WO2004039879A1 - Method for making fire-retarded polycarbonate and related compositions - Google Patents
Method for making fire-retarded polycarbonate and related compositions Download PDFInfo
- Publication number
- WO2004039879A1 WO2004039879A1 PCT/US2003/027048 US0327048W WO2004039879A1 WO 2004039879 A1 WO2004039879 A1 WO 2004039879A1 US 0327048 W US0327048 W US 0327048W WO 2004039879 A1 WO2004039879 A1 WO 2004039879A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sulfonate
- potassium
- sulfonic acid
- salt
- toluene sulfonic
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
Definitions
- This application relates to a method for imparting fire-retardant properties to polycarbonate resins, to compositions useful in the method, and to fire-retarded polycarbonate resins of the type produced by the method.
- the fire-retarded polycarbonates are suitably used to make molded articles, particularly thin-walled articles.
- polycarbonate resins Because of their strength and clarity, polycarbonate resins have a great many significant commercial applications. Unfortunately, polycarbonate resins are inherently flammable and can drip hot molten material causing nearby materials to catch fire as well. Thus, in order to safely utilize polycarbonates in many applications . it is necessary to include additives which retard the flammability of the material and/or which reduce dripping. The challenge is to identify additives which accomplish this purpose without compromising the desirable properties of strength and clarity, without introducing new problems (such as the potential environmental problems associated with some halogenated additives) and without prohibitively increasing the price.
- organic salts particularly sulfonic acid salts.
- these salts are perfluoroalkane sulfonates, such as potassium perfluorobutane sulfonate ("KPFBS", also known as “Rimar salt") and potassium diphenylsulfone sulfonate (“KSS”) yield haze free compositions when blended with polycarbonate resin.
- KPFBS potassium perfluorobutane sulfonate
- KSS potassium diphenylsulfone sulfonate
- KPFBS potassium perfluorobutane sulfonate
- KSS potassium diphenylsulfone sulfonate
- the use of perfluoroalkane sulfonates in polycarbonate resins is described in U.S. Pat. No. 3,775,367. However, the benefits which can be obtained using these materials alone are limited and indeed additional additives are generally included.
- the conventional means for enhancing the fire-retardant properties of these type of compositions while retaining transparency has been the addition of soluble organic halogen additives.
- commercial grades of LEXAN polycarbonate resin eg. 940A, 920A
- KSS 0.3 phr
- a tetrabromo- bisphenol /bisphenol A copolymer 0.5 phr, net 0.13 phr bromine content
- the 920A and 940A grades have inconsistent/unreliable performance in the UL94 NO 125 mil flammability test that these grades are designed to meet.
- the brominatedadditive is unsuitable for compositions which are required to meet "ECOs-friendly" tandards, since these standards prohibit the inclusion of bromine or chlorine based FR additive
- US Patent No. 3,933,734 discloses the use of monomeric or polymeric aromatic sulfonates or mixtures thereof as fire-retardant additives for polycarbonates.
- US Patent No. 6,353,046 issued March 5, 2002 discloses that improved fireproperties can be imparted to polycarbonate resin composition by incorporating into the polycarbonate a firecomponent comprising a perfluoroalkane sulfonate, such as potassium perfluorobutane sulfonate, and a cyclic siloxane, such as octaphenylcycl otetrasil oxane .
- the present invention provides a method for making a flame-retarded polycarbonate resin comprising adding to the high melt-strength polycarbonate resin an effective flame-retardant amount of a potassium salt of a perfluoroalkane sulfonate and a sodium salt of toluene sulfonic acid.
- melt strength of the polycarbonate is enhanced by the addition of an antidrip agent.
- the two salts may be formulated in advance into a composition in accordance with the invention. Use of such a composition, particularly in an aqueous carrier, results in superior fire-retardant performance.
- the present invention provides a method for making a flame-retarded polycarbonate resin by adding to a high melt strength polycarbonate resin (for example produced by addition of an antidrip) an effective fla e-retardant amount of a potassium salt of a perfluoroalkane sulfonate, aand sodium salt of toluene sulfonic acid.
- a high melt strength polycarbonate resin for example produced by addition of an antidrip
- the present invention provides a high melt strength polycarbonate resin composition with flame-retarded properties.
- the composition comprises a high melt strength polycarbonate resin and an effective flame-retardant amount of a potassium salt of a perfluoroalkane sulfonate and a sodium salt of toluene sulfonic acid.
- the invention provides a flame-retardant composition
- a flame-retardant composition comprising a potassium salt of a perfluoroalkane sulfonate and a sodium salt of toluene sulfonic acid in a ratio which provides synergistic effectiveness as a flame-retardant additive for polycarbonate.
- the polycarbonate resin used in the method and composition of the invention may be of any grade and made by any method.
- the polycarbonate may be made via interfacial processes or by melt process (catalytic transesterification).
- the polycarbonate may be either branched or linear in structure, and may include functional substituents.
- Polycarbonate copolymers are also included within the invention. Techniques for manufacture of polycarbonates by these processes are well known, for example from U.S. Pat. Nos. 3,030,331, 3,169,121, 4,130,548, 4,286,083, 4,552,704, 5,210,268 and 5,606,007.
- the polycarbonate is one which can be characterized as having high melt strength, i.e.
- R* 1.8.
- R* is the viscosity ratio at 1 rad/s and at 100 rad/s measured at a temperature when the viscosity at 100 rad/s is equal to 20,000 poise.
- High melt strength can be an inherent property of the polycarbonate, for example as a result of a branched polycarbonate structure, or can be achieved through the addition of an antidrip agent.
- the potassium salt of a perfluoroalkane sulfonate is preferably one having a to 4 carbon atoms in the alkane group. Specific, non-limiting examples of suitable compounds are potassium perfluorobutane sulfonate and potassium trifluoromethane sulfonate.
- the sodium salt of toluene sulfonic acid is preferably sodium toluene sulfonic acid.
- the potassium salt of perfluoroalkane sulfonate and the sodium salt of the toluene sulfonic acid are blended with molten polycarbonate, for example in a screwe-type xtruder, and extruded and molded into parts of desired shapes. They may be added to the polycarbonate in combination, for example as a fireadditive composition comprising a potassium salt of a perfluoroalkane sulfonate and a sodium salt of toluene sulfonic acid, or sequentially in either order.
- the potassium salt of the perfluoroalkane sulfonate and the sodium salt of the toluene sulfonic acid are combined with the polycarbonate resin in an effective flame- retardant amount.
- An effective, flame-retardant amount is one that increases the flame-resistant properties of the polycarbonate, as compared to an otherwise identical composition without the salts of a perfluoroalkane sulfonate and a toluene sulfonic acid. While the specific method for testing for flame-retardant properties is not critical, one common method that may be employed involves the formation of bars molded from extruded polycarbonate and tested using the standard Underwriters Laboratory UL 94 test method.
- the data may be analyzed by calculation of the average flame out time (avFOTsec), standard deviation of the flame out time (sdFOTsec) and the total number of drips, and using statistical methods to convert that data to a prediction of the probability of first time pass, or "p(FTP)" that a particular sample formulation would achieve a V0 "pass” rating in the conventional UL94 testing of 5 bar.
- p(FTP) will be as close to 1 as possible, for example greater than 0.9 and more preferably greater than 0.95, for maximum flame-retardant performance in UL Testing.
- the amount of postassium salt of perfluoroalkane sulfonate is suitably low, to minimize cost, for example in the range of 0.004 to 0.05 weight %, more preferably from 0.008 to 0.03 weight %.
- the amount of the sodium salt of the toluene sulfonic acid is suitably from 0.001 to 0.1 weight %, more preferably from 0.005 to 0.05 weight %.
- the fire-retarded polycarbonate resins of the invention may also include an antidrip agent.
- an antidrip agent refers to an additive which increases the melt strength of the polycarbonate, thereby reducing the tendency of the resin, when heated to close to melting, to drip.
- suitable antidrip agents include PTFE-based antidrip agents, such as 1/1 dispersion of PTFE in styrene acrylonitrile resin, emulsion based PTFE, and steam-precipitated PTFE.
- the antidrip agent is added in an amount effective to increase the melt strength and reduce drip, for example in the range of from 0.05 to 0.5 weight %.
- additives which are conventional in the art may also be added to the polycarbonate resin in the method and compositions of the invention.
- additives include but are not limited to stabilizers, mold release agents, light stabilizers, heat stabilizers, pigments, dyes, PTFE, glass fibers, and fillers.
- Polycarbonate resin in accordance with the invention containing a fire-retardant comprising a potassium salt of a perfluoroalkane sulfonate and a sodium salt of toluene sulfonic acid is suitably used for making molded articles.
- the polycarbonate is particularly suitable for making thin walled articles, for examples articles having a wall thickness of less than 1.5 mm, i.e., 1mm to 1.5 mm, because of its ability to achieve good fire-retardance even for thin pieces of material. These articles may be formed by extrusion, or blow molding.
- the fire-retardant additive in accordance with the invention suitably comprises potassium salt of a perfluoroalkane sulfonate and a sodium salt of toluene sulfonic acid in a ratio which provides synergistic effectiveness as a flame-retardant additive for polycarbonate.
- the composition suitably contains the potassium salt of a perfluoroalkane sulfonate and a sodium salt of toluene sulfonic acid in a ratio of from about 0.1 to 2.0 by weight, more preferably 0.18 to 1.8 by weight. This composition is added to polycarbonate resin in an amount appropriate to achieve the levels of the individual additives described above.
- Example 1 A set of experiments was performed using different formulations of polycarbonate with combinations of potassium perfluorobutane sulfonate (Rimar salt) and sodium toluene sulfonic acid (NaTS). Since the two additives were in low loading, resin powder concentrates of each were made and the same added to the formulation. The data in Table 1 indicates that the flame performance at 0.1-0.2 loading levels of NaTS is inconsistent, and thus suggests that the loadings should preferably be ⁇ 0.1.
- Flammability testing was conducted using the statistical "UL Tool” in which 20 bars, at the specified thickness, rather than the usual 5 bars, are burned using the UL94 test protocol and the average flame-out times and Standard Deviation (SD) of the flame- out times are calculated and subsequently converted to a numerical estimate of the probability of a first time pass "p[FTP] "value instead of the simple and less informative pass/fail criteria in UL94 testing.
- SD Standard Deviation
- Example 2 A further set of experiments was performed at very low loading of 0.009 RIMAR with 0.05 NaTS. For this experiment, both the additives were dissolved in water and the respective solution was used to make separate resin powder concentrates. As summarized in Table 2, this formulation results in a robust p[FTP] value of 0.93. In addition, the flame results indicate that increasing levels of NaTS doenot necessarily increase the fire-retardant properties.
- Example 3 Further experiments were performed using resin powder concentrate of the individual water solution at different levels. As summarized in Table 3, in these experiments, the optimal loading of RIMAR, and NaTS was 0.01, and 0.025 respectively. Table 3
- Example 4 A further set of experiments was performed in which RIMAR loading was held constant at 0.009 and the NaTS loading was varied between 0-0.03. As shown in Table 4, the data indicates that NaTS loading range of 0.005-0.05 at 0.009 RIMAR should result in p[FTP] > 0.9. These results also confirms the need for both the additives being present for good FR performance at the low levels of additives used. Batch 1, which had only RIMAR at 0.009, resulted in a very low p[FTP] of 0.1067.
- Example 5 A further set of experiments was performed in which the NaTS loading was held constant at 0.015 and the RIMAR loading was varied. These experiments again confirmed the need for both the additives to achieve p[FTP] > 0.9 at the low concentrations used. The minimum amount of RIMAR required in these experiments to achieve p[FTP] > 0.9 was 0.006 and that of NaTS is 0.015 Table 5
- Example 6 Further experiments were performed in which a higher amount of High Flow resin was used. The melt flows ranged from 14.3-15.3. Further for Batch 1, both RIMAR and NaTS were dissolved together in water and then blended in resin powder to form the concentrate. This was done for ease of extrusion process if this were to run on a manufacturing scale. This also allows the use of very small amount of both the additives, thus making it economically more attractive. In batches 2 5 the two additives were added separately in the powder form. The results are summarized in Table 6. As shown, batch 1, in which the Rimar and NaTs were pre-mixed exhibited much better fire retardant properties at much lower levels.
- Example 7 Since the flame performance for the Rimar, NaTS combination was so robust at 62 mils, it was desirable to confirm if it was equally robust at a lower gauge of 45 mils. As shown below in Table 7, flame performance for this thickness measured at two melt flows, namely 940, Batch 7-1 (melt flow range 8-12) and 920, Batch 2 (meltflow range 12-16) were very good with p[FTP] values of 0.97, and 0.96, respectively. These formulations also showed robust 5V performance at 125 mils.
- both the salts were dissolved in water and the same was dispersed in the formulation. It seems the synergistic activity of both the salts is enhanced when first dissolved together in water. It is not exactly understood how this enhancement in flame retardant activity occurs. Although not intending to be bound by any specific mechanism, one may hypothesize that by dissolving both the salts together in water results in complexation of both the salts which has a superior flame retardant synergist activity compared to the synergist activity of them when dispersed individually as water solutions in the resin powder.
- Example 8 The next step was to confirm if the combination of NaTS with potassium trifluoromethane sulfonate (Triflate, Cl salt) was as good as the NaTS + Rimar combination. Since the Rimar + NaTS combination gave good flame performance at loading of 0.009 RIMAR, the same amount was used for Cl salt since the Cl salt is structurally similar to Rimar salt. The amount of NaTS was varied as shown below in Table 8. For all the following formulations, flame performance was measured at 45 mils. Table 8
- Example 9 Since the Cl salt was at a constant level in Example 8, the next step was keeping NaTS constant and varying the am. > . of Cl salt as shown in Table 9. These experiments confirm that the combination of Cl salt with NaTS also yields robust flame retardant activity.
- Triflate-C1 Salt 0 0.006 0.009 0.012 0.015
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003272245A AU2003272245A1 (en) | 2002-10-29 | 2003-08-27 | Method for making fire-retarded polycarbonate and related compositions |
EP03754419A EP1558676A1 (en) | 2002-10-29 | 2003-08-27 | Method for making fire-retarded polycarbonate and related compositions |
JP2004548303A JP2006504823A (en) | 2002-10-29 | 2003-08-27 | Process for producing flame retardant polycarbonate and related compositions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/065,545 US6790899B2 (en) | 2002-10-29 | 2002-10-29 | Method for making fire-retarded polycarbonate and related compositions |
US10/065,545 | 2002-10-29 |
Publications (1)
Publication Number | Publication Date |
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WO2004039879A1 true WO2004039879A1 (en) | 2004-05-13 |
Family
ID=32106069
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2003/027048 WO2004039879A1 (en) | 2002-10-29 | 2003-08-27 | Method for making fire-retarded polycarbonate and related compositions |
Country Status (7)
Country | Link |
---|---|
US (1) | US6790899B2 (en) |
EP (1) | EP1558676A1 (en) |
JP (1) | JP2006504823A (en) |
CN (1) | CN1312205C (en) |
AU (1) | AU2003272245A1 (en) |
TW (1) | TW200420644A (en) |
WO (1) | WO2004039879A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009029780A1 (en) * | 2007-08-30 | 2009-03-05 | Sabic Innovative Plastics Ip B.V. | Polyestercarbonate compositions |
CN109810404A (en) * | 2018-12-24 | 2019-05-28 | 浙江大学宁波理工学院 | A kind of polypropylene/metal hydroxides/rare earth compound fire proofing |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7728059B2 (en) * | 2006-02-14 | 2010-06-01 | Sabic Innovative Plastics Ip B.V. | Polycarbonate compositions and articles formed therefrom |
US20070191519A1 (en) * | 2006-02-14 | 2007-08-16 | General Electric Company | Halogen-free polycarbonate compositions and articles formed therefrom |
US7632881B2 (en) * | 2006-06-22 | 2009-12-15 | Sabic Innovative Plastics Ip B.V. | Polycarbonate compositions and articles formed therefrom |
US20080015292A1 (en) * | 2006-07-12 | 2008-01-17 | General Electric Company | Flame retardant and scratch resistant thermoplastic polycarbonate compositions |
US7732516B2 (en) * | 2008-01-31 | 2010-06-08 | Sabic Innovative Plastics Ip B.V. | Flame retardant polyimide/polyester-polycarbonate compositions, methods of manufacture, and articles formed therefrom |
US20090227707A1 (en) * | 2008-03-07 | 2009-09-10 | Domenico La Camera | Flame retardant polycarbonate based composition including carbon |
JP5364653B2 (en) * | 2010-06-14 | 2013-12-11 | 三菱エンジニアリングプラスチックス株式会社 | Flame retardant polycarbonate resin composition and molded product comprising the same |
CN103333478A (en) * | 2013-06-26 | 2013-10-02 | 江苏启蓝新材料有限公司 | Halogen-free flame-retardant polycarbonate and preparation method thereof |
US9840586B2 (en) * | 2013-11-15 | 2017-12-12 | Sabic Global Technologies B.V. | Methods for measuring properties in crosslinked polycarbonate |
Citations (3)
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US3775367A (en) * | 1969-06-13 | 1973-11-27 | Bayer Ag | Flame resistant polycarbonates |
US4104253A (en) * | 1976-10-15 | 1978-08-01 | General Electric Company | Flame retardant polycarbonate composition |
US6462111B1 (en) * | 2001-12-10 | 2002-10-08 | General Electric Company | Translucent flame retardant polycarbonate compositions |
Family Cites Families (13)
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US3933734A (en) | 1973-12-28 | 1976-01-20 | General Electric Company | Flame retardant polycarbonate composition |
US3971756A (en) | 1974-08-09 | 1976-07-27 | General Electric Company | Flame retardant polycarbonate composition |
US4028297A (en) | 1975-07-18 | 1977-06-07 | General Electric Company | Novel flame retardant polycarbonate compositions |
US4110299A (en) | 1976-10-15 | 1978-08-29 | General Electric Company | Flame-retardant polycarbonate composition |
US4130299A (en) | 1977-09-12 | 1978-12-19 | Monsanto Company | Low-odor dye solvents for pressure-sensitive copying systems |
US4201832A (en) * | 1978-06-23 | 1980-05-06 | General Electric Company | Non melt-drip flame retardant polycarbonate composition |
US4303575A (en) | 1980-02-07 | 1981-12-01 | Mobay Chemical Corporation | Flame retardant polycarbonate compositions |
US4335038A (en) | 1980-09-26 | 1982-06-15 | The Dow Chemical Company | Polycarbonate containing a metal perfluoroborate and an organosilane as ignition depressants |
DE3203905A1 (en) | 1982-02-05 | 1983-08-11 | Bayer Ag, 5090 Leverkusen | POLYCARBONATE MOLDS WITH IMPROVED FLAME RETENTION |
GB8806497D0 (en) | 1988-03-18 | 1988-04-20 | Mortile Acoustic Ind Ltd | Non-toxic fire retardant thermoplastic material |
US4916194A (en) | 1989-03-06 | 1990-04-10 | General Electric Company | Flame retardant aromatic polycarbonate blends |
US5508323A (en) | 1992-06-29 | 1996-04-16 | Dow Corning Corporation | Method for imparting fire retardancy to organic resins |
US6353046B1 (en) | 2000-04-28 | 2002-03-05 | General Electric Company | Fire-retarded polycarbonate resin composition |
-
2002
- 2002-10-29 US US10/065,545 patent/US6790899B2/en not_active Expired - Lifetime
-
2003
- 2003-08-27 EP EP03754419A patent/EP1558676A1/en not_active Ceased
- 2003-08-27 CN CNB038257394A patent/CN1312205C/en not_active Expired - Fee Related
- 2003-08-27 WO PCT/US2003/027048 patent/WO2004039879A1/en not_active Application Discontinuation
- 2003-08-27 AU AU2003272245A patent/AU2003272245A1/en not_active Abandoned
- 2003-08-27 JP JP2004548303A patent/JP2006504823A/en active Pending
- 2003-10-14 TW TW092128452A patent/TW200420644A/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US3775367A (en) * | 1969-06-13 | 1973-11-27 | Bayer Ag | Flame resistant polycarbonates |
US4104253A (en) * | 1976-10-15 | 1978-08-01 | General Electric Company | Flame retardant polycarbonate composition |
US6462111B1 (en) * | 2001-12-10 | 2002-10-08 | General Electric Company | Translucent flame retardant polycarbonate compositions |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009029780A1 (en) * | 2007-08-30 | 2009-03-05 | Sabic Innovative Plastics Ip B.V. | Polyestercarbonate compositions |
CN109810404A (en) * | 2018-12-24 | 2019-05-28 | 浙江大学宁波理工学院 | A kind of polypropylene/metal hydroxides/rare earth compound fire proofing |
CN109810404B (en) * | 2018-12-24 | 2021-11-23 | 浙江大学宁波理工学院 | Polypropylene/metal hydroxide/rare earth compound flame-retardant material |
Also Published As
Publication number | Publication date |
---|---|
CN1720288A (en) | 2006-01-11 |
CN1312205C (en) | 2007-04-25 |
US20040082691A1 (en) | 2004-04-29 |
AU2003272245A1 (en) | 2004-05-25 |
TW200420644A (en) | 2004-10-16 |
JP2006504823A (en) | 2006-02-09 |
EP1558676A1 (en) | 2005-08-03 |
US6790899B2 (en) | 2004-09-14 |
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