according to ASTM D1003-00 (2000) using procedure A and CIE illuminant C and 2 degree observer on an X-Rite i7 spectrophotometer using an integrating sphere with 8/diffuse geometry, specular component included, UV included, 6 mm small area view lens, and 25 mm large area view transmission port, with the percent transmittance value reported as Y (luminous transmittance) taken from the CIE 1931 tristimulus values XYZ. The YI (yellowness index) was determined according to ASTM D1925-95 (1995) CIE illuminant C and 2 degree observer on a X-Rite i7 spectrophotometer using an integrating sphere with 8/diffuse geometry, specular component included, UV included, 6 mm small area view lens, and 25 mm large area view transmission port.

(122) The results of the testing showed measurable differences in the rate of discoloration between the samples throughout the six illumination intervals, with sample 1 failing (melted) at 1,197 hours exposure, sample 2 having a yellowness index of 2.14 and a % transmittance ratio of 98.86% at 1,729 hours exposure, sample 3 having a yellowness index of 0.46 and a % transmittance ratio of 98.67 at 1,729 hours exposure, and sample 4 having a yellowness index of 0.19 and a % transmittance ratio of 98.82% at 1,729 hours exposure.

Example 2White Opaque Polymer Test

(123) Testing using the method according to the invention was conducted on four different white opaque polymer formulations. The samples for each formulation comprised square plates approximately 3030 mm and 1.5 mm thick. Each sample polymer formulation was illuminated with light having a peak intensity centered on 447 nm (measured radiometrically) at an irradiance of 50,000 W/m.sup.2 (calibration via a power meter). The illumination of the samples was performed in an oven within which the sample temperature (in this instance, an average of two samples) was maintained at a temperature of 90 C. Illumination was provided over a single interval for a total of 33 hours or until failure of the sample. Samples that experienced catastrophic failure (i.e., melting, charring) were removed from the oven between successive periods of illumination. At the end of the interval the samples were allowed to cool and their degree of discoloration, as determined using the Yellowness Index, was measured using a spectrophotometer. The YI (yellowness index) was determined according to ASTM D1925-95 (1995) CIE illuminant C and 2 degree observer on a X-Rite i7 spectrophotometer using an integrating sphere with 8/diffuse geometry, specular component included, UV included, 6 mm small area view at the port.

(124) The results of the testing showed measurable differences in the rate of discoloration between the samples, with sample 1 (a polycarbonate) having a yellowness index of 5.33, sample 2 (a polycarbonate having a higher glass transition temperature than sample 1) having a yellowness index of 8.75, sample 3 (a polyester) having a yellowness index of 0.0, and sample 4 (a glass filled polyester) having a yellowness index of 34.33.

(125) These foregoing results show that the disclosed methods are effective in that the methods produce meaningful quantitative measurements of the rate of thermoplastic degradation in a reasonable time frame.