CA1257947A - Carbonate polymer composition - Google Patents

Carbonate polymer composition

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Publication number
CA1257947A
CA1257947A CA000487000A CA487000A CA1257947A CA 1257947 A CA1257947 A CA 1257947A CA 000487000 A CA000487000 A CA 000487000A CA 487000 A CA487000 A CA 487000A CA 1257947 A CA1257947 A CA 1257947A
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Prior art keywords
bisulfate
carbonate polymer
composition
sulfate
metal
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Expired
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CA000487000A
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French (fr)
Inventor
Samuel A. Ogoe
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Dow Chemical Co
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Dow Chemical Co
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Priority to CA000487000A priority Critical patent/CA1257947A/en
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Abstract

ABSTRACT OF THE DISCLOSURE
The present invention is a carbonate polymer composition comprising a carbonate polymer having dispersed therein a metal salt of an aromatic sulfimide and a metal sulfate or bisulfate having a pka from 1 to 5 inclusive whereby the sulfimide is used in an amount to provide improved flame retardancy and sulfate or bisulfate is used in an amount to provide increased processing stability. The use of metal sulfates or metal bisulfates is effective in reducing molecular weight changes during melt shearing.

Description

CARBONATE POLYMER COMPOSITION

This invention rela-tçs to carbonate polymer compositions containing an additive which acts as a flame retardant together with an additive which improves processing ~tability.

It is known from U.S. 4,201,382 that various metalic salts can be used as fillers for polycarbonate compositions. However, these salts are used in substant-ial amounts as fillers and do not have the requisite pka value to be useful in this invention.

Carbonate polymers derived from reactions of dihydroxyorganic compounds, particularly the dihydric phenols, and carbonic acid derivatives such as phosgene, have found extensive commercial application because of their excellent physical properties. These thermo-plastic polymers are suitable for the manufacture of molded parts wherein impact strength, rigidity, toughness, heat resistance, and excellent electrical properties are required.

31,380A-F -1-
-2~ 3~

Unfortunately, however, these polymers exhibit a brief but definite burning time when contacted with an open flame. More importantly, as is often the case, the carbonate polymers contain stabilizers and o-ther additives which are often more combustible than the unmodified carbonate polymer. As a result, the modified carbonate polymers frequently exhibit subs-tantially poorer resistance to combustion than does the unmodi-fied carbonate polymer.

In attempts to increase the combustion resis-tance of carbonate polymers including the modified forms thereof, it has been a common practice to employ monomeric phosphites, phosphoric acid esters, thiophos-phoric acid esters containing halogenated alkyl radicals and halogenated organic compounds into the carbonate polymer. ~owever, in order to obtain any noticeable improvement in combustion resis~ance, these additives have been employed in such large quantities that they often adversely affect many of -the desirable physical and mechanical properties of the carbonate polymer.

The use of aromatic sulfimides as flame retardants in carbonate polymers is suggested in U.S.
patent 4,254,015 granted March 3, 1981. However, it was found that while these additives are efficient as flame retardants, they also adversely effec-t the pro-cessing stability of the carbonate polymers. In other words, during melt processing, such as extruding into pellets, there is a considerable lowering of the molecular weight.

The use of metal salts of inorganic acids such as sodium bisulfate as flame retardants is sug-gested in U.S. Patent 4,486,560 granted December 4, 1984.

31,380A-F -2-~257~3~ 7 However, this application does not suggest the use o~
these compounds as processing aids.

The present invention is a carbonate polyrner composition comprising a carbonate polymer having S dispersed therein a metal salt of an aromatic sulfi-mide and a metal sulfate or bisulfate having a pka from 1 to 5 inclusive whereby the sulfimide is used in an amount to provide improved flame retardancy and the sulfate or bisu]fate is used in an amount to pro-vide increased processing stability. Elereinafter,such compositions will be re~erred to as fir retardant carbonate polymer compositions and they exhibit sur-prisingly high resistance to combustion. In addi-tion, the compositions exhibit physical properties comparable to a carbonate polymer containing no ~ire retardant additive.

The fire retardant carbonate polymer composi-tions of the present invention are suitably employed in most applications in which opague polycarbonates have been previously utilized. Applications of particular interest for the utilization of the carbonate polymer compositions of this invention are pigmented and/or colored carbonate polymers useful as: automobile parts, e.y., air filters, fan housings, exterior com-ponents, housings for electrical motors, appliances,business and office equipment, photographic equipment, and aircraft applications.

The carbonate polymers employed in the present invention are advantageously aroma-tic carbonate polymers such as the trityl diol carbonates described in U.S.
patent Nos. 3,036,036, 3,036,037, 3,036,038 and 3,036,039, 31,380A-F -3-Yr~ J~7 polycarbonates of bis(ar-hydroxyphenyl)-alkylidenes (often called bisphenol-A kype diols) including their aromatically and aliphatically substituted derivatives such as disclosed in UOS. Patent Nos. 2,999,835,
3,038,365 and 3,334,154, and carbonate polymers derived from other aromatic diols SUCh as described in U.S.
Patent No. 3,169,121.

It is understood, of course, that the poly-carbonate may be derived rom ~1) two or more different dihydric phenols or (2) a dihydr.ic phenol and a glycol or a hydroxy- or acid-terminated polyester or a dibas.ic acid in the event a carbonate copolymer or interpolymer rather than a homopolymer is desired. Also suitable for the practice of this invention are blends of any one of the above carbonate polymers. Also included in the term "carbonate polymer" are the ester/carbonate copolymers of the types described in U . S . Patent Nos.
3,169,121, 4,287,787, 4,156,069, 4,260,731 and 4,105,533.
Of the aforementioned carbonate polymers, the poly~
carbonates of bisphenol-A and derivatives, including copolycarbonates of bisphenol-A, are preferred. Methods for preparing carbonate polymers for use in the practice of this invention are well known, for example, several suitable methods are disclosed in the aforementioned patents.

The salt form of aromatic sulfimides which are employed herein are advantageously represented by the formula:
r~ o o ( rS ~ M ~M or Ar-S-N~-S-Ar M

31,380A-F -4-~5~

wherein Ar is an aromatic or substituted aromatic group, M is a suitable cation such as a metal cation.
M is preferably an alkali metal such as sodium or potassium. Alternatively, M is a divalent cation, preferably alkaline earth or multivalent cation obtained from, for example, copper, aluminum, or antimony. Representative preferred sulfimide salts include the alkali metal salts of saccharin, N-(p-tolylsulfonyl)-p-toluenesulfimide, N~(N'-benzyl-aminocarbonyl)sulfanilimide, N--(phenylcarboxyl)-sulfa-nilimide, N-(2-pyrimidinyl)-sulfanilimide, N-(2-thiazolyl)-sulanilimide and other salts of the sulfimides dis-closed in U.S. Patent No.4,254,015. Combinations of the above-identified salts can also be employed.

Useful processing additives are metal bisul-fates or sulfates having a pka from 1 to 5 and prefer-rably 1 to 3. Examples of useful metal bisulfates or sulfates are sodium bisulfate, potassium bisulfate, lithium bisulfate, rubidi~m bisulfate, cesium bisulfate, and aluminum sulfate.

The fire retardant carbonate polymer composi~
tions of the present invention are suitably prepared by combining the carbonate polymer with an effective amount of the ire retardant addi-tive and the processiny additive using any of a variety of blendin~ procedures conventionally employed for incorporating additives into carbonate polymer resins. For example, dry particulates of the carbonate polymer and the additives can be dry blended and the resulting dry blend extruded into the desired shape. By "effective amount" is meant ; that combina-tion of the desired additive components is sufficient to provide improved fire retardant character 31,380A F -5-i7~47 and processing stability to the carbonate polymer with which it is blended.

While any amount of the fire retardant addi-tive that imparts -to the carbonate polymer an improved fire retardancy is suitable, preerred amounts oE the fire retardant additive are in the range from 0.001 to 10 percent, especially from 0.005 to 2 weight percent based on the weight of the carbonate polymer.

The amount o the metal sulfate or bisulfate used to provide increased processing stability can be any amount that is suitable. Preferrably, an amount from 0.001 to 1.0 weight percen-t based on the carbonate polymer will be suitable. The most preferred range is from 0.01 to 0.1% percent by weight.
.

In addition to the aforementioned fire retar-dant additives, other additives can be included in the carbonate polymer composition of the present invention such as fillers (i.e., a tetrafluoroethylene polymer or glass fibers), pigments, dyes, antioxidants, heat stabilizers, ultraviolet light absorbers, mold release agents and other additives commonly employed in carbonate polymer compositions.

The following examples are given to further illustrate the invention and should not be construed as limiting its scope. In the :ollowing examples, all parts and percentages are by weight unless otherwise indicated.

31,380A-F -6-~5~4~
Example 1 A polycarbonate formulation containing 0.03%
and 0.02% by weiyht of potassium para-tolylsulfimide (KpTSM) and potassium bisulfate (KHSO~) respectively is prepared by mixing a bisphenol A polycarbona-te resin having a molecular weight of about 31,000 with the additives for about 45 minutes on a Hobart mixer.
The formulated sample is dried for 3 hours at 125C
(257F). The drled sample is extruded to pellets at 329~C (625F). The extruded pellets are redried in a forced draft oven for 3 hours at 125C (257F). A
portion of the dried sarnple is subjected to melt shear-ing at 282C (540F) by torque rheometer over a 30 minute time period (see Table I). The remainder of the sample i5 injection molded at 302C (575F) into bars or flammability tests (see Table II).

Modified flammability polycarbonate without potassium bisulfate as well as heat stabilized poly-carbonate are similarly prepared and evaluated as - 20 controls. All the controls and the examples contained 0O1% by weight of a diphosphonite stabilizer "P-EPQ"
~rom Sandoz (U.S. 3,825,629) and 0.05% by weight of a hindered phenolic stabilizer "IrganoxT~ 1076~ from Gelgy Chemical Corporation (U.S. 3,330,859).

Molecular weight by size exclusion chromato-graphy is measured and compared to the original sample.
By this test, it can be deduced that the greater the drop in molecular weight, the less stable the polymer to high temperature melt processing. See the following tables:

31,380A-F -7-9'~7 TABLE I

Tor~ue, Meter-Grams ~M) Sample _ nitial _ Flnal _ Tor~ue Change Control 1 625 (6.13) 510 (5.00) 115 (1.13) (Heat stabilized Polymer~
Control 2 590 (5.79) 365 (3.58) 225 (2.21) (Control 1 with 0.03% KpTSM) Example 1 560 (5.49) 470 (4.61) gO (0.88) (Control 1 with 0.03% KpTSM/0.02%
KHS04 ) Molecular Weight (Mw)__ _ Sample Initial Final Mw Change Control 1 31200 28700 2500 Control 2 29600 24400 5200 Ex~mple 1 29700 27000 2700 Table II shows that modified flammability polycarbonate with 0.02% KHS04 has significantly improved melt processing stability over the sample without KHS04 ~2). Table I shows decreased tor~ue change when the sample with KHS04 iS subjected to melt shearing at 282C by torque rheometer for 30 minutes.

31,380A-F -8-_9- ~ ~'J7~3'~7 TABLE III
Flammability Tests _ UL-94 ~ L.O.I.
Control 1 V-2 30.5 5Control 2 V-0 41.0 Example 1 V-0 40.0 The UL-94 and Limiting Oxygen Index (L.O.I.) te~ts in Table III show no significant change between the sam~le with KHSO4 and the one without KHSO~.

Example 2 Procedure in Exc~mple 1 was repeated except that 0.06% KPTSM and 0.04% KHSO~ buffer were incorpo-rated. The results are as follows:

T~BLE IV

_ Molecular Weight (Mw) _ _ Sample Init al Final Mw_Change Control 1 ~ (Heat S-tabilized pol~mer) 27400 25200 2200 Control 3 (Control 1 with 0.06% KPTSM) 28000 23000 5000 Example 2 (Control 1 with 250.06% KPTSM/
0.04%
KHSO4) 27300 25200 2100 31,380A-F g_ lo ~ 7~3~ ~

TABLE V

Torque, Meter - Grams (N M) Sdmple Initial Final Torque Change Control 1 640 t6.28) 545 (5 34) 95 (0-94) 5Control 3 440 (4.31) 260 (2.55) 180 (1.76) Example 2 460 (4.51) 390 (3.82) 70 (0.69) Tables II and IV show that increasing the concentrations of both KPTS~ and KHS04 do not have any adverse effect on the processing stability of the polymer. Similarly, Tables I and V do not show significant torque change regardless of the difference in KPTSM/KHSO4 levels.

T LE VI

Flammability Tests 15Sample UL-94 % LOI
Control 1 V-2 29.5 Control 3 V-O 41.0 Example 2 V-O 40.0 Table VI indicates that using higher levels of 20 KHSO4 buffer do not significantly affect the modified fla~mability properties of the polycarbonate.

Exam~es 3 and 4 The procedure of Example 1 was repeated except that 0.06% KPTSM, 0.05% KHSO4 and 0.05%
Al2( SO4 ) 3 were incorporated.

31,380A-F -10-~ ,t~7~)4~

The results are shown in Tables VI - VIII.

TABLE VI

Molecular Weight (Mw) ~ Initial Final Mw Change Control 1 (Heat stabilized polymer) 27400 25200 2200 Conkrol 3 (Control 1 with 0.06% KPTSM) 28000 23000 5000 Examp:Le 3 (Control 1 with O.06% KPTSM/0.05%
KHS04) 27300 25300 2000 E~ample 4 (Control 1 with 0.06% KPTSM/0.05%
Al2 ( S04 ) 3 ) 27700 25700 2000 TABLE VII

20 _Tor~ue, Meter - Grams (N-M~
Sample Inltial _ Final _ Torque Change Control 1 640 (6.28) 545 (5.34) 95 (0.94) Control 3 440 (4.31) 260 (2.55) 180 ~1.76) Example 3 460 (4.51) 400 (3.92) 60 (0.59) Example 4 450 (4.41) 410 (4.02) 40 (0.39) 31,380A-F

5~.~3~7 TABLE VIII
__ Flammability Tests Sample UL-94 % LOI
Control l V 2 30.5 5Control 3 V-0 40.0 Example 3 V 0 40.0 Example 4 V-0 40.0 31,380A-F -12-

Claims (9)

1. A carbonate polymer composition com-prising a carbonate polymer having dispersed therein a metal salt of an aromatic sulfimide and a metal sulfate or bisulfate having a pka from 1 to 5 inclusive whereby the sulfimide is used in an amount to provide improved flame retardancy and the sulfate or bisulfate is used in an amount to provide increased processing stability.
2. The composition of Claim 1 wherein the metal salt of an aromatic sulfimide is represented by the formula:

or M?

wherein Ar is an aromatic or substituted aromatic group, M is a metal cation.
3. The composition of Claim 2 wherein M is a metal cation selected from the group consisting of sodium, potassium, lithium, rubidium, cesium, calcium, magnesium, strontium, copper, aluminum and antimony.
4. The composition of Claim 1 wherein the metal sulfate or bisulfate is selected from the group consisting of sodium bisulfate, potassium bisulfate, lithium bisulfate, rubidium bisulfate, cesium bisulfate, and aluminum sulfate.
5. The composition of Claim 1 wherein the sulfimide is present in an amount from 0.001 to 10 weight percent based on the weight of the carbonate polymer.
6. The composition of Claim 1 wherein the sulfimide is present in an amount from 0.005 to 2 weight percent based on the weight of the carbonate polymer.
7. The composition of Claim 1 wherein the metal sulfate or bisulfate is present in an amount from 0.001 to 1.0 weight percent based on the weight of the carbonate polymer.
8. The composition of Claim 1 wherein the metal sulfate or bisulfate is present in an amount from 0.01 to 0.1 weight percent based on the weight of the carbonate polymer.
9. The composition of Claim 1 wherein the carbonate polymer is a polycarbonate of bisphenol-A, and the sulfimide comprises the alkali metal salt of N-(p-tolylsulfonyl)-p-toluenesulfimide and the bisulfate or sulfate is a member of the group consisting of an alkali metal bisulfate and aluminum sulfate.
CA000487000A 1985-07-18 1985-07-18 Carbonate polymer composition Expired CA1257947A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CA000487000A CA1257947A (en) 1985-07-18 1985-07-18 Carbonate polymer composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CA000487000A CA1257947A (en) 1985-07-18 1985-07-18 Carbonate polymer composition

Publications (1)

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CA1257947A true CA1257947A (en) 1989-07-25

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