Copolymers and polymer blends having improved refractive indices

Information

  • Patent Grant
  • 8691915
  • Patent Number
    8,691,915
  • Date Filed
    Monday, April 23, 2012
    12 years ago
  • Date Issued
    Tuesday, April 8, 2014
    10 years ago
Abstract
This disclosure relates generally to methods for the manufacture of transparent polymer compositions exhibiting refractive indices similar or even identical to the refractive index of polycarbonate. Also disclosed are polymer blends comprising the disclosed polymer compositions blended with one or more convention polycarbonate.
Description
BACKGROUND OF THE INVENTION

Blends of polycarbonate and various other polymer compositions such as acrylonitrile-butadiene-styrene (ABS) and styrene-acrylonitrile (SAN) are well known for their advantageous performance properties. However, polycarbonate blends with other non-polycarbonate material often lack the desired level of transparency and haze. To that end, several attempts have been made to improve the transparency and to reduce the haze of polycarbonate blends with various combinations of acrylonitrile-butadiene-styrene, styrene, acrylonitrile, and other monomers. However, none of these attempts were able to produce a polycarbonate blend that exhibits a relatively high transparency and relatively low haze characterized by a refractive index similar or the same as that of the polycarbonate itself. There remains a need in the art for such polycarbonate blends and for polymer compositions that are capable of providing such polycarbonate blends.


SUMMARY OF THE INVENTION

This invention relates generally to polymer compositions having refractive indices similar or the same as the refractive index of a conventional polycarbonate. These polymer compositions can in turn be blended with one or more polycarbonates to provide a polycarbonate polymer blend that exhibits a refractive index of a conventional polycarbonate without affecting its blend compatibility and other performance and processing properties similar to that of other compatible ABS polymers when blended with polycarbonate.


According to aspects of the invention, a cotetrapolymer composition is provided that exhibits a refractive index value “n” at least substantially similar to a refractive index value “n” of a conventional polycarbonate of Bisphenol-A. The cotetrapolymer composition comprises styrene, acrylonitrile, methylmethacrylate, and α-methylstyrene. The disclosed tetrapolymer composition can be prepared by any conventional method for co-polymerizing the four co-monomers, such as emulsion, suspension, and bulk or mass polymerization.


In other aspects, the present invention provides polymer blend compositions comprising one or more conventional polycarbonates of Bisphenol-A blended together with one or more of the disclosed tetrapolymer compositions summarized above and described herein. The polymer blend can comprise from about 1 to about 99 parts by weight polycarbonate and from about 99 to about 1 parts by weight of a disclosed tetrapolymer. The polymer blend further exhibits a refractive index value “n” at least substantially similar or even identical to the refractive index value “n” of the conventional polycarbonate of Bisphenol-A present in the blend.


Other advantages will be set forth in part in the description which follows or may be learned by practice. The advantages will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive, as claimed.


In other aspects, the present invention provides polymer blend compositions comprising one or more conventional polycarbonates other than a Bisphenol-A polycarbonate blended together with one or more of the disclosed tetrapolymer compositions summarized above and described herein. The polymer blend compositions according to these aspects can comprise from about 1 to about 99 parts by weight conventional polycarbonate and from about 99 to about 1 parts by weight of a disclosed tetrapolymer.







DETAILED DESCRIPTION Of The INVENTION

The present invention can be understood more readily by reference to the following detailed description, examples, drawings, and claims, and their previous and following description. However, before the present devices, systems, and/or methods are disclosed and described, it is to be understood that this invention is not limited to the specific devices, systems, and/or methods disclosed unless otherwise specified, as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting.


The following description of the invention is provided as an enabling teaching of the invention in its best, currently known embodiment. To this end, those of ordinary skill in the relevant art will recognize and appreciate that many changes can be made to the various aspects of the invention described herein, while still obtaining the beneficial results of the present invention. It will also be apparent that some of the desired benefits of the present invention can be obtained by selecting some of the features of the present invention without utilizing other features. Accordingly, those of ordinary skill in the relevant art will recognize that many modifications and adaptations to the present invention are possible and can even be desirable in certain circumstances and are a part of the present invention. Thus, the following description is provided as illustrative of the principles of the present invention and not in limitation thereof.


As used throughout, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a “branching agent” can include two or more such branching agents unless the context indicates otherwise.


Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, another aspect 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 aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.


All ranges disclosed herein are inclusive of the endpoints and are independently combinable. The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value; they are sufficiently imprecise to include values approximating these ranges and/or values. 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. As an example, for the recitation of numeric ranges herein, each intervening number there between with the same degree of precision is explicitly contemplated—for the range of 6-9, the numbers 7 and 8 are contemplated in addition to 6 and 9, and for the range 6.0-7.0, the number 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, and 7.0 are explicitly contemplated.


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.


As used herein, the terms “optional” or “optionally” mean that the subsequently described event, condition, component, or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.


As used herein, the term polycarbonate is not intended to refer to a specific polycarbonate or group of polycarbonate but rather refers to the any one of the class of compounds containing a repeating chain of carbonate groups. Exemplary polycarbonates include aromatic polycarbonates. Aromatic Polycarbonates conventionally manufactured through a transesterification reaction of an one or more aromatic dihydroxy compound(s) and a carbonic acid diester in the presence of one or more catalyst(s). The one or more dihydroxy aromatic compound(s)s that may be used in the transesterification reaction may include a dihydric phenol or a combination of dihydric phenols or a bisphenol or a combination of bisphenols or a combination of one more dihydric phenol(s) with one or more bisphenol(s). As one of ordinary skill in the art will appreciate, commonly used examples of dihydric phenols include but are not limited to resorcinol, catechol, hydroquinone, or 2-methyl hydroquioninone and the like. Examples of bisphenols include but are not limited to, Bisphenol A (BPA), 4,4′dihydroxybiphenyl, 1,1-bis(4-dihydroxy-3-methylphenyl)cyclohexane, 4,4′-(1-phenylethylidene)bisphenol, 4,4′dihydroxydiphenylsulfone, 4,4′-cyclohexylidenebisphenol and the like. Similarly, commonly used carbon acid diester reactants include diaryl carbonates, such as diphenyl carbonate (DPC) or activated diaryl carbonates, such as bismethylsalicylcarbonate (BMSC). In the following discussions of specific embodiments of the invention, DPC and BPA will be used as exemplary reactants for the formation of a polycarbonate. However, this usage is for convenience only and reflects the fact that DPC and BPA are among the most common reactants used in production of polycarbonates. It is not intended to limit the invention to these starting materials.


As used herein, the term “transparent” includes embodiments where the level of transmittance for a disclosed polymer is greater than 50%, including exemplary transmittance values of at least 60%, 70%, 80%, 85%, 90%, and 95%, or any range of transmittance values derived from the above exemplified values. Transmittance can be measured for a disclosed polymer according to ASTM method D1003.


As used herein, the term “haze” includes embodiments where the level of haze for a disclosed polymer is less than 80%, including haze values of less than 70%, 60%, 50%, 40%, 30%, 20%, 10%, 5%, and 1%, or any range derived from these values. Haze can be measured for a disclosed polymer according to ASTM method D1003.


As summarized above, in a first aspect the present invention provides a transparent tetrapolymer composition that is capable of use in forming polymer blends with any one or more conventional polycarbonate polymers. As the name tetrapolymer implies, the tetrapolymer comprises four co-monomer components: a styrene component, and acrylonitrile, a methylmethacrylate component, and an α-methylstyrene component. Further, the tetrapolymer exhibits a refractive index value “n” that is at least substantially similar to a refractive index value “n” of a conventional polycarbonate such that any resulting blend of the disclosed tetrapolymer with a conventional polycarbonate exhibits a refractive index value “n” that itself is at least substantially similar to a refractive index value “n” of a conventional polycarbonate. Optionally, the disclosed tetrapolymer compositions may also comprise minor amounts of one or more refractive index modifier additives to ensure that the refractive index of the composition is substantially similar to the refractive index value “n” of a conventional polycarbonate of Bisphenol-A. To the extent that one or more optional refractive index modifier additives are to be used, one or ordinary skill in the art could readily determine the desired additive and the desired amount to be used through no more than routine experimentation.


As one of ordinary skill in the art will appreciate, a refractive index or index of refraction of a substance or medium is a measure of the speed of light in that substance or medium. It is typically expressed as a ratio of the speed of light in vacuum relative to that in the considered substance or medium. This can be written mathematically as:

n=speed of light in a vacuum/speed of light in medium

For example, the refractive index of water is 1.33, meaning that light travels 1.33 times faster in vacuum than it does in water. Conventional polycarbonate has a refractive index “n” within the range of about 1.584 to 1.588, with a targeted value of about 1.586. As such, according to embodiments of the invention, the tetrapolymer exhibits a refractive index value “n” that is similarly in the range of from 1.584 to 1.588. In a further embodiment, the tetrapolymer exhibits a refractive index value “n” of about 1.586.


Each of the four co-monomers present in the tetrapolymer also exhibit their own specific refractive indices “n.” Specifically, styrene monomer exhibits a refractive index of about 1.5894, acrylonitrile monomer exhibits a refractive index of about 1.5187; methylmethacrylate monomer exhibits a refractive index of about 1.4893; and α-methylstyrene monomer exhibits a refractive index of about 1.6100. Thus, when utilized to prepare the tetrapolymer of the invention, each co-monomer should be present in a relative weight percent or part by weight amount such that the refractive index of the resulting tetrapolymer exhibits the desired refractive index.


For example, according to embodiments of the invention the tetrapolymer comprises “w” parts by weight styrene; “x” parts by weight acrylonitrile; “y” parts by weight methylmethacrylate; and “z” parts by α-methylstyrene, wherein the values of w, x, y, and z satisfy the following relationship:









(

w
×
1.5894

)

+

(

x
×
1.5187

)

+

(

y
×
1.4893

)

+

(

z
×
1.6100

)


100

=

1.5869
.






Exemplary tetrapolymer compositions can therefore comprise: a) about 1 to 68 parts by weight styrene; b) about 1 to 17 parts by weight acrylonitrile; c) about 0.5 to 13 parts by weight methylmethacrylate; and d) about 22 to 78 parts by α-methylstyrene, wherein the total parts by weight of components a), b), c), and d) is about 100 parts by weight. To that end, it will be appreciated in view of the foregoing description that specific tetrapolymer formulations as disclosed herein exhibiting the desired refractive index can be identified by one of ordinary skill in the art through routine experimentation. Further, specific non-limiting examples of tetrapolymer formulations of the invention having the desired refractive index are set forth in the Examples which follow.


According to aspects of the invention, the disclosed cotetrapolymers are preferably transparent. To that end, the disclosed tetrapolymers can exhibit a level of transmittance that is greater than 50%, including exemplary transmittance values of at least 60%, 70%, 80%, 85%, 90%, and 95%, or any range of transmittance values derived from the above exemplified values. In still further aspects, the disclosed cotetrapolymers exhibit relatively high levels of transparency characterized by exhibiting a transmittance of at least 80%. Transparency can be measured for a disclosed polymer according to ASTM method D1003.


According to aspects of the invention, the disclosed cotetrapolymers preferably exhibit a level of “haze” that is less than 80%, including haze values of less than 70%, 60%, 50%, 40%, 30%, 20%, 10%, 5%, and 1%, or any range derived from these values. In still further aspects, the disclosed cotetrapolymers exhibit relatively low levels of haze characterized by exhibiting a “haze” value that is less than 20%. Haze can be measured for a disclosed polymer according to ASTM method D1003.


The tetrapolymers of the present invention can be prepared by any conventionally known copolymerization techniques whereby an appropriate amount of a styrene component, an acrylonitrile component, a methylmethacrylate component, and an α-methylstyrene component are copolymerized. In further aspects of the invention, the disclosed tetrapolymers can be blended with a conventional polycarbonate component to provide a resulting polymer blend exhibiting a refractive index “n” substantially similar or even the same as the refractive index of the conventional polycarbonate present in the polymer blend. As such, according to embodiments of the invention, polymer blends comprising the disclosed tetrapolymer exhibit a refractive index value “n” that is similarly in the range of from 1.584 to 1.588. In a further embodiment, the disclosed polymer blends can exhibit a refractive index value “n” of about 1.586.


Disclosed polymer blends can comprise any desired amount of the conventional polycarbonate component relative to the this disclosed tetrapolymer component. For example, disclosed polymer blends can comprise from 1 to 99 weight % of a conventional polycarbonate, including exemplary amounts of 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, and even 95 weight %. Likewise, the disclosed polymer blends can also comprise any desired amount of the tetrapolymer component. For example, disclosed polymer blends can comprise from 1 to 99 weight % of the disclosed tetrapolymer, including exemplary amounts of 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, and even 95 weight %.


The disclosed polymer blends according to the invention may further comprise conventionally used additives for polymers or for polymer mixtures, for example, fillers, reinforcing fibres, stabilisers, flame-retardants, dyes and pigments. Still further, the polymer blends according to the invention may be prepared according to the conventionally used methods of preparing polymer mixtures.


In still further aspects of the invention, it should be understood and appreciated that the disclosed polymer blends can further exhibit levels of haze and transparency that are at least substantially similar to the levels of haze and transparency that can be exhibited by the disclosed tetrapolymers. For example, and without limitation, a disclosed polymer blend can exhibit a level of transmittance that is greater than 50%, including exemplary transmittance values of at least 60%, 70%, 80%, 85%, 90%, and 95%, or any range of transmittance values derived from the above exemplified values. In still further aspects, the disclosed polymer blends can exhibit relatively high levels of transparency characterized by exhibiting a transmittance of at least 80%. The disclosed polymer blends can also exhibit a level of “haze” that is less than 80%, including haze values of less than 70%, 60%, 50%, 40%, 30%, 20%, 10%, 5%, and 1%, or any range derived from these values. In still further aspects, the disclosed polymer blends exhibit relatively low levels of haze characterized by exhibiting a “haze” value that is less than 20%.


EXAMPLES

The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the methods, devices, and systems disclosed and claimed herein are made and evaluated, and are intended to be purely exemplary and are not intended to limit the disclosure. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in C or is at ambient temperature, and pressure is at or near atmospheric.


In this example, a design of experiment analysis was performed to evaluate possible combinations of the four disclosed co-monomer components: styrene, acrylonitrile, methylmethacrylate, and α-methylstyrene component. The target of the study was to synthesize copolymers having a refractive index of a conventional polycarbonate of bisphenol A (1.5869), by copolymerizing the appropriate amounts of each of the four comonomers without affecting its blend compatibility and other performance and processing properties when blended with polycarbonate. The respective refractive index values for the four co-monomers used in synthesizing the disclosed tetrapolymers are set forth in Table 1 below:












TABLE 1







Co-monomer
Refractive Index




















A
Styrene
1.5894



B
Acrylonitrile
1.5187



C
Methylmethacrylate
1.4893



D
α-methylstyrene
1.6100










The overall refractive index for the co-polymers generated in the design of experiment study was calculated on the basis of weight percent of respective monomer in total 100 parts by weight of a respective polymer formulation. The design of experiment results for various combinations of the four respective monomers are set forth in Table 2 below, where column A represents the parts by weight amount of styrene comonomer, column B represents the parts by weight amount of acrylonitrile monomer, column C represents the parts by weight amount of methylmethacrylate monomer, and column D represents the parts by weight amount of α-methylstyrene monomer. Column RI reports the calculated refractive index for the respective copolymers.
















TABLE 2








A
B
C
D
RI























1
80
0
20
0
1.5694



2
55
15
10
20
1.5729



3
60
20
20
0
1.5552



4
0
20
0
80
1.5917



5
80
20
0
0
1.5753



6
0
20
20
60
1.5676



7
0
0
20
80
1.5859



8
30
20
20
30
1.5614



9
45
10
0
45
1.5916



10
80
20
0
0
1.5753



11
80
6.7
6.7
6.7
1.5794



12
20
0
0
80
1.6059



13
45
0
10
45
1.5887



14
0
0
20
80
1.5859



15
80
0
0
20
1.5935



16
20
15
10
55
1.5801



17
0
20
0
80
1.5917



18
80
0
20
0
1.5694



19
45
10
0
45
1.5916



20
0
10
10
80
1.5888










Further review and analysis of the design of experiment results set forth in Table 2 provided 9 specific exemplary formulations that can be prepared from the four co-monomers described above and which results in a refractive index value “n” of 1.5869. These 9 additional formulations are set forth in Table 3 below:















TABLE 3









Methyl-





Styrene
Acrylonitrile
methacrylate
α-methylstyrene
RI





















1
35.85
12.92
3.24
47.88
1.5869


2
8.12
8.59
11.25
72.03
1.5869


3
28.83
14.45
3.29
53.43
1.5869


4
38.87
4.16
9.36
47.61
1.5869


5
68.46
9.16
0.52
21.85
1.5869


6
1.10
8.23
12.72
77.95
1.5869


7
18.27
17.05
3.13
61.56
1.5869


8
54.07
0.96
9.18
35.79
1.5869


9
66.77
7.16
2.33
23.74
1.5869









A second design of experiment analysis was performed to further evaluate possible combinations of the four disclosed co-monomer components that are capable of providing a refractive index at least substantially similar to a conventional polycarbonate of bisphenol A and which similarly exhibit a relatively high level of transparency (at least 80%) and a relatively low level of haze (less than 20%). In this study, various combinations and amounts of the co-monomers were copolymerized. The respective refractive index values for the four co-monomers used in synthesizing the disclosed tetrapolymers are again those as set forth in Table 1 above. The overall refractive index for the co-polymers generated in the design of experiment study was calculated on the basis of weight percent of respective monomer in total 100 parts by weight of a respective polymer formulation.


The results of this second design of experiment analysis are set forth in Table 4 where the calculated refractive index, measured percent transparency, and measured percent haze are shown. As before, column A represents the parts by weight amount of styrene comonomer, column B represents the parts by weight amount of acrylonitrile monomer, column C represents the parts by weight amount of methylmethacrylate monomer, and column D represents the parts by weight amount of α-methylstyrene monomer. Column RI reports the calculated refractive index for the respective copolymers. The percent transmission and percent haze were measured for a blend of 95% Lexan 101-111N and 5% of the indicated copolymer. Sample C0 represents a Lexan 101-111N polycarbonate resin control available from SABIC Innovative Plastics.


Comparative samples C1 through C21 depict the results of several samples where a combination of relatively high transparency and relatively low haze was not achieved. Though many of the reported comparative samples C1 through C21 are themselves inventive cotetrapolymers of the invention, samples C2-C4, C6-C7, C11-C12, C14-C16, and C19-C20 represent comparative samples of copolymers where all four co-monomers were not present. Further, samples Ex. 1, Ex. 2, and Ex. 3 represent three specific and exemplary inventive samples that were identified as exhibiting a calculated refractive index identical to that of the control polycarbonate resin and which exhibited a relatively high transparency (greater than 80%) and a relatively low level of haze (less than 20%).

















TABLE 4







A
B
C
D
RI
% Trans
% Haze























C0
0
0
0
0
1.5860
90.1
1.1


C1
53.0
11.0
11.0
25.0
1.5758
70.1
55.0


C2
70.0
0.0
2.5
27.5
1.5926
77.8
11.5


C3
37.5
25.0
0.0
37.5
1.5795
75.5
16.8


C4
25.0
0.0
25.0
50.0
1.5747
75.1
20.4


C5
25.0
25.0
25.0
25.0
1.5519
64.2
84.3


C6
25.0
15.0
0.0
60.0
1.5912
78.6
18.0


C7
50.0
0.0
0.0
50.0
1.5997
78.4
31.4


C8
25.0
25.0
12.5
37.5
1.5669
67.2
34.9


C9
37.5
12.5
25.0
25.0
1.5607
66.6
35.3


C10
37.5
25.0
12.5
25.0
1.5644
63.6
47.6


C11
50.0
25.0
0.0
25.0
1.5769
72.5
30.5


C12
70.0
0.0
2.5
27.5
1.5926
79.2
32.9


C13
37.8
8.0
16.4
37.8
1.5750
78.0
23.3


C14
50.0
0.0
25.0
25.0
1.5695
65.6
37.0


C15
25.0
0.0
25.0
50.0
1.5747
75.4
21.2


C16
25.0
15.0
0.0
60.0
1.5912
77.7
18.1


C17
34.9
3.9
5.1
56.1
1.5931
79.0
25.4


C18
50.0
0.0
25.0
25.0
1.5695
69.0
28.4


C19
75.0
25.0
0.0
0.0
1.5717
71.9
22.9


C20
40.0
25.0
35.0
0.0
1.5367
47.7
98.7


C21
0.0
25.0
35.0
40.0
1.5449
53.6
94.4


Ex 1
38.32
16.32
1.00
44.36
1.586
83.8
10.1


Ex 2
27.33
11.56
6.48
54.64
1.586
83.6
17.2


Ex 3
32.26
4.13
10.74
49.87
1.586
83.8
12.5









Review of the data in Table 4 shows that for the exemplified samples tetrapolymer polymer formulations comprising all four of the comonomers in Table 1 were necessary in order to obtain both high transparency (>80%) and low haze (<20%). In contrast, comparative examples C2, C3, C6 and C16 are tripolymers that show haze values less than 20%, but did not achieve percent transmission values of over 80%.

Claims
  • 1. A tetrapolymer composition, comprising: a) styrene;b) acrylonitrile;c) methylmethacrylate; andd) α-methylstyrene,
  • 2. The tetrapolymer composition of claim 1, wherein the tetrapolymer exhibits a refractive index value “n” of about 1.586.
  • 3. The tetrapolymer composition of claim 1, comprising: a) 1 to 68 parts by weight styrene;b) 1 to 17 parts by weight acrylonitrile;c) 0.5 to 13 parts by weight methylmethacrylate; andd) 22 to 78 parts by α-methylstyrene,
  • 4. The tetrapolymer composition of claim 1, comprising: a) about 35.85 parts by weight styrene;b) about 12.92 parts by weight acrylonitrile;c) about 3.24 parts by weight methylmethacrylate; andd) about 47.98 parts by α-methylstyrene.
  • 5. The tetrapolymer composition of claim 1, comprising: a) about 8.12 parts by weight styrene;b) about 8.59 parts by weight acrylonitrile;c) about 11.26 parts by weight methylmethacrylate; andd) about 72.03 parts by α-methylstyrene.
  • 6. The tetrapolymer composition of claim 1, comprising: a) about 28.83 parts by weight styrene;b) about 14.45 parts by weight acrylonitrile;c) about 3.29 parts by weight methylmethacrylate; andd) about 53.43 parts by α-methylstyrene.
  • 7. The tetrapolymer composition of claim 1, comprising: a) about 38.87 parts by weight styrene;b) about 4.16 parts by weight acrylonitrile;c) about 9.36 parts by weight methylmethacrylate; andd) about 47.61 parts by α-methylstyrene.
  • 8. The tetrapolymer composition of claim 1, comprising: a) about 68.46 parts by weight styrene;b) about 9.16 parts by weight acrylonitrile;c) about 0.52 parts by weight methylmethacrylate; andd) about 21.85 parts by α-methylstyrene.
  • 9. The tetrapolymer composition of claim 1, comprising: a) about 1.10 parts by weight styrene;b) about 8.23 parts by weight acrylonitrile;c) about 12.72 parts by weight methylmethacrylate; andd) about 77.95 parts by α-methylstyrene.
  • 10. The tetrapolymer composition of claim 1, comprising: a) about 18.27 parts by weight styrene;b) about 17.05 parts by weight acrylonitrile;c) about 3.13 parts by weight methylmethacrylate; andd) about 61.56 parts by α-methylstyrene.
  • 11. The tetrapolymer composition of claim 1, comprising: a) about 54.07 parts by weight styrene;b) about 0.96 parts by weight acrylonitrile;c) about 9.18 parts by weight methylmethacrylate; andd) about 35.79 parts by α-methylstyrene.
  • 12. The tetrapolymer composition of claim 1, comprising: a) about 66.77 parts by weight styrene;b) about 7.16 parts by weight acrylonitrile;c) about 2.33 parts by weight methylmethacrylate; andd) about 23.74 parts by α-methylstyrene.
  • 13. The tetrapolymer composition of claim 1, comprising: a) about 23.4 parts by weight styrene;b) about 12.0 parts by weight acrylonitrile;c) about 6.0 parts by weight methylmethacrylate; andd) about 58.6 parts by α-methylstyrene.
  • 14. The tetrapolymer composition of claim 1, comprising: a) about 38.32 parts by weight styrene;b) about 16.32 parts by weight acrylonitrile;c) about 1.0 parts by weight methylmethacrylate; andd) about 44.36 parts by α-methylstyrene.
  • 15. The tetrapolymer composition of claim 1, comprising: a) about 27.33 parts by weight styrene;b) about 11.56 parts by weight acrylonitrile;c) about 6.48 parts by weight methylmethacrylate; andd) about 54.63 parts by α-methylstyrene.
  • 16. The tetrapolymer composition of claim 1, comprising: a) about 32.26 parts by weight styrene;b) about 4.13 parts by weight acrylonitrile;c) about 10.74 parts by weight methylmethacrylate; andd) about 49.87 parts by α-methylstyrene.
  • 17. The tetrapolymer composition of claim 1, wherein the composition exhibits a level of transparency greater than 80% and a level of haze less than 20%.
  • 18. The tetrapolymer composition of claim 1, comprising: a) “w” parts by weight styrene;b) “x” parts by weight acrylonitrile;c) “y” parts by weight methylmethacrylate; andd) “z” parts by α-methylstyrene,
  • 19. A polymer blend composition, comprising: a) 1 to 99 parts by weight polycarbonate; andb) 1 to 99 parts by weight of the tetrapolymer of claim 1,
  • 20. The polymer blend composition of claim 19, wherein the tetrapolymer of b) exhibits a refractive index value “n” of about 1.586.
  • 21. The polymer blend composition claim 19, wherein the tetrapolymer of b) comprises: a) 1 to 68 parts by weight styrene;b) 1 to 17 parts by weight acrylonitrile;c) 0.5 to 13 parts by weight methylmethacrylate; andd) 22 to 78 parts by α-methylstyrene,
  • 22. The polymer blend composition of claim 19, wherein the tetrapolymer of b) comprises: a) “w” parts by weight styrene;b) “x” parts by weight acrylonitrile;c) “y” parts by weight methylmethacrylate; andd) “z” parts by α-methylstyrene,
  • 23. The polymer blend composition of claim 19, wherein the composition exhibits a level of transparency greater than 80% and a level of haze less than 20%.
  • 24. The polymer blend composition of claim 23, comprising: a) about 95 parts by weight polycarbonate; andb) about 5 parts by weight of the tetrapolymer of claim 1.
  • 25. The polymer blend composition of claim 23, comprising: a) about 90 parts by weight polycarbonate; andb) about 10 parts by weight of the tetrapolymer of claim 1.
US Referenced Citations (320)
Number Name Date Kind
6184312 Yamamoto et al. Feb 2001 B1
6187896 Nakajima et al. Feb 2001 B1
6194497 Willems et al. Feb 2001 B1
6194536 Schmidt et al. Feb 2001 B1
6239216 Montanari et al. May 2001 B1
6251975 Kobayashi et al. Jun 2001 B1
6274670 Adedeji et al. Aug 2001 B1
6281299 Saito et al. Aug 2001 B1
6284824 Iji et al. Sep 2001 B1
6291585 Tomari et al. Sep 2001 B1
6294251 Minagawa et al. Sep 2001 B1
6296785 Nelson et al. Oct 2001 B1
6296920 Buehler et al. Oct 2001 B1
6297303 Kobayashi et al. Oct 2001 B1
6297314 Hintze-Bruning et al. Oct 2001 B1
6313254 Meijs et al. Nov 2001 B1
6313259 Miyamoto et al. Nov 2001 B1
6329060 Barkac et al. Dec 2001 B1
6335061 Kanamori et al. Jan 2002 B1
6337139 Sapper Jan 2002 B1
6348604 Nelson et al. Feb 2002 B1
6359069 Moulinie et al. Mar 2002 B1
6372304 Sano et al. Apr 2002 B1
6376606 Adedeji Apr 2002 B1
6383625 Shoshi et al. May 2002 B1
6383641 Kondou et al. May 2002 B1
6399205 Sandlin et al. Jun 2002 B1
6399718 Rink et al. Jun 2002 B1
6410678 Ishida et al. Jun 2002 B1
6426128 Kimmel et al. Jul 2002 B1
6428856 Masuda et al. Aug 2002 B1
6448365 Funakoshi et al. Sep 2002 B1
6458913 Honigfort et al. Oct 2002 B1
6465953 Duggal Oct 2002 B1
6509406 Brenner et al. Jan 2003 B1
6512026 Ott et al. Jan 2003 B1
6512044 Wilke Jan 2003 B1
6518340 Fishburn et al. Feb 2003 B1
RE38050 Hachiya et al. Mar 2003 E
6537636 Wisnudel et al. Mar 2003 B1
6569919 Noguchi et al. May 2003 B1
6620868 Wilke Sep 2003 B1
6623858 Yabe et al. Sep 2003 B1
6656601 Kawachi et al. Dec 2003 B1
6660374 Smetana et al. Dec 2003 B2
6680350 Dobler Jan 2004 B1
6696148 Seino et al. Feb 2004 B1
6716368 Schottland et al. Apr 2004 B1
6740730 Kratschmer et al. May 2004 B1
6818258 Kaneko et al. Nov 2004 B2
6818304 Miyako et al. Nov 2004 B2
6846567 Ekinaka et al. Jan 2005 B1
6855779 Nagata et al. Feb 2005 B1
6979704 Mayer et al. Dec 2005 B1
7074351 Dobler et al. Jul 2006 B2
7169834 Dobler et al. Jan 2007 B2
7217749 Gencer et al. May 2007 B2
7253215 Takahashi et al. Aug 2007 B2
7270775 Kubik et al. Sep 2007 B2
7479308 Baumgart et al. Jan 2009 B2
7517944 Kunishi et al. Apr 2009 B2
7541418 Gerace et al. Jun 2009 B2
7592070 Takanami et al. Sep 2009 B2
7678881 Nishichi et al. Mar 2010 B2
7767738 Gaggar et al. Aug 2010 B2
20010018487 Itagaki et al. Aug 2001 A1
20010021742 Finberg et al. Sep 2001 A1
20010028569 Hanasaki Oct 2001 A1
20010034419 Kanayama et al. Oct 2001 A1
20010036557 Ingrim et al. Nov 2001 A1
20010036986 Matsumura et al. Nov 2001 A1
20010044003 Gallucci et al. Nov 2001 A1
20010050356 Crano et al. Dec 2001 A1
20020002225 Reil Jan 2002 A1
20020007078 Lin Jan 2002 A1
20020010273 Matsumura et al. Jan 2002 A1
20020032299 Matsumoto et al. Mar 2002 A1
20020035207 Hariharan et al. Mar 2002 A1
20020082310 Barnes, II et al. Jun 2002 A1
20020086962 Upper Jul 2002 A1
20020103328 Funakoshi et al. Aug 2002 A1
20020107334 Krishnan et al. Aug 2002 A1
20020111428 Gaggar et al. Aug 2002 A1
20020127395 Kuwabara Sep 2002 A1
20020128357 Goossens et al. Sep 2002 A1
20020132122 Marutsuka Sep 2002 A1
20020135092 Risley Sep 2002 A1
20020155296 Jonas et al. Oct 2002 A1
20030007764 Hirota Jan 2003 A1
20030022963 Parsons Jan 2003 A1
20030022967 Dobler et al. Jan 2003 A1
20030022971 Boyd et al. Jan 2003 A1
20030025228 Prieur-Blanc et al. Feb 2003 A1
20030026992 Anada et al. Feb 2003 A1
20030027905 Mahood et al. Feb 2003 A1
20030032725 Gaggar et al. Feb 2003 A1
20030060548 Goossens et al. Mar 2003 A1
20030071247 Petrovskaia et al. Apr 2003 A1
20030087102 Yamaya et al. May 2003 A1
20030108716 Nun et al. Jun 2003 A1
20030108735 Hoppe et al. Jun 2003 A1
20030113544 Tokuda et al. Jun 2003 A1
20030117707 Uchida et al. Jun 2003 A1
20030124351 Sakamoto et al. Jul 2003 A1
20030129409 Tacke-Willemsen Jul 2003 A1
20030129931 Konno et al. Jul 2003 A1
20030130381 Joachimi et al. Jul 2003 A1
20030130390 Gorny et al. Jul 2003 A1
20030134130 Yano et al. Jul 2003 A1
20030158309 Ono et al. Aug 2003 A1
20030158321 Watanabe et al. Aug 2003 A1
20030162025 Gorny et al. Aug 2003 A1
20030164477 Zhou et al. Sep 2003 A1
20030173546 Hiroshi et al. Sep 2003 A1
20030175499 Phillips Sep 2003 A1
20030195295 Mahood et al. Oct 2003 A1
20030195329 Funakoshi et al. Oct 2003 A1
20030197301 Winkler et al. Oct 2003 A1
20030219549 Shimizu Nov 2003 A1
20040009346 Jang et al. Jan 2004 A1
20040023041 O'Keefe et al. Feb 2004 A1
20040028908 Vollenberg et al. Feb 2004 A1
20040028920 Fujita et al. Feb 2004 A1
20040071998 Higuchi et al. Apr 2004 A1
20040091725 Chang et al. May 2004 A1
20040096683 Ikeda et al. May 2004 A1
20040096776 Tanigawa et al. May 2004 A1
20040106732 Tsuji et al. Jun 2004 A1
20040122168 Murray Jun 2004 A1
20040127594 Yang et al. Jul 2004 A1
20040127653 Ellington et al. Jul 2004 A1
20040152806 Koga et al. Aug 2004 A1
20040152810 Takenaka et al. Aug 2004 A1
20040176600 Juhue et al. Sep 2004 A1
20040180193 Oda et al. Sep 2004 A1
20040185198 Sisson et al. Sep 2004 A1
20040185268 Kumar et al. Sep 2004 A1
20040186216 Satoh et al. Sep 2004 A1
20040202879 Xia et al. Oct 2004 A1
20040220330 DeRudder et al. Nov 2004 A1
20040224111 Sisson et al. Nov 2004 A1
20040236069 Clements et al. Nov 2004 A1
20040241375 Koya et al. Dec 2004 A1
20040249061 Sunkara et al. Dec 2004 A1
20040249069 Nakai et al. Dec 2004 A1
20040253402 Der Wal et al. Dec 2004 A1
20040266942 Ramlow Dec 2004 A1
20050009968 Singh et al. Jan 2005 A1
20050017384 Tamai et al. Jan 2005 A1
20050065293 Vollenberg et al. Mar 2005 A1
20050075466 Oguro et al. Apr 2005 A1
20050084643 Steinberger et al. Apr 2005 A1
20050101687 Kim et al. May 2005 A1
20050101757 Glasgow et al. May 2005 A1
20050106394 Osterloh May 2005 A1
20050118429 Taylor Jun 2005 A1
20050137358 Zhang et al. Jun 2005 A1
20050137359 Agarwal et al. Jun 2005 A1
20050137360 Shaikh et al. Jun 2005 A1
20050143553 Morishita et al. Jun 2005 A1
20050147778 Tai et al. Jul 2005 A1
20050158555 Anders et al. Jul 2005 A1
20050182167 Goodson et al. Aug 2005 A1
20050188895 Chamberlain et al. Sep 2005 A1
20050196618 Knox et al. Sep 2005 A1
20050196626 Knox et al. Sep 2005 A1
20050203257 Uchida et al. Sep 2005 A1
20050215677 Gaggar et al. Sep 2005 A1
20050215750 Koga et al. Sep 2005 A1
20050233070 Pellerite et al. Oct 2005 A1
20050234178 Andrews Oct 2005 A1
20060004152 Acar et al. Jan 2006 A1
20060014880 Zhong et al. Jan 2006 A1
20060020075 Basham et al. Jan 2006 A1
20060052486 Fujita Mar 2006 A1
20060063891 Ruzette et al. Mar 2006 A1
20060078688 DeSimone et al. Apr 2006 A1
20060078717 Yamaya et al. Apr 2006 A1
20060084732 Shakely et al. Apr 2006 A1
20060106159 Ogawa et al. May 2006 A1
20060121204 Nakae et al. Jun 2006 A1
20060132912 Haese et al. Jun 2006 A1
20060134366 Haese et al. Jun 2006 A1
20060134426 Horio et al. Jun 2006 A1
20060135690 Juikar et al. Jun 2006 A1
20060142527 Glasgow et al. Jun 2006 A1
20060148986 Glasgow et al. Jul 2006 A1
20060197246 Hale et al. Sep 2006 A1
20060198999 Rudiger et al. Sep 2006 A1
20060235116 Lazzari et al. Oct 2006 A1
20060247372 Faler et al. Nov 2006 A1
20060264582 Mullen et al. Nov 2006 A1
20060281846 Hager et al. Dec 2006 A1
20060281860 Higuchi et al. Dec 2006 A1
20060289841 Ito et al. Dec 2006 A1
20060292306 Goebel et al. Dec 2006 A1
20070015881 Hale Jan 2007 A1
20070032607 Fuji Feb 2007 A1
20070045596 King et al. Mar 2007 A1
20070054983 Pudleiner et al. Mar 2007 A1
20070077399 Borowiec et al. Apr 2007 A1
20070077414 Rudiger et al. Apr 2007 A1
20070078220 Pudleiner et al. Apr 2007 A1
20070088126 Pudleiner et al. Apr 2007 A1
20070100088 Gallucci et al. May 2007 A1
20070112123 Sekine May 2007 A1
20070128442 Buehler Jun 2007 A1
20070135586 Chakravarti et al. Jun 2007 A1
20070155867 Ikari et al. Jul 2007 A1
20070173581 Hager et al. Jul 2007 A1
20070179252 Lamberts et al. Aug 2007 A1
20070191519 Jiao et al. Aug 2007 A1
20070210287 Guerra Sep 2007 A1
20070213451 Nabeshima et al. Sep 2007 A1
20070213459 Tamai et al. Sep 2007 A1
20070224367 Rudiger et al. Sep 2007 A1
20070225416 Faber et al. Sep 2007 A1
20070225436 Tamai et al. Sep 2007 A1
20070228587 Ikari Oct 2007 A1
20070259117 Archey et al. Nov 2007 A1
20070270530 Kamo et al. Nov 2007 A1
20070275234 Lim et al. Nov 2007 A1
20070293600 Tamura Dec 2007 A1
20080000917 Agarwal et al. Jan 2008 A1
20080012032 Bhandarkar et al. Jan 2008 A1
20080014451 Metz et al. Jan 2008 A1
20080021177 Boyles et al. Jan 2008 A1
20080029933 Higashiizumi et al. Feb 2008 A1
20080038549 Griswold et al. Feb 2008 A1
20080071020 Kobayashi Mar 2008 A1
20080075936 McGurran et al. Mar 2008 A1
20080090958 Rudiger et al. Apr 2008 A1
20080102262 Esaki et al. May 2008 A1
20080103235 Hale May 2008 A1
20080107858 Meyer et al. May 2008 A1
20080119618 Agarwal et al. May 2008 A1
20080142761 Charati et al. Jun 2008 A1
20080145547 Schneider et al. Jun 2008 A1
20080146759 Takashima et al. Jun 2008 A1
20080161483 Kind Jul 2008 A1
20080182094 Meyer et al. Jul 2008 A1
20080182930 Adachi Jul 2008 A1
20080194732 Patterson Aug 2008 A1
20080214706 Peter et al. Sep 2008 A1
20080227901 Lefevre et al. Sep 2008 A1
20080233395 Masuda Sep 2008 A1
20080233405 Dronzek, Jr. Sep 2008 A1
20080242873 Basale et al. Oct 2008 A1
20080262117 Avakian et al. Oct 2008 A1
20080269386 Chakravarti et al. Oct 2008 A1
20080269399 Chakravarti et al. Oct 2008 A1
20080269400 Chakravarti et al. Oct 2008 A1
20080283189 Dhawan et al. Nov 2008 A1
20090012205 Nakada et al. Jan 2009 A1
20090014687 Kaskel et al. Jan 2009 A1
20090029147 Tang et al. Jan 2009 A1
20090029154 Hala et al. Jan 2009 A1
20090029172 Isozaki Jan 2009 A1
20090030129 Chakravarti et al. Jan 2009 A1
20090040618 Iyama Feb 2009 A1
20090043053 Gorny et al. Feb 2009 A1
20090062436 Breiner Mar 2009 A1
20090062438 van de Grampel et al. Mar 2009 A1
20090076222 Pugne Mar 2009 A1
20090093568 Lacock et al. Apr 2009 A1
20090111951 Lin et al. Apr 2009 A1
20090123698 Nishino et al. May 2009 A1
20090123721 Yang May 2009 A1
20090124744 Ishizaka et al. May 2009 A1
20090130295 Broguiere et al. May 2009 A1
20090136730 Nakano et al. May 2009 A1
20090142537 Hong et al. Jun 2009 A1
20090156732 Rajaraman et al. Jun 2009 A1
20090156737 Schindler et al. Jun 2009 A1
20090186967 Akada et al. Jul 2009 A1
20090203852 Urakami et al. Aug 2009 A1
20090208755 Isozaki et al. Aug 2009 A1
20090209707 Okunaka et al. Aug 2009 A1
20090259000 Urakami et al. Oct 2009 A1
20090274896 Takeshi et al. Nov 2009 A1
20090284603 Hsieh Nov 2009 A1
20090326110 Tanaka et al. Dec 2009 A1
20090326129 Rogunova et al. Dec 2009 A1
20100010172 Hong et al. Jan 2010 A1
20100021709 Niimi et al. Jan 2010 A1
20100028640 Isozaki et al. Feb 2010 A1
20100029855 Matsuoka et al. Feb 2010 A1
20100032608 Peri et al. Feb 2010 A1
20100048805 Nakabayashi Feb 2010 A1
20100048855 Kato et al. Feb 2010 A1
20100051882 Li et al. Mar 2010 A1
20100062272 Wursche et al. Mar 2010 A1
20100068504 Lin et al. Mar 2010 A1
20100069537 Breiner Mar 2010 A1
20100069543 Monden et al. Mar 2010 A1
20100076130 Miyake et al. Mar 2010 A1
20100076172 Tanabe et al. Mar 2010 A1
20100087578 Kawano et al. Apr 2010 A1
20100092755 Pudleiner et al. Apr 2010 A1
20100098943 Temchenko et al. Apr 2010 A1
20100104805 Ebina et al. Apr 2010 A1
20100105846 Kogure Apr 2010 A1
20100129649 Malinoski et al. May 2010 A1
20100152357 Kwon et al. Jun 2010 A1
20100160511 Jung et al. Jun 2010 A1
20100160545 Page Jun 2010 A1
20100160557 Murofushi et al. Jun 2010 A1
20100168272 Park et al. Jul 2010 A1
20100168295 Breiner et al. Jul 2010 A1
20100168370 Hatano et al. Jul 2010 A1
20100173134 Khokhlov et al. Jul 2010 A1
20100179286 Oda et al. Jul 2010 A1
20100180938 Nagato et al. Jul 2010 A1
20100184884 Miyake et al. Jul 2010 A1
20100184905 Chen Jul 2010 A1
20100186891 Ruch et al. Jul 2010 A1
20100190897 Maletzko et al. Jul 2010 A1
20100190953 Fuji et al. Jul 2010 A1
20100195313 Hiraishi et al. Aug 2010 A1
20100197867 Niimi et al. Aug 2010 A1
Foreign Referenced Citations (108)
Number Date Country
575810 Aug 1998 EP
628064 Apr 1999 EP
759459 Jan 2001 EP
704067 Aug 2001 EP
769508 Oct 2001 EP
803548 Oct 2001 EP
1142932 Oct 2001 EP
1142933 Oct 2001 EP
801750 Nov 2001 EP
1162482 Dec 2001 EP
703934 Feb 2002 EP
781792 Feb 2002 EP
1037885 Mar 2002 EP
728164 Apr 2002 EP
792468 Apr 2002 EP
960174 Apr 2002 EP
1195758 Apr 2002 EP
646446 Aug 2002 EP
786675 Nov 2002 EP
1112264 Nov 2002 EP
698631 Dec 2002 EP
1273935 Jan 2003 EP
797627 Apr 2003 EP
863185 May 2003 EP
994911 Aug 2003 EP
996692 Sep 2003 EP
1173509 Sep 2003 EP
1104794 Oct 2003 EP
1357145 Oct 2003 EP
912648 Nov 2003 EP
906366 Dec 2003 EP
970996 Jan 2004 EP
951390 Mar 2004 EP
1134075 Mar 2004 EP
1075963 May 2004 EP
736574 Jun 2004 EP
748259 Sep 2004 EP
834535 Sep 2004 EP
893481 Sep 2004 EP
829520 Oct 2004 EP
1085974 Nov 2004 EP
1475362 Nov 2004 EP
1484349 Dec 2004 EP
1022129 Jul 2005 EP
1550699 Jul 2005 EP
930341 Sep 2005 EP
954522 Oct 2005 EP
1595920 Nov 2005 EP
994871 Feb 2006 EP
1403842 Feb 2006 EP
1632514 Mar 2006 EP
1757422 Feb 2007 EP
1558402 Apr 2007 EP
1772667 Apr 2007 EP
1777255 Apr 2007 EP
1265944 May 2007 EP
890119 Jun 2007 EP
1925427 May 2008 EP
1856199 Jun 2008 EP
1583799 Nov 2008 EP
2009057 Dec 2008 EP
2045294 Apr 2009 EP
1543069 Dec 2009 EP
2172521 Apr 2010 EP
2206738 Jul 2010 EP
2213490 Aug 2010 EP
WO-0170719 Sep 2001 WO
WO-0183615 Nov 2001 WO
WO-0187267 Nov 2001 WO
WO-0196469 Dec 2001 WO
WO-0230682 Apr 2002 WO
WO-02079336 Oct 2002 WO
WO-02079342 Oct 2002 WO
WO-03004561 Jan 2003 WO
WO-03025638 Mar 2003 WO
WO-03050176 Jun 2003 WO
WO-03074579 Sep 2003 WO
WO-2004007587 Jan 2004 WO
WO-2004033543 Apr 2004 WO
WO-2004047674 Jun 2004 WO
WO-2004060999 Jul 2004 WO
WO-2004094142 Nov 2004 WO
WO-2004101653 Nov 2004 WO
WO-2004108815 Dec 2004 WO
WO-2005049729 Jun 2005 WO
WO-2005062081 Jul 2005 WO
WO-2005073268 Aug 2005 WO
WO-2005105938 Nov 2005 WO
WO-2007005429 Jan 2007 WO
WO-2007015273 Feb 2007 WO
WO-2007021555 Feb 2007 WO
WO-2007037859 Apr 2007 WO
WO-2007067538 Jun 2007 WO
WO-2007070092 Jun 2007 WO
WO-2007082811 Jul 2007 WO
WO-2008056851 May 2008 WO
WO-2008133776 Nov 2008 WO
WO 2008149260 Dec 2008 WO
WO-2008152741 Dec 2008 WO
WO-2009005318 Jan 2009 WO
WO-2009028817 Mar 2009 WO
WO-2009074554 Jun 2009 WO
WO-2009080974 Jul 2009 WO
WO-2009086246 Jul 2009 WO
WO-2009091155 Jul 2009 WO
WO-2009105565 Aug 2009 WO
WO-2010051525 May 2010 WO
WO-2010066982 Jun 2010 WO
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