CA1085083A - Thermoplastic molding composition comprising styrene- maleimide and polycarbonate - Google Patents
Thermoplastic molding composition comprising styrene- maleimide and polycarbonateInfo
- Publication number
- CA1085083A CA1085083A CA290,874A CA290874A CA1085083A CA 1085083 A CA1085083 A CA 1085083A CA 290874 A CA290874 A CA 290874A CA 1085083 A CA1085083 A CA 1085083A
- Authority
- CA
- Canada
- Prior art keywords
- maleimide
- styrene
- polycarbonate
- composition
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/06—Copolymers with vinyl aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Abstract
ABSTRACT OF THE DISCLOSURE Thermoplastic molding compositions consist of: a) 10-90% by weight copolymer of maleimide and styrene containing about 5-35% maleimide and 60-95% styrene; and b) 10-90% by weight of a polycarbonate of a dihydric phenol and a derivative of carbonic acid.
Description
1085~83 BACKGROUND 0~ INVENTION
; This invention relates to thermoplastic molding composition having an advantageous combination of charac-teristics not readily attainable from competitive materials.
Heretofore prior technologists have established that most thermoplastic polymers are insoluble in other thermoplastic polymers. Most attempts to mix pellets of different molding pellets at the time they are fed to an extruder lead to extrudates having fracture lines at the boundaries amongst the different compositions. Plastic "alloys" which contain a plurality of thermoplastic composi-tions have been discovered, but represent a minority of the theoretical number of possible mixtures. As greater know-ledge of attractive compatibilities of blends has accumulated through the decades, some basis has evolved for selecting plausible fields for research on thermoplastic blends.
Because incompatibility remains the dominating rule, any ` discovery of a useful blend of different thermoplastics represents a pragmatic invention which could not have been ` 20 predicted on the basis of previous publications.
Example 7 of Elghani et al 3,882,192 describes a -thermoplastic molding composition blended from 40 parts of polycarbonates of a dihydric phenol and a derivative of carbonic acid, 35 parts of polyvinylchloride, and 25 parts of a copolymer of styrene and maleic anhydride (88:12 molar ratio) having a Vicat temperature of 110C.
Maleimide, N-methyl maleimide, maleic diamide, bis(N-methyl) maleic diamide, and related compounds have been studied by scholars but have not been employed to a significant extent in the production of copolymers, except in research projects. Outstandingly advantageous properties
; This invention relates to thermoplastic molding composition having an advantageous combination of charac-teristics not readily attainable from competitive materials.
Heretofore prior technologists have established that most thermoplastic polymers are insoluble in other thermoplastic polymers. Most attempts to mix pellets of different molding pellets at the time they are fed to an extruder lead to extrudates having fracture lines at the boundaries amongst the different compositions. Plastic "alloys" which contain a plurality of thermoplastic composi-tions have been discovered, but represent a minority of the theoretical number of possible mixtures. As greater know-ledge of attractive compatibilities of blends has accumulated through the decades, some basis has evolved for selecting plausible fields for research on thermoplastic blends.
Because incompatibility remains the dominating rule, any ` discovery of a useful blend of different thermoplastics represents a pragmatic invention which could not have been ` 20 predicted on the basis of previous publications.
Example 7 of Elghani et al 3,882,192 describes a -thermoplastic molding composition blended from 40 parts of polycarbonates of a dihydric phenol and a derivative of carbonic acid, 35 parts of polyvinylchloride, and 25 parts of a copolymer of styrene and maleic anhydride (88:12 molar ratio) having a Vicat temperature of 110C.
Maleimide, N-methyl maleimide, maleic diamide, bis(N-methyl) maleic diamide, and related compounds have been studied by scholars but have not been employed to a significant extent in the production of copolymers, except in research projects. Outstandingly advantageous properties
- 2 - ~
, .
have been discovered for copolymers of styrene and such compounds, conveniently designated as styrene-maleimide ; copolymers. Notwithstanding the superior characteristics of such styrene-maleimide copolymers, the market for such " copolymers has been small enough that it has been efficient to produce such copolymers by copolymerizing styrene and maleic anhydride and thereafter treating the copolymer with methyl amine or ammonia to obtain such styrene-maleimide copolymers. DiGiulio 3,998,907 describes a method of pre-paring maleimide-containing copolymers by reacting amine or .. . .
,~ ammonia with particles of the copolymer comprising maleic anhydride under autogenous pressure at 125 to 200 C.
,...
~ Notwithstanding the abundance of literature perti-~' .
' nent to polycarbonates and blends comprising polycarbonates, there continued to be a persistent demand for a polycarbonate . , .
I blend suitable for molding items at a convenient temperature, ,' and a failure by others to meet such demand satisfactorily.
" SUMMARY OF INVENTION
In accordance with the present invention, an advantageous thermoplastic composition is prepared by heat ; blending polycarbonate and the imino derivative of styrene-` maleic anhydride, each thermoplastic component being present ^ in a concentration within the range from 10% to 90~.
;,.
The invention is further clarified by reference to a plurality of examples.
Examples 1-3 A series of samples were prepared by melting plastic pellets in an extruder, mixing much more thoroughly in the extruder than is conventional, whereby a complete blending of the thermoplastic materials was achieved, and then extruding the thoroughly mixed thermoplastic compositions.
`::
:
~085083 Composition A was a polycarbonate prepared from ;:, the high molecular weight carbonate ester derivative of bis(4 hydroxyphenyl)-2,-2-propane.
Composition B was a copolymer of styrene and about 8% maleimide prepared by the method of Example 1 of DiGiulio
, .
have been discovered for copolymers of styrene and such compounds, conveniently designated as styrene-maleimide ; copolymers. Notwithstanding the superior characteristics of such styrene-maleimide copolymers, the market for such " copolymers has been small enough that it has been efficient to produce such copolymers by copolymerizing styrene and maleic anhydride and thereafter treating the copolymer with methyl amine or ammonia to obtain such styrene-maleimide copolymers. DiGiulio 3,998,907 describes a method of pre-paring maleimide-containing copolymers by reacting amine or .. . .
,~ ammonia with particles of the copolymer comprising maleic anhydride under autogenous pressure at 125 to 200 C.
,...
~ Notwithstanding the abundance of literature perti-~' .
' nent to polycarbonates and blends comprising polycarbonates, there continued to be a persistent demand for a polycarbonate . , .
I blend suitable for molding items at a convenient temperature, ,' and a failure by others to meet such demand satisfactorily.
" SUMMARY OF INVENTION
In accordance with the present invention, an advantageous thermoplastic composition is prepared by heat ; blending polycarbonate and the imino derivative of styrene-` maleic anhydride, each thermoplastic component being present ^ in a concentration within the range from 10% to 90~.
;,.
The invention is further clarified by reference to a plurality of examples.
Examples 1-3 A series of samples were prepared by melting plastic pellets in an extruder, mixing much more thoroughly in the extruder than is conventional, whereby a complete blending of the thermoplastic materials was achieved, and then extruding the thoroughly mixed thermoplastic compositions.
`::
:
~085083 Composition A was a polycarbonate prepared from ;:, the high molecular weight carbonate ester derivative of bis(4 hydroxyphenyl)-2,-2-propane.
Composition B was a copolymer of styrene and about 8% maleimide prepared by the method of Example 1 of DiGiulio
3,998,907, using aqueous ammonia at a temperature of about 147C. for about 12 hours at a pressure of about 5 atm~s-pheres.
Compositions C, D, and E were blends containing 25%, 50% and 75% respectively of styrene-maleimide (8%) ~j copolymer (Composition B) and the balance polycarbonate ~ (Composition A).
rl Data relating to the controls and examples are shown in Table 1.
Table 1 -~
Control Example Control JJ 1 2 3l K
Code composition A B
% polycarbonate100 75 50 25 % styrene-maleimide 0 255 50 75 100 Z~ 20 {, Tensile yield psi8,300 9,100 NA NA NA -~
Tensile break psi10,000 7,600 8,500 6,800 7,600 Tensile elong psi270 54 2.3 1.5 1.8 Modulus (105 psi)3.3 4.0 4.5 4.7 5.4 Flexure mod51us3.1 3.8 4.1 4.5 4.7 .' (10 pSi) ; Flexural break (psi) NA NA NA 13,300 13,000 Izod (ft lb/in)9.2 o.6 0-5 0.2 0.2 Vicat (F) 310 296 287 - 268 265 Said data establish that the transparent macromole- -cular organic alloy has a high heat resistance and a highly advantageous superior stiffness to that of polycarbonate.
Moreover, styrene-maleimide resin is less costly than _ 4 _ . :
.. . ,. .. . . - . - .:
, . .
-: ' ~ . ' ~ . :
1C~85~83 polycarbonate, whereby some of the advantages of polycarbon-., ates can be utilized in the production of articles sold at a price significantly below the price at which a molded pure polycarbonate article would be expected to sell.
Example 4 Compositions are prepared from thermoplasticly blended polycarbonates and styrene-maleimide using concen-trations of polycarbonate within the 9-25% range, showing many of the advantages of the 25% blend. Compositions are prepared from thermoplastically blended polycarbonates and styrene-maleimide concentrations of styrene-maleimide within the 9-25% range, showing many of the advantages of the 25%
blend.
Example 5 Blends of 50~ polyphenylenecarbonate and 50% co-polymer of styrene-maleimide containing about 8% maleimide are prepared by preparing solutions of components in halo-genated organic solvent, mixing such solutions, volatilizing the solvents, and extruding the thus precipitated mixture.
A basis is thus established for the conclusion that the advantageous results of Example 2 are attributable to the advantageous alloying propensities of the components and not primarily to the method of blending.
Example 6 Blends of polycarbonate and styrene-maleimide are prepared throughout the 10 to 90% and 90 to 10% ranges, using a series of styrene-maleimide copolymers. It is thus established that the method of preparing the maleimide, the use of ammonia, a lower alkyl primary amine, or mixtures thereof, does not jeopardize the attainment of advantageous results. The minimum amount of maleimide in the copolymer 1085~83 must be at least 5~, and lesser amounts fail to impart to the blends the stiffness which characterize the blends of the present invention. The maximum amount of maleimide in the copolymer must not be greater than 35~ because the extrudability of the hot mix is impaired by excessive con-centrations of the maleimide. Some association of the ;~
, imide group of the copolymer chain and the carbonate group of the polycarbonate chain is indicated as a synergistic i~ advantage of the unique alloys of the present invention.
Example 7 ;~ Blends of polycarbonate and styrene-maleimide are prepared throughout the 10 to 90~ and 90 to 10~ ranges, using a series of polycarbonates. Satis~actory results are obtained only with polycarbonates which are predominantly aromatic. Polycarbonates derived from hydroquinone, bis
Compositions C, D, and E were blends containing 25%, 50% and 75% respectively of styrene-maleimide (8%) ~j copolymer (Composition B) and the balance polycarbonate ~ (Composition A).
rl Data relating to the controls and examples are shown in Table 1.
Table 1 -~
Control Example Control JJ 1 2 3l K
Code composition A B
% polycarbonate100 75 50 25 % styrene-maleimide 0 255 50 75 100 Z~ 20 {, Tensile yield psi8,300 9,100 NA NA NA -~
Tensile break psi10,000 7,600 8,500 6,800 7,600 Tensile elong psi270 54 2.3 1.5 1.8 Modulus (105 psi)3.3 4.0 4.5 4.7 5.4 Flexure mod51us3.1 3.8 4.1 4.5 4.7 .' (10 pSi) ; Flexural break (psi) NA NA NA 13,300 13,000 Izod (ft lb/in)9.2 o.6 0-5 0.2 0.2 Vicat (F) 310 296 287 - 268 265 Said data establish that the transparent macromole- -cular organic alloy has a high heat resistance and a highly advantageous superior stiffness to that of polycarbonate.
Moreover, styrene-maleimide resin is less costly than _ 4 _ . :
.. . ,. .. . . - . - .:
, . .
-: ' ~ . ' ~ . :
1C~85~83 polycarbonate, whereby some of the advantages of polycarbon-., ates can be utilized in the production of articles sold at a price significantly below the price at which a molded pure polycarbonate article would be expected to sell.
Example 4 Compositions are prepared from thermoplasticly blended polycarbonates and styrene-maleimide using concen-trations of polycarbonate within the 9-25% range, showing many of the advantages of the 25% blend. Compositions are prepared from thermoplastically blended polycarbonates and styrene-maleimide concentrations of styrene-maleimide within the 9-25% range, showing many of the advantages of the 25%
blend.
Example 5 Blends of 50~ polyphenylenecarbonate and 50% co-polymer of styrene-maleimide containing about 8% maleimide are prepared by preparing solutions of components in halo-genated organic solvent, mixing such solutions, volatilizing the solvents, and extruding the thus precipitated mixture.
A basis is thus established for the conclusion that the advantageous results of Example 2 are attributable to the advantageous alloying propensities of the components and not primarily to the method of blending.
Example 6 Blends of polycarbonate and styrene-maleimide are prepared throughout the 10 to 90% and 90 to 10% ranges, using a series of styrene-maleimide copolymers. It is thus established that the method of preparing the maleimide, the use of ammonia, a lower alkyl primary amine, or mixtures thereof, does not jeopardize the attainment of advantageous results. The minimum amount of maleimide in the copolymer 1085~83 must be at least 5~, and lesser amounts fail to impart to the blends the stiffness which characterize the blends of the present invention. The maximum amount of maleimide in the copolymer must not be greater than 35~ because the extrudability of the hot mix is impaired by excessive con-centrations of the maleimide. Some association of the ;~
, imide group of the copolymer chain and the carbonate group of the polycarbonate chain is indicated as a synergistic i~ advantage of the unique alloys of the present invention.
Example 7 ;~ Blends of polycarbonate and styrene-maleimide are prepared throughout the 10 to 90~ and 90 to 10~ ranges, using a series of polycarbonates. Satis~actory results are obtained only with polycarbonates which are predominantly aromatic. Polycarbonates derived from hydroquinone, bis
4-hydroxy diphenylmethane, 2,6-dimethyl hydroquinone, and other types of phenylene carbonate polymers are established as useful polycarbonates for the advantageous blends of the present invention.
Various modifications of the invention are possi-ble without departn~ng from the scope of the invention as set forth in the claims.
. , .
:, : .
. .
~ 3o
Various modifications of the invention are possi-ble without departn~ng from the scope of the invention as set forth in the claims.
. , .
:, : .
. .
~ 3o
Claims (5)
The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A thermoplastic molding composition which comprises:
A. from about 10% to about 90% by weight of a polycarbonate;
B. from about 10% to about 90% by weight of a copolymer of maleimide and styrene containing from about 5% to about 35% maleimide and from about 65% to about 95%
styrene.
A. from about 10% to about 90% by weight of a polycarbonate;
B. from about 10% to about 90% by weight of a copolymer of maleimide and styrene containing from about 5% to about 35% maleimide and from about 65% to about 95%
styrene.
2. The composition of claim 1 in which the con-centration range of each component is from about 25% to about 75%.
3. The composition of claim 2 in which the con-centration of each component is about 50%.
4. The composition of claim 1 in which the poly-carbonate is a polyphenylene carbonate.
5. The composition of claim 1 in which the copolymer of maleimide and styrene is prepared by subjecting a copolymer of maleic anhydride and styrene to a basic aqueous nitrogenous system at a temperature of from about 125° to about 200°C. at an autogenous pressure for 0.5 to 48 hours and thereafter depressurizing and devolatilizing the product.
7.
7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US78915277A | 1977-04-19 | 1977-04-19 | |
| US789,152 | 1977-04-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1085083A true CA1085083A (en) | 1980-09-02 |
Family
ID=25146740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA290,874A Expired CA1085083A (en) | 1977-04-19 | 1977-11-15 | Thermoplastic molding composition comprising styrene- maleimide and polycarbonate |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS53129245A (en) |
| BE (1) | BE863034A (en) |
| CA (1) | CA1085083A (en) |
| DE (1) | DE2811846A1 (en) |
| FR (1) | FR2388019A1 (en) |
| GB (1) | GB1579907A (en) |
| IT (1) | IT1090566B (en) |
| NL (1) | NL7800025A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1150879A (en) * | 1980-06-23 | 1983-07-26 | Edwin D. Hornbaker | Polyethylene terephthalate blends |
| JPS57125241A (en) * | 1981-01-28 | 1982-08-04 | Denki Kagaku Kogyo Kk | Heat-resistant resin composition |
| US4410662A (en) | 1981-03-30 | 1983-10-18 | Mobay Chemical Corporation | Polycarbonate having an improved impact performance |
| US4493920A (en) * | 1983-12-27 | 1985-01-15 | Atlantic Richfield Company | Polymer compositions |
| US4663386A (en) * | 1984-12-24 | 1987-05-05 | Atlantic Richfield Company | Flame-retardant molded composition which incorporates a poly(styrene-co-N-phenylmaleimide-co-dibromostyrene)copolymer |
| US4604422A (en) * | 1984-12-24 | 1986-08-05 | Atlantic Richfield Company | Flame-retardant molded composition incorporating a poly[N-(bromophenyl)maleimide-co-styrene-co-maleic anhydride] copolymer |
| US4609711A (en) * | 1984-12-24 | 1986-09-02 | Atlantic Richfield Company | Flame retardant molded composition which incorporates a poly(N-(bromophenyl)maleimide-Co-styrene-Co-N-phenylmaleimide) copolymer |
| JP2501555B2 (en) * | 1986-02-03 | 1996-05-29 | 電気化学工業株式会社 | Transparent thermoplastic resin composition |
-
1977
- 1977-11-15 CA CA290,874A patent/CA1085083A/en not_active Expired
- 1977-12-06 JP JP14631977A patent/JPS53129245A/en active Pending
- 1977-12-13 IT IT52194/77A patent/IT1090566B/en active
-
1978
- 1978-01-02 NL NL7800025A patent/NL7800025A/en not_active Application Discontinuation
- 1978-01-18 BE BE184417A patent/BE863034A/en unknown
- 1978-01-26 FR FR7802194A patent/FR2388019A1/en active Pending
- 1978-03-17 DE DE19782811846 patent/DE2811846A1/en not_active Withdrawn
- 1978-04-19 GB GB15493/78A patent/GB1579907A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| BE863034A (en) | 1978-07-18 |
| FR2388019A1 (en) | 1978-11-17 |
| NL7800025A (en) | 1978-10-23 |
| GB1579907A (en) | 1980-11-26 |
| DE2811846A1 (en) | 1978-10-26 |
| IT1090566B (en) | 1985-06-26 |
| JPS53129245A (en) | 1978-11-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry | ||
| MKEX | Expiry |
Effective date: 19970902 |