US 4,174,359 AGrant
Flame Retardant Polycarbonate Polyblends
Issue Date:1979-11-13
•31 Claims
Abstract
The present invention pertains to a halogen-containing, copolycarbonate blend having improved critical thickness and flammability properties comprising an aromatic copolycarbonate comprising the reaction product of an aromatic diphenol, an aromatic thiodiphenol and a carbonic acid derivative, such as phosgene or carbonyl bromide, blended with an effective amount of a halogen-containing compound. In a preferred embodiment, the copolycarbonate blend also contains small amounts of a perfluoro sulfonic or carboxylic acid salt.
Metadata
Assignee
- Mobay Chemical Corporation
Inventors
- Parameswar Sivaramakrishnan
- Arthur L. Baron
Application Information
Application Number:US 8912521
Filing Date:1978-03-29
Priority Date:1977-09-06
Art Unit:142
Classifications
IPC:
C08L 6700
Field of Search:
260528860;866;869;873;45.7 R;45.7 L;45.85 R;45.85 T;45.95 G204;198;486;493;491;492
Patent Drawings
This patent does not have any drawings.
Description
EXAMPLES
Preparation of an aromatic diphenol-halogenated aromatic diphenol copolycarbonate
An aromatic diphenol-halogenated aromatic diphenol copolycarbonate was prepared by reacting a mixture of the disodium salts of 2,2-bis-(4-hydroxyphenyl)-propane (BPA) and 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane (TBBPA) with phosgene in accordance with the interfacial polycondensation synthesis hereinbefore discussed. The resulting copolycarbonate resin had a bromine content of about 9 percent by weight and a melt index of 5.9 gm/10 min. (ASTM D-1238).
Preparation of aromatic diphenol-aromatic thiodiphenol copolycarbonates
(A) An aromatic diphenol-aromatic thiodiphenol copolycarbonate was prepared by reacting a 60/40 mol % mixture of the disodium salts of 2,2-bis-(4-hydroxyphenyl)propane (BPA) and 4,4'-thiodiphenol (TDP) with phosgene in accordance with the interfacial polycondensation synthesis hereinbefore discussed. The resulting copolycarbonate had a melt index of 7.4 gm/10 min. (ASTM D-1238).
(B) An aromatic diphenol-aromatic thiodiphenol copolycarbonate was prepared as in (A) above except that a 70/30 mol % BPA/TDP mixture was used. The resulting copolycarbonate had a melt index of 5.7 gm/10 min. (ASTM D-1238).
(C) An aromatic diphenol-aromatic thiodiphenol copolycarbonate was prepared as in (A) above except that a 80/20 mol % BPA/TDP mixture was used. The resulting copolycarbonate had a melt index of 2.5 gm/10 min. (ASTM D-1238).
(D) A copolycarbonate having a melt index of 7.2 g/10 min. was prepared by reacting a mixture of the disodium salt of 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A) (BPA) and 4,4'-thiodiphenol (TDP) with phosgene in accordance with the interfacial polycondensation synthesis hereinbefore discussed. 85 mol % of bisphenol A and 15 mol % of 4,4'-thiodiphenol, based on the total mols of dihydroxyl compounds, were used.
EXAMPLE 1
The BPA/TBBPA copolycarbonate was blended with the BPA/TDP copolycarbonate prepared in (A) above in a 56/44 wt. % ratio. The polyblend was tested for impact, critical thickness and flammability properties with the test results reported in Table 1. The polyblend was found to be highly transparent.
EXAMPLE 2
The BPA/TBBPA copolycarbonate was blended with the BPA/TDP copolycarbonate prepared in (B) above in a 56/44 wt. % ratio. The test results of the Example 2 polyblend are reported in Table 1. The polyblend was found to be highly transparent.
EXAMPLE 3
The BPA/TBBPA copolycarbonate was blended with the BPA/TDP copolycarbonate prepared in (C) above in a 56/44 wt. % ratio. The test results of the Example 3 polyblend are reported in Table 1. The polyblend was found to be highly transparent.
EXAMPLE 4 (Comparison)
The BPA/TBBPA copolycarbonate was blended with a BPA polycarbonate having a melt index of 3-5.9 gm/10 min. (ASTM D-1238) in a 56/44 wt. % ratio. The test results of the Example 4 comparison polyblend are reported in Table 1.
EXAMPLE 5
The BPA/TDP (85/15) copolycarbonate prepared in (D) was intimately blended with 0.10 weight % of potassium perfluorobutane sulfonate, based on the weight of the copolycarbonate blend and then extruded, pelletized and molded into standard test samples for evaluation of physical properties. The properties measured are reported in Table 2.
EXAMPLE 6
Copolycarbonate (D) was intimately blended with a sufficient quantity of decabromodiphenyl ether to provide the copolycarbonate blend with a 5 wt. % bromine content, based on the weight of the copolycarbonate blend. The properties measured are reported in Table 2. The molded copolycarbonate blend was found to be highly transparent at a 1/16" thickness. Additionally, the molded copolycarbonate blend was found to be highly transparent at a 1/16" thickness.
EXAMPLE 7
Copolycarbonate (D) was intimately blended with 0.10 wt. % of potassium perfluorobutane sulfonate and a sufficient quantity of decabromodiphenyl ether to provide the copolycarbonate blend with a 5 weight % bromine content, based on the weight of the copolycarbonate blend. The properties measured are reported in Table 2. Additionally, the molded copolycarbonate blend was found to be highly transparent at a 1/16" thickness.
EXAMPLE 8
Copolycarbonate (D) was intimately blended only with a sufficient quantity of decabromodiphenyl ether to provide the copolycarbonate blend with a 4 weight % bromine content, based on the weight of the copolycarbonate blend. The properties measured are reported in Table 2.
EXAMPLE 9
Copolycarbonate (D) was intimately blended with 0.10 weight % of potassium perfluorobutane sulfonate and a sufficient quantity of decabromodiphenyl ether to provide the copolycarbonate blend with a 4 weight % bromine content, based on the weight of the copolycarbonate blend. The properties measured are reported in Table 2. Additionally, the molded copolycarbonate blend was found to be highly transparent at a 1/16" thickness.
EXAMPLE 10
Copolycarbonate (D) was intimately blended only with a sufficient quantity of decabromodiphenyl ether to provide the copolycarbonate blend with a 3 weight % bromine content, based on the weight of the copolycarbonate blend. The properties measured are repeated in Table 2.
EXAMPLE 11
Copolycarbonate (D) was intimately blended with 0.10 weight % of potassium perfluorobutane sulfonate and a sufficient quantity of decabromodiphenyl ether to provide the copolycarbonate blend with a 3 weight % bromine content, based on the weight of copolycarbonate blend. The properties measured are reported in Table 2. Additionally, the molded copolycarbonate blend was found to be highly transparent at a 1/16" thickness.
EXAMPLE 12
Copolycarbonate (D) was intimately blended with 0.10 weight % of potassium perfluorobutane sulfonate and a sufficient quantity of decabromodiphenyl ether to provide the copolycarbonate blend with a 2.5 weight % bromine content, based on the weight of the copolycarbonate blend. The properties measured are reported in Table 2. Additionally, the molded copolycarbonate blend was found to be highly transparent at a 1/16" thickness.
EXAMPLE 13
Copolycarbonate (D) was intimately blended only with a sufficient quantity of decabromodiphenyl ether to provide the copolycarbonate blend with a 2 weight % bromine content, based on the weight of the copolycarbonate blend. The properties measured are reported in Table 2.
EXAMPLE 14
Copolycarbonate (D) was intimately blended with 0.10 weight % of potassium perfluorobutane sulfonate and a sufficient quantity of decabromodiphenyl ether to provide the copolycarbonate blend with a 2.0 weight % bromine content, based on the weight of the copolycarbonate blend. The properties measured are reported in Table 2. Additionally, the molded copolycarbonate blend was found to be highly transparent at a 1/16" thickness.
EXAMPLE 15
Copolycarbonate (D) was intimately blended only with a sufficient quantity of decabromodiphenyl ether to provide the copolycarbonate blend with a 1 weight % bromine content based on the weight of the copolycarbonate blend. The properties measured are reported in Table 2.
EXAMPLE 16
Copolycarbonate (D) was intimately blended with 0.10 weight % of potassium perfluorobutane sulfonate and a sufficient quantity of decabromodiphenyl ether to provide the copolycarbonate blend with a 1 weight % bromine content, based on the weight of the copolycarbonate blend. The properties measured are reported in Table 2. Additionally, the molded copolycarbonate blend was found to be highly transparent at a 1/16" thickness.
EXAMPLE 17
BPA/TDP Copolycarbonate (D) was intimately blended with 0.10 weight % of potassium perfluorobutane sulfonate and a sufficient quantity of the bisphenol A/tetrabromobisphenol A copolycarbonate having a 9 weight % bromine content and a melt flow rate of 5.9 g/10 min. to provide the BPA/TDP copolycarbonate blend with a 2 weight % bromine content, based on the weight of the copolycarbonate blend. The properties measured are reported in Table 3. Additionally, the molded copolycarbonate blend was found to be highly transparent at a 1/16" thickness.
EXAMPLE 18
Example 17 was repeated except that the BPA/TDP copolycarbonate was intimately blended with 0.10 weight % of potassium perfluorobutane sulfonate and a sufficient quantity of the bisphenol A/tetrabromobisphenol A copolycarbonate to provide the BPA/TDP copolycarbonate blend with a 3 weight % bromine content, based on the weight of the copolycarbonate blend. The properties measured are reported in Table 3. Additionally, the molded copolycarbonate blend was found to be highly transparent at a 1/16" thickness.
EXAMPLE 19
Example 5 was repeated except that the BPA/TDP copolycarbonate was intimately blended with 0.10 weight % of potassium perfluorobutane sulfonate and a sufficient quantity of tetrabromobisphenol A homopolycarbonate having a number average molecular weight, Mn, of 4000 and a relative viscosity of 1.03 to provide the BPA/TDP copolycarbonate blend with a 1 weight % bromine content, based on the weight of the copolycarbonate blend. The properties measured are reported in Table 3. Additionally, the molded copolycarbonate blend was found to be highly transparent at a 1/16" thickness.
EXAMPLE 20
Example 19 was repeated except that the BPA/TDP copolycarbonate was intimately blended with 0.10 weight % of potassium perfluorobutane sulfonate and a sufficient quantity of the tetrabromobisphenol A homopolycarbonate to provide the BPA/TDP copolycarbonate blend with a 2 weight % bromine content, based on the weight of the copolycarbonate blend. The properties measured are reported in Table 3. Additionally, the molded copolycarbonate blend was found to be highly transparent at a 1/16" thickness.
EXAMPLE 21
Example 19 was repeated except that the BPA/TDP copolycarbonate was intimately blended with 0.10 weight % of potassium perfluorobutane sulfonate and a sufficient quantity of the tetrabromobisphenol A homopolycarbonate to provide the BPA/TDP copolycarbonate blend with a 3 weight % bromine content, based on the weight of the copolycarbonate blend. The properties measured are reported in Table 3. Additionally, the molded copolycarbonate blend was found to be highly transparent at a 1/16" thickness.
As is demonstrated by the foregoing examples, the halogen-containing, aromatic copolycarbonate blends of the invention exhibit both improved flame retardant characteristics and improved critical thickness values.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made without departing from the spirit and scope of the invention except as it may be limited by the claims.
Claims
What is claimed is:
1. A halogen-containing aromatic copolycarbonate blend comprising (a) an aromatic diphenol-aromatic thiodiphenol copolycarbonate comprising the reaction product of (i) an aromatic diphenol having the structural formula ##STR6## wherein R is identical or different and denotes H or C.sub.1 -C.sub.4 -alkyl, and wherein X is a bond, C.sub.1 -C.sub.8 -alkylene, C.sub.2 -C.sub.8 -alkylidene, C.sub.5 -C.sub.15 -cycloalkylene, C.sub.5 -C.sub.15 -cycloalkylidene, --SO.sub.2 --, --SO--, --CO-- or ##STR7## (ii) an aromatic thiodiphenol having the structural formula ##STR8## wherein R", which may be identical or different, is H or C.sub.1 -C.sub.4 -alkyl, and n is 0, 1 or 2, and (iii) a member selected from the group consisting of carbonyl bromide, phosgene, bischloroformic esters of (i) and (ii) and diaryl carbonates (b) intimately blended with an effective amount of a halogen-containing compound whereby the critical thickness and flammability properties of the halogen-containing, aromatic copolycarbonate blend is improved.
2. The halogen-containing, aromatic copolycarbonate blend of claim 1 wherein said blend contains a sufficient amount of the halogen-containing compound to produce an about 0.01 to 8 wt. % halogen content, based on the weight of the aromatic copolycarbonate blend.
3. The halogen-containing, aromatic copolycarbonate blend of claim 1 wherein said halogen-containing compound is an aromatic diphenol-halogenated aromatic diphenol copolycarbonate comprising the reaction product of (i) an aromatic diphenol, (ii) a halogenated, aromatic diphenol, and (iii) a member selected from the group consisting of carbonyl bromide, phosgene, bischloroformic esters of (i) or (ii) and diaryl carbonates.
4. The halogen-containing, aromatic copolycarbonate blend of claim 3 wherein the aromatic diphenol of said aromatic diphenol-halogenated aromatic diphenol copolycarbonate is of the structural formula ##STR9## wherein R is identical or different and denotes H or C.sub.1 -C.sub.4 -alkyl, and wherein X is a bond, C.sub.1 -C.sub.8 -alkylene, C.sub.2 -C.sub.8 -alkylidene, C.sub.5 -C.sub.15 -cycloalkylene, C.sub.5 -C.sub.15 -cycloalkylidene, --SO.sub.2 --, --SO--, --CO-- or ##STR10##
5. The halogen-containing, aromatic copolycarbonate blend of claim 3 wherein the halogenated aromatic diphenol of said aromatic diphenol-halogenated aromatic diphenol copolycarbonate is of the structural formula ##STR11## wherein R' is identical or different and denotes H, C.sub.1 -C.sub.4 -alkyl or halogen, and at least one R' is halogen, and wherein X' is a bond; C.sub.1 -C.sub.8 -alkylene, C.sub.2 -C.sub.8 -alkylidene, C.sub.5 -C.sub.15 -cycloalkylene, C.sub.5 -C.sub.15 -cycloalkylidene, --SO.sub.2 --, --SO--, --CO-- or ##STR12##
6. The halogen-containing, aromatic copolycarbonate blend of claim 3 wherein the aromatic diphenol-halogenated aromatic diphenol copolycarbonate has a halogen content of from about 3 to 10 percent by weight, based on the weight of the aromatic diphenol-halogenated aromatic diphenol copolycarbonate.
7. The halogen-containing, aromatic copolycarbonate blend of claim 3 wherein the aromatic diphenol of said aromatic diphenol-halogenated aromatic diphenol copolycarbonate is bisphenol A and the halogenated aromatic diphenol of said aromatic diphenol-halogenated aromatic diphenol copolycarbonate is tetrabromobisphenol A.
8. The halogen-containing, aromatic copolycarbonate blend of claim 1 wherein said halogen-containing compound is a halogenated homopolycarbonate.
9. The halogen-containing, aromatic copolycarbonate blend of claim 8 wherein the halogenated homopolycarbonate is a tetrabromobisphenol A-based homopolycarbonate.
10. The halogen-containing, aromatic copolycarbonate blend of claim 1 wherein said halogen-containing compound is a monomeric halogen-containing compound.
11. The halogen-containing, aromatic copolycarbonate blend of claim 10 wherein the monomeric halogen-containing compound is decabromodiphenyl ether.
12. The halogen-containing, aromatic copolycarbonate blend of claim 1 wherein the aromatic diphenol-aromatic thiodiphenol copolycarbonate contains from about 2 to 50 mol % of the aromatic thiodiphenol, based on the total mols of diphenol used in the preparation of said aromatic diphenol-aromatic thiodiphenol copolycarbonate.
13. The halogen-containing, aromatic copolycarbonate blend of claim 1 wherein the aromatic thiodiphenol is 4,4'-thiodiphenol.
14. The halogen-containing, aromatic copolycarbonate blend of claim 1 wherein the aromatic diphenol of said aromatic diphenol-aromatic thiodiphenol copolycarbonate is bisphenol A.
15. The halogen-containing, aromatic copolycarbonate blend of claim 1 wherein the halogen-containing compound is a bromine- or chlorine-containing compound.
16. The halogen-containing, aromatic copolycarbonate blend of claim 15 wherein the halogen-containing compound is a bromine-containing compound.
17. The halogen-containing, aromatic copolycarbonate blend of claim 1 wherein about 0.01 to 3 wt. % of a sulfonic or carboxylic acid salt, based on the weight of the aromatic copolycarbonate blend, is present.
18. The halogen-containing, aromatic copolycarbonate blend of claim 17 wherein about 0.05 to 1 wt. % of a sulfonic or carboxylic acid salt, based on the weight of the aromatic copolycarbonate blend, is present.
19. The halogen-containing, aromatic copolycarbonate blend of claim 17 wherein the sulfonic or carboxylic acid salt is a perfluoro sulfonic or carboxylic acid salt.
20. The halogen-containing, aromatic copolycarbonate blend of claim 19 wherein the perfluoro sulfonic or carboxylic acid salt is a potassium or sodium perfluoroalkane sulfonate.
21. The halogen-containing, aromatic copolycarbonate blend of claim 20 wherein the perfluoro sulfonic or carboxylic acid salt is potassium or sodium perfluorobutane sulfonate.
22. The halogen-containing, aromatic copolycarbonate blend of claim 1 wherein said blend contains a sufficient amount of the halogen-containing compound to produce an about 1 to 5 wt. % halogen content and about 0.05 to 1 wt. % of a perfluoro sulfonic or carboxylic acid salt, based on the weight of the aromatic copolycarbonate blend.
23. A process for preparing a halogen-containing aromatic copolycarbonate blend having improved flame retardancy and critical thickness properties comprising intimately blending (a) an aromatic diphenol-aromatic thiodiphenol copolycarbonate comprising the reaction product of (i) an aromatic diphenol having the structural formula ##STR13## wherein R is identical or different and denotes H or C.sub.1 -C.sub.4 -alkyl, and wherein X is a bond, C.sub.1 -C.sub.8 -alkylene, C.sub.2 -C.sub.8 -alkylidene, C.sub.5 -C.sub.15 -cycloalkylene, C.sub.5 -C.sub.15 -cycloalkylidene, --SO.sub.2 --, --SO--, --CO-- or ##STR14## (ii) an aromatic thiodiphenol having the structural formula ##STR15## wherein R", which may be identical or different, is H or C.sub.1 -C.sub.4 -alkyl, and n is 0, 1 or 2, and (iii) a member selected from the group consisting of carbonyl bromide, phosgene, bischloroformic esters of (i) or (ii) and diaryl carbonates (b) with a sufficient amount of halogen-containing compound to produce a blend having an about 0.01 to 8 wt. % halogen content, based on the weight of the aromatic copolycarbonate blend.
24. The process of claim 23 wherein the halogen-containing compound is a bromine- or chlorine-containing compound.
25. The process of claim 24 wherein the halogen-containing compound is a bromine-containing compound.
26. The process of claim 23 wherein about 0.01 to 3 wt. % of a perfluoro sulfonic or carboxylic acid salt, based on the weight of the aromatic copolycarbonate blend, is present.
27. The process of claim 26 wherein the perfluoro sulfonic or carboxylic acid salt is a potassium or sodium perfluoroalkane sulfonate.
28. The process of claim 27 wherein the organic acid salt is potassium or sodium perfluorobutane sulfonate.
29. The process of claim 23 wherein said blend contains a sufficient amount of the halogen-containing compound to produce an about 1 to 5 wt. % halogen content and 0.05 to 1 wt. % of a perfluoro sulfonic or carboxylic acid salt, based on the weight of the aromatic copolycarbonate blend.
30. A halogen-containing, aromatic copolycarbonate blend comprising (a) an aromatic diphenol-aromatic thiodiphenol copolycarbonate comprising the reaction product of (i) an aromatic diphenol having the structural formula ##STR16## wherein R is identical or different and denotes H or C.sub.1 -C.sub.4 -alkyl, and wherein X is a bond, C.sub.1 -C.sub.8 -alkylene, C.sub.2 -C.sub.8 -alkylidene, C.sub.5 -C.sub.15 -cycloalkylene, C.sub.5 -C.sub.15 -cycloalkylidene, --SO.sub.2 --, --SO--, --CO-- or ##STR17## (ii) an aromatic thiodiphenol having the structural formula ##STR18## wherein R", which may be identical or different, is H or C.sub.1 -C.sub.4 -alkyl, and n is 0, 1 or 2, and (iii) a member selected from the group consisting of carbonyl bromide, phosgene, bischloroformic esters of (i) or (ii) and diaryl carbonates (b) intimately blended with an effective amount of a bromine- or chlorine-containing compound whereby the critical thickness and flammability properties of the halogen-containing, aromatic copolycarbonate blend is improved.
31. The halogen-containing, aromatic copolycarbonate blend of claim 30 wherein said blend contains a sufficient amount of the bromine- or chlorine-containing compound to produce an about 0.01 to 8 wt. % bromine or chlorine content, based on the weight of the aromatic copolycarbonate blend.
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