CA2178718A1 - New flame retardant polymeric compositions - Google Patents
New flame retardant polymeric compositionsInfo
- Publication number
- CA2178718A1 CA2178718A1 CA002178718A CA2178718A CA2178718A1 CA 2178718 A1 CA2178718 A1 CA 2178718A1 CA 002178718 A CA002178718 A CA 002178718A CA 2178718 A CA2178718 A CA 2178718A CA 2178718 A1 CA2178718 A1 CA 2178718A1
- Authority
- CA
- Canada
- Prior art keywords
- composition according
- nylon
- oxide
- group
- forming agent
- 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.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- 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
- C08K5/43—Compounds containing sulfur bound to nitrogen
Abstract
A flame retardant polymer comprising at least one polymer selected from the group consisting of a polyamide, polyolefin, polyester, polyacrile, polystyrene and polyurethane, a flame retardant effective amount of an additive comprising at least one (a) hexavalent oxygenated sulfur compound and optionally at least one of (b) a char-forming agent, (c) a metal compound, (d) a filler or reinforcing agent, and (e) a flow modifier. By excluding halogens and phosphorus beneficial results are achieved without the negative consequences attending their presence.
Description
W095tl8841 2 1 7 8 7 1 ~ Pcr/usg5/ooo70 l~TLE
NEW FLAME RETARDANT POLYMERIC COMPOSl rIONS
BACKGROUND OF THE INVENTION
The present invention relates to the flame retardation of polymers 5 with particular regard to non-halogen and non-phosphorus-based flame retarding materials.
Flame retardation (FR) of polymers is at present m~nd~tory for many of their applic~tions~ due to strict laws and re~ tions in many countries. Accordingly, many systems for rendering various plastics flame retald~l have been developed. These systems involve mixing or blending the plastic m~teri~lC v~rith one or more additives, e.g., flame retarding chP~ c. Most of these chemicals are either based on halogens or on phosphorus and conctitute~ in most cases, low molec~ r weight compounds.
They are sometimes applied in conjunction with co-additives: synergists, such as ~ntimQny oxide, which is added to halogen de~ivali~es, and nitrogen col~ oullds~ added to phosphorus flame retardants. The halogen-based additives, while providing a reasonable degree of are safety, suffer from a number of inadequacies: they generate collosive l~ydrogell halides and smoke upon combustion and they are suspected of elllitLin~ highly toxic sllbst~ncec- High lo~-ling of the halogen-based flame retardant are usually neederl, which impact the desirable physical plo~cllies of the polymer.
Similarly phosphorus deriv~lives are used in relatively high lo~-lirl&c since in many cases, such as in polyamides, their effectiveness is relatively low. They may also cause plasticization and degr~d~tion. Red phosphorus~ in particular, which is used for polyamides, can cause the emiCcion of the lmde-cirable phosphine during and after procescine Due to the high amounts of the above-mentioned additives required for effective flame retardation, the cost of treatment is relatively high.
An i~ ol lant development in flame retaldance of polymers was based on the principle of intl~mescence. It employs ~mmonillm polyphosphate (A`PP), which is blended with coadditives, a char-forming material, usually a polyhydric alcohol such as pentaerythritol (petol) and a nitrogen delivative, such as melamine, guanidine or urea as a blowing agent, producing non-combustible gases. The APP is believed to serve as a dehydration catalyst of the polyhydric alcohol, creating double bonds, which 2 17 8 7 1 ~3 PCT/US95/00070 later crosslinlc and produce a char network. The gases evolve from the simlllt~neously decolllposing nillogeneous blowing agent, eYr~nd and swell tbe crosslinked structure cont~inine the plastic, the crosclinked petol and APP.
S While the catalytic action of the APP has not been completely eluçitl~te~l, it is believed tbat the Iyd~o~l groups in the petol as well as thehydl~Ayl groups formed on the methylenic segments of tbe polymer by i-i~tinn witb air during combustion are being phosphorylated and sllbse(llle-ntly depllosl)hol~lated, thereby c~llcing dehydration. This process is not very efficient, since relatively large quantities are usually required.
Sul~ illgly, it has been found, and this is tbe objective of this invention, that a very high degree of flame retardance can be obtained by applying ~A~ tecl bexavalent sulfur derivatives incte~(l of phosphorus derivatives for flame retarding polymers, in particular poly~mi~es These dclivali~res are less toxic, less collosive and considerably less ~Al,cnsive than h~lQ~en and P compounds. In this invention, the sulfur derivative serves as the catalyst in an intllmescence system, which also includes a char-forming agent and other necess~ry ingredients, depending on the polymeric system.
The catalytic effect of the hexavalent sulfur delivalive might consist of the slllf~tion of the h~droAyl groups and subsequent deslllf~tion~
thereby ~ff~cting a dehydration, double bond for...ation and crosslinking.
This invention aims at the flame retardation of ther noplastic polyrners by non-halogen and non-phosphorus colllpoullds. It is centered on the ~ ising discovery that hexavalent sulfur de~ ati~es are highly effective 25 in flame retardation of a large range of thermoplastic polymers. Among these polymers are poly~mides, polyolefins, polyesters, polyacrylics, polystyrenes, polyurethanes, polycarbonates, and polymer blends. The present invention is especially useful for polyamides, such as nylon 6, nylon 66, nylon 11, nylon 12, nylon 4.4, nylon 6.3, nylon 6.4, nylon 6.10 and nylon 30 6.12. These polyamide names are well known in the scientific world, and defined, for in~t~nce, in the article on polyamides in the Encyclopedia of Polymer Science and Engineering, 2nd edition.
The hexavalent sulfur derivatives for use as additives in the present invention can be inorganic or organic derivatives of sulfuric and 35 slllf~mic acids. Among these materials are s~llf~mic acid salts, H2NSO3 Metal, condensation products of sl-lf~mic acids, such as imidobi-sulfonic W095/18841 2 1 7 8 7 1 8 PCT/U~g51~070 acid, NH(SO3H)2 and its salts, such as mono- and di-~mmoni~lm salts, alkali metal salts, ~lk~line earth and other divalent and multivalent metal salts.
The invention also incl~ldes aliphatic and aromatic sl~lf~mine-s, such as s~lf~mide (I), imido-sulf~mide (II), substituted sulf~mides (III) in which the 5 R, Rl, R2, R3 and R4 can be different aliphatic or aromatic groups, condenc~tion products of sulfi~Iudes with aldehydes (IV) and cyclic tri-sl~lf~mi~les (V). Advantageously the various R radicals are Cl l6-alkyl, phenyl or naphthyl, each optionally substituted by any h~lo~eTl-free moiety.
In ~dtlition, the invention inrhltles sulfate esters of alcohols of the type of 10 ROSO3 and ~yclic s--lf~te~, such as VI, VII and VIII from mono- and poly-pentaerythritol, IX sirnilar sulfate esters of 1,4-anhydrosorbitol (X) and 1,4-anhydlv...s~ ...;lol, XI,y-sultones such as XII and XIII, and snbstit~tedy-sultone~.
(I) (NH2S02)2NH
(II) (III) [RCH(OH)NHkSO2 (IV) WogS/18841 21 7 8 7 3 ~ PCT/US9S/00070 _ 4 _ r~
r (v) (HOC H2)2C (C H20S 03H)2 (VI) (VII) WO 95tl8841 2 1 7 8 7 1 8 PCI/US95/00070 ._ -- 5 --H OC ~ C~)n a~
~S02~
(VIII) H2C~\
\o/
(IX) ~:OH
HOCH
~OH
C~OH
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O
I~TH
HC
H~OH
CHpH
(XI) ~
C~
(~I) ~ f~
/~
HXH~
(~II) WO g5/18841 2 1 7 8 7 1 8 PCI/US95/00070 . -7 Whereas all the above materials insludetl in the invention share the ability to bring about dehydration of polymers at combustion temperatures, they differ in their ~ropcl lies, such as solubility, hygroscopicity, molecular weight, thermal stability, volatility and other properties, depending on their structure. It is therefore possible according to the invention to adapt hexavalent sulfur derivatives to polymers pocceccing a wide variety of properties especially that of varied processing temperalùres.
The preferred materials for additives in this invention are the salts of th¢ irnido-bisulfonic acid and especially the di-ammonium imido-bi-snlfon~te (DIBS), NH(SO3NH4)2, which is prepared from ammonium sulf~m~t~ by vacuum he~tin~ at 200C. Surprisingly, it has been found that this col~ound is particularly suitable and highly effective for flame retardancy of polyamide 6 and 66, as shown in the examples below. The desirable feature of DIBS, in addition to its FR effect, is its relatively high heat stability. In thermogravimetric me~Curements it was found that the onset of its dcco~ )osilion is above 310C, and it is therefore possible to use it both for nylon 6, which is processed at 240C, and for nylon 66, which is processed at 280C, as well as for other nylons and other polymers which are processed at a range of temperatures from 140-310C.
The arnounts of additive (a) for use in the invention depends on the nature of the polymer, on its procescing temperalu~ and on the degree of flame r~ardancy desired and the nature and amounts of the additives (b) and (c). They range from 0.1 to 40 wt % of the colllposilion. Higher amounts are nee(3ed for polymers with lower melting points than for polymers of higher melting points. For example, for nylon 6, higher amounts of DIBS are required than for nylon 66. In the presence of fillers, such as glass fibers compounded with the polymer, different ~molln~C of additive (a) are needed than without the filler, the amount depending on the nature and wt % of thç filler, and can be easily determined by those skilled in the art.
The flame retarding effect of di-ammonium imido-bi-sulfonate and the other materials listed above on thermoplastic polymers has not been hitherto described in the technical literature and is disclosed here for the first time.
Another basic feature of this invention is that the hexavalent sulfur compound can be an effective flame retardant by itself; however, it is WO 95/18841 2 1 7 8 7 1 8 PCT/US95tO0070 preferably applied together with a char-forming agent, additive (b), such as pentaerythritol and its oligomers, or other polyhydric alcohols, such as glycols and their derivatives, m~nnitol, sorbitol and other three, four, five and six-membered sugar molecules and other derivatives. One may also use 5 polymeric carbohydrates such as starch, xylans, m~nn~n.C and other hemi~ellu~Qses derived from wood and other plants, which are commercially av~ bl~
In this invention, it is sometimes advisable to co~bille the sulfur de~ e and the char-forming agent in one molecule. Such cornpounds, 10 for ~Y~mple are p,e~arcd by esterifying, or otherwise combining, one or more l~ ls in pentaerythritol with sulf~tes, sulf~m~te-s, sulf~mi(les~
slllfimides or imido-slllf~m~tes. Several such materials are, for example, VI, VII, IX, XII, as well as XIII.
Polyhydric alcohols are not the only char-fo....;ng agents used in 15 the present invention. Polyphenylene oxide (PPO) and polyphenylene sulfide (PPS) have been also sul~lisingly found highly suitable char-forming agents in c~ c! ;on with the hexavalent sulfur derivatives. Advantageously they range in mole.~ r weight from about 2,000 to 100,000. Blends of PPO
with poly~mides are well known and are described for example by Aycock, 20 U.S. Patent No. 4,600,741. Additionally, PPO is known to be used as a flame rctardillg coll.~ollent in low amounts in polyamides, as taught by Freitag in U.S. Patent No. 4,888,370 (1989). Only a veIy low degree of flame ret~d~ucy, ho.._~er, has been achieved by this co~ ollent alone. It has been found, for example by Taubitz, et al., U.S. Patent No. 4,866,114 (1989) that high oxygen indices can be achieved only when applied together with phosphorus or halogen derivatives.
PPO and PPS are very stable at the processin~ te-l-peratures of poly~mi~les They have aromatic rings on the backbone. They are virtually Y
free of volatile components at the polymer procescing temperatures. The molecular weight of PPO and PPS can be between 2,000 and 100,000. It is not critical since these materials flux easily with the polyamide during blen~ling. Other polymers to be used as char-foll--il-g agents in the invention inrlude aromatic polysulfides, polysulfones, polyketones, polyimides, polyetherirnides and polyarylates.
The preferred aromatic char-forming agents for the invention are PPS and PPO. High or low molecular weight polymers can be used in the WO 95/18841 2 ~ 7 8 7 t 8 PCI/US95/00070 . .
g invention. The char-forlllilJg agents can be applied in the form of powder, granules, flakes, beads or diced cubes.
The amounts of additive (b), such as pentasl ~lhritol or PPS to be used in the invention is about 0.0% to 50%, preferably from 0.5% to about 5 40%. It will be evident to those skilled in the art of polyrner compounding and flame Fetardancy that the exact amount will depend on the polymeric system and on the degree of flame retardancy required. The ~mount of (b) is to be adapted to the amount of (a).
The metal colllpoullds for use as additive (c) in the invention 10 co..-l..; e oxides and salts of alkali, ~lk~line earth, divalent and multivalent metals. 04e or several such colll~oullds may be used together in the invention, dependin~ on the nature of the polymeric system and according to the function required. It is believed that there are three major functions which the metal colllpounds may fulfill in the invention:
A. Regnlation of the acidity of the co~ osilion during processing, storage and co~l~u~lion. The additive (a) releases a relatively strong acid which may degrade the polymer ~Ace~sively and bring about a deterioration of its physical l,f~ellies and a decrease in molecular weight, which in~lcas~s its fl~mm~hility. Whereas a limitet3 degree of degradation is 20 needed during the co...b~.~l;on to f~cilit~te the dehydration and the crocclinhne, excessive degr~ tion is detriment~l. It has sul~lisingly been found that zinc oxide as additive (c) can co~lnteract this excessive degr~ tif)n by buffering the system and reg~ tir~ the acidity. The identity of the metal oxide and its concenllation are most illl~ollant and have to be 25 strictly regvl~te~ An excess in the (c) concentration may decrease the effc~livclless of additives (a) and (b). If the concentration is too low, a degr?~l~tio~ is perceived. It has further sul~Jri~ingly been discovered that a similar effect can be obtained by ~drling~ incte~d of (c), a basic nitrogen deli~,ali~c, such as mel~mine, which l,res~ bly pel~lllls the same 30 b~lffçrir~ f~tnction- It can be seen by coln~al ing Examples 14, lS and 16 hereinbelow. Thus it is clear that melamine may be optional ~or the invention, but it is not es.ce.nti~l B. A char stabilizing effect. The integrity and me~nical strength of the char is known to contribute greatly to flame retaldancy. The 35 char has to perform the function of a barrier to the passage of fl~mm~ble gases and rnolten mass out of the polymer and to the transfer of heat from WO g5/18841 2 1 7 8 7 1 8 pCT/U:,~5J'~ 70 the flarne to the polymer. Low melting glasses such as zinc borate have been used as a flarne retard~lt and smoke su~pressant additive in conjunction with h~lo~enc for polyvinyl chloride [see R. E. Meyers et al., J. Fire Sci, (1985) ~, 415~31]. It has also been disclosed as a component in conjunction S with magnesium l~d~Aide for PE (Nakagoma et al., Japan Patent No.
02,150,436) and with triphenyl phosphate for polycall,onate (Watanabi, J.
Eur~ean Patent Application 0520186 A1 (1992). Zinc borate has up to now not been iicclQsed as a collll)ollent in a sulfur-based flame retardant CO1I1~JOS;~ n According to the present invention, zinc borate can serve in a 10 dual r~p~ity: a char-stabilizer and a buffer.
The low meltine glasses according to the invention co~ rise borates o ~ ..gP~-Pse, iron and ~refe,ably zinc, for example Zn;~B402, ZnB2O4 or ZnB4O4. Other low-melting glasses are, for inct~nre, lead borate glass and aLkali phosphate glass with meltine points of 200 - 600C
15 and plefe~ably 300 - 500C. They are cornrnercially available as solder gl~cces~ frits and glazes. Such glasses include those described by R. E.
Meyers (see above) and incol~ol~ted by reference in its entirety herein.
Borophosph~tes are also incl~ ed in these gl~cces.
C. The third flmGtion of the additive (c) is as crosslinkine catalyst.
20 Many m~t~llic co.~oullds are known to catalyze cro~slinkinE, as described by Petersen in Handbook of Fiber Science and Technology, Vol. II, mi~l Procc;s - .~g of Fibers and Fabrics, Part A, Functinn~l Finishes, M.
L~vrin and S. B. Sello, editors, Marcel dekker, Publishers, pages 205 - 210 (1983). The preferred catalysts for the invention are m~g,.e~ .... hydrogen 25 phosphate, ~rCQ~ lll oxide or ~ ... oxide. Whereas the above crosslinki~g agents are a part of the invention, their use is optional.
Additive (c) can be col.")osed of one, two or three of the above-mentione~l materials.
The amounts of additive (c) applied accordi--~ to the invention 30 are 0.0 to 40 wt % of the co.ll~osilion. It will be evident to those skilled in the art that the amount will valy according to the polymer system and to the degree of flame retardance desired, and for a given level of flame retardancy the composition of (c) can be varied and its amount can be lower as the amount of (a) and (b) is higher, and conversely. The amount of the 35 thermoplastic polymer is at a minim~lm 20% by weight of the total col,-posiliQn.
The polyrner mLxtures of the invention may also inrlllde additive (d) such as reinforch~g agents and fillers: glass fibers, rnineral fibers, carbon fibers, ararnide ~lbers, talc, mica, gypsum, wollastonite, etc. They may also in~ de pigmentc~ stabilizers, processing aids, coupling agents, lubricants, 5 mold-release agents, electro-conductive additives and impact modifiers.
The polymer ~ ures may also include, according to the invention, flow modifiers (additive (e)) such as Teflon (polytetrafluoroethylene) p-~wder. The amounts of the powdered Teflon~9 may vary from 0.0 to 3 wt % of the composition.
Other flame retardants such as phosphorus- and halogen-co~ g agents can be present in the composition and they contribute partly to the flarne retardance of the polymers. Ho..~.er, an important advantage of the present invention is that no halogen- or phosphorus-based flarne r~tardant additives are needed for obtaining a very high degree of flame rel~udancy, which are ~ ressed in LOI values above 30 and UL94 rating of VO.
The rnLxing and blen~iing of the ingre-lient~ of the invention can be carried out by any method suitable for obtaining lmi~oll-- dispersions of part~ te solids, such as mixing in the Brabender rmLYer or in an extruder.
EX~MPLES
The present invention is further illustrated, but not lirnited to, the following exarnples.
Varying al--ol-~ls of ingre-lient~ (a), (b) and (c) were ~dmiyed with the powdered polymer in a Brabender mixer of 240 grams capacity for a time and at a temperalure dependent upon the polymer used, at 40 rotations per minnte. Sarnples were prepared by conll)ression molding in a hot press at a temperature dependent on the polymer used, cooled to room temperature and cut to standard test pieces. The mixing and co..,l)ression molding for nylon 6 was 240C and the time of mixing was 4 min~ltes For 30 nylon 66, the tirne of rnixing was 5 minutes, the telll~efalulc; was 270C. The nylon used was commercial-grade powder, produced by Rhone Pou lenc, France.
The fl~mm~bility was tested by the limitin~ oxygen index (LOI) method, accordil~g to ASTM D-2863 and by UL (Underwriters 35 Laboratories) 94 configuration-bottom ignition by a st~nd~rd burner flame for two successive 10-second intervals, with averaging of the after flame WO gS/18841 ~ 1 7 ~ 7 1 8 PCT/US95/00070 time. Ten test pieces were tested and the burning times given in each example are averages of all ten test pieces.
The DIBS used in most examples was ~ mm~nillm imido bi~lllfon~te. It was prepared by vacuum heating at 200C of ~mmonium 5 slllf~m~te. Its formula is NH(SO3NH4)2.
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WO g5/18841 2 1 7 8 7 1 8 PCI~/US95/00070 Some comp~rative materials not within the invention are also in~ (le-l, viz. Examples 6, 7, 8, 9, 13, 20, 26, 28, and 31. It can be seen thatno signific~nt flame retardancy effect is obtained in the absence of additive (a). FY~mpl~ 7 shows that (a) without (b) or (c) is inadequate. Example 8 shows that mel~mine plus ammonium slllf~m~te without (b) is inadequate, although it shows an increased LOI. Comparing Examples 14, 15 and 16 show that the same wt ~o of DIBS yields a similar result in the presence of m~l~mine or when, incte^ 1 of m~!~mine, additive (c), e.g., ZnO, is added.
This shows that the m~l~min~ is not needed for the perro~ ance of the invention, ~lthollgh it may be optionally used. Comparing examples 15 and 16, it can be seen that a high degree of flame retardance can be obtained without additive (e), and its use is optional.
Examples 21, æ and 23 (see Table 3) show that a high degree of F~ is ol)tai~ed when only additives (a) and (c) are ~rescn~ in the case of glass fiber ~ orced nylon 6, while additive (c) alone (Example 26) yields a very mode~ i~up~o.e~llent.
It is clearly evident from the examples that, in order to ~e.roll,-the invention, it is escenti~l to blend the polymer with (a) or with (a) and (b)or (a) and (c) or (a), (b) and (c), depending on the polymer ~ ule.
While only a few exemplary embodiments of this invention have been desc ibed in detail, those skilled in the art will rCco~ 7c that there are many possible variations and modifications possible; many of the novel and advantageous fealures of the invention can be formed. Accordillgly, it is intende-l that the following claims cover all such modifications and 2S v~ri~tion.c,
NEW FLAME RETARDANT POLYMERIC COMPOSl rIONS
BACKGROUND OF THE INVENTION
The present invention relates to the flame retardation of polymers 5 with particular regard to non-halogen and non-phosphorus-based flame retarding materials.
Flame retardation (FR) of polymers is at present m~nd~tory for many of their applic~tions~ due to strict laws and re~ tions in many countries. Accordingly, many systems for rendering various plastics flame retald~l have been developed. These systems involve mixing or blending the plastic m~teri~lC v~rith one or more additives, e.g., flame retarding chP~ c. Most of these chemicals are either based on halogens or on phosphorus and conctitute~ in most cases, low molec~ r weight compounds.
They are sometimes applied in conjunction with co-additives: synergists, such as ~ntimQny oxide, which is added to halogen de~ivali~es, and nitrogen col~ oullds~ added to phosphorus flame retardants. The halogen-based additives, while providing a reasonable degree of are safety, suffer from a number of inadequacies: they generate collosive l~ydrogell halides and smoke upon combustion and they are suspected of elllitLin~ highly toxic sllbst~ncec- High lo~-ling of the halogen-based flame retardant are usually neederl, which impact the desirable physical plo~cllies of the polymer.
Similarly phosphorus deriv~lives are used in relatively high lo~-lirl&c since in many cases, such as in polyamides, their effectiveness is relatively low. They may also cause plasticization and degr~d~tion. Red phosphorus~ in particular, which is used for polyamides, can cause the emiCcion of the lmde-cirable phosphine during and after procescine Due to the high amounts of the above-mentioned additives required for effective flame retardation, the cost of treatment is relatively high.
An i~ ol lant development in flame retaldance of polymers was based on the principle of intl~mescence. It employs ~mmonillm polyphosphate (A`PP), which is blended with coadditives, a char-forming material, usually a polyhydric alcohol such as pentaerythritol (petol) and a nitrogen delivative, such as melamine, guanidine or urea as a blowing agent, producing non-combustible gases. The APP is believed to serve as a dehydration catalyst of the polyhydric alcohol, creating double bonds, which 2 17 8 7 1 ~3 PCT/US95/00070 later crosslinlc and produce a char network. The gases evolve from the simlllt~neously decolllposing nillogeneous blowing agent, eYr~nd and swell tbe crosslinked structure cont~inine the plastic, the crosclinked petol and APP.
S While the catalytic action of the APP has not been completely eluçitl~te~l, it is believed tbat the Iyd~o~l groups in the petol as well as thehydl~Ayl groups formed on the methylenic segments of tbe polymer by i-i~tinn witb air during combustion are being phosphorylated and sllbse(llle-ntly depllosl)hol~lated, thereby c~llcing dehydration. This process is not very efficient, since relatively large quantities are usually required.
Sul~ illgly, it has been found, and this is tbe objective of this invention, that a very high degree of flame retardance can be obtained by applying ~A~ tecl bexavalent sulfur derivatives incte~(l of phosphorus derivatives for flame retarding polymers, in particular poly~mi~es These dclivali~res are less toxic, less collosive and considerably less ~Al,cnsive than h~lQ~en and P compounds. In this invention, the sulfur derivative serves as the catalyst in an intllmescence system, which also includes a char-forming agent and other necess~ry ingredients, depending on the polymeric system.
The catalytic effect of the hexavalent sulfur delivalive might consist of the slllf~tion of the h~droAyl groups and subsequent deslllf~tion~
thereby ~ff~cting a dehydration, double bond for...ation and crosslinking.
This invention aims at the flame retardation of ther noplastic polyrners by non-halogen and non-phosphorus colllpoullds. It is centered on the ~ ising discovery that hexavalent sulfur de~ ati~es are highly effective 25 in flame retardation of a large range of thermoplastic polymers. Among these polymers are poly~mides, polyolefins, polyesters, polyacrylics, polystyrenes, polyurethanes, polycarbonates, and polymer blends. The present invention is especially useful for polyamides, such as nylon 6, nylon 66, nylon 11, nylon 12, nylon 4.4, nylon 6.3, nylon 6.4, nylon 6.10 and nylon 30 6.12. These polyamide names are well known in the scientific world, and defined, for in~t~nce, in the article on polyamides in the Encyclopedia of Polymer Science and Engineering, 2nd edition.
The hexavalent sulfur derivatives for use as additives in the present invention can be inorganic or organic derivatives of sulfuric and 35 slllf~mic acids. Among these materials are s~llf~mic acid salts, H2NSO3 Metal, condensation products of sl-lf~mic acids, such as imidobi-sulfonic W095/18841 2 1 7 8 7 1 8 PCT/U~g51~070 acid, NH(SO3H)2 and its salts, such as mono- and di-~mmoni~lm salts, alkali metal salts, ~lk~line earth and other divalent and multivalent metal salts.
The invention also incl~ldes aliphatic and aromatic sl~lf~mine-s, such as s~lf~mide (I), imido-sulf~mide (II), substituted sulf~mides (III) in which the 5 R, Rl, R2, R3 and R4 can be different aliphatic or aromatic groups, condenc~tion products of sulfi~Iudes with aldehydes (IV) and cyclic tri-sl~lf~mi~les (V). Advantageously the various R radicals are Cl l6-alkyl, phenyl or naphthyl, each optionally substituted by any h~lo~eTl-free moiety.
In ~dtlition, the invention inrhltles sulfate esters of alcohols of the type of 10 ROSO3 and ~yclic s--lf~te~, such as VI, VII and VIII from mono- and poly-pentaerythritol, IX sirnilar sulfate esters of 1,4-anhydrosorbitol (X) and 1,4-anhydlv...s~ ...;lol, XI,y-sultones such as XII and XIII, and snbstit~tedy-sultone~.
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(~II) WO g5/18841 2 1 7 8 7 1 8 PCI/US95/00070 . -7 Whereas all the above materials insludetl in the invention share the ability to bring about dehydration of polymers at combustion temperatures, they differ in their ~ropcl lies, such as solubility, hygroscopicity, molecular weight, thermal stability, volatility and other properties, depending on their structure. It is therefore possible according to the invention to adapt hexavalent sulfur derivatives to polymers pocceccing a wide variety of properties especially that of varied processing temperalùres.
The preferred materials for additives in this invention are the salts of th¢ irnido-bisulfonic acid and especially the di-ammonium imido-bi-snlfon~te (DIBS), NH(SO3NH4)2, which is prepared from ammonium sulf~m~t~ by vacuum he~tin~ at 200C. Surprisingly, it has been found that this col~ound is particularly suitable and highly effective for flame retardancy of polyamide 6 and 66, as shown in the examples below. The desirable feature of DIBS, in addition to its FR effect, is its relatively high heat stability. In thermogravimetric me~Curements it was found that the onset of its dcco~ )osilion is above 310C, and it is therefore possible to use it both for nylon 6, which is processed at 240C, and for nylon 66, which is processed at 280C, as well as for other nylons and other polymers which are processed at a range of temperatures from 140-310C.
The arnounts of additive (a) for use in the invention depends on the nature of the polymer, on its procescing temperalu~ and on the degree of flame r~ardancy desired and the nature and amounts of the additives (b) and (c). They range from 0.1 to 40 wt % of the colllposilion. Higher amounts are nee(3ed for polymers with lower melting points than for polymers of higher melting points. For example, for nylon 6, higher amounts of DIBS are required than for nylon 66. In the presence of fillers, such as glass fibers compounded with the polymer, different ~molln~C of additive (a) are needed than without the filler, the amount depending on the nature and wt % of thç filler, and can be easily determined by those skilled in the art.
The flame retarding effect of di-ammonium imido-bi-sulfonate and the other materials listed above on thermoplastic polymers has not been hitherto described in the technical literature and is disclosed here for the first time.
Another basic feature of this invention is that the hexavalent sulfur compound can be an effective flame retardant by itself; however, it is WO 95/18841 2 1 7 8 7 1 8 PCT/US95tO0070 preferably applied together with a char-forming agent, additive (b), such as pentaerythritol and its oligomers, or other polyhydric alcohols, such as glycols and their derivatives, m~nnitol, sorbitol and other three, four, five and six-membered sugar molecules and other derivatives. One may also use 5 polymeric carbohydrates such as starch, xylans, m~nn~n.C and other hemi~ellu~Qses derived from wood and other plants, which are commercially av~ bl~
In this invention, it is sometimes advisable to co~bille the sulfur de~ e and the char-forming agent in one molecule. Such cornpounds, 10 for ~Y~mple are p,e~arcd by esterifying, or otherwise combining, one or more l~ ls in pentaerythritol with sulf~tes, sulf~m~te-s, sulf~mi(les~
slllfimides or imido-slllf~m~tes. Several such materials are, for example, VI, VII, IX, XII, as well as XIII.
Polyhydric alcohols are not the only char-fo....;ng agents used in 15 the present invention. Polyphenylene oxide (PPO) and polyphenylene sulfide (PPS) have been also sul~lisingly found highly suitable char-forming agents in c~ c! ;on with the hexavalent sulfur derivatives. Advantageously they range in mole.~ r weight from about 2,000 to 100,000. Blends of PPO
with poly~mides are well known and are described for example by Aycock, 20 U.S. Patent No. 4,600,741. Additionally, PPO is known to be used as a flame rctardillg coll.~ollent in low amounts in polyamides, as taught by Freitag in U.S. Patent No. 4,888,370 (1989). Only a veIy low degree of flame ret~d~ucy, ho.._~er, has been achieved by this co~ ollent alone. It has been found, for example by Taubitz, et al., U.S. Patent No. 4,866,114 (1989) that high oxygen indices can be achieved only when applied together with phosphorus or halogen derivatives.
PPO and PPS are very stable at the processin~ te-l-peratures of poly~mi~les They have aromatic rings on the backbone. They are virtually Y
free of volatile components at the polymer procescing temperatures. The molecular weight of PPO and PPS can be between 2,000 and 100,000. It is not critical since these materials flux easily with the polyamide during blen~ling. Other polymers to be used as char-foll--il-g agents in the invention inrlude aromatic polysulfides, polysulfones, polyketones, polyimides, polyetherirnides and polyarylates.
The preferred aromatic char-forming agents for the invention are PPS and PPO. High or low molecular weight polymers can be used in the WO 95/18841 2 ~ 7 8 7 t 8 PCI/US95/00070 . .
g invention. The char-forlllilJg agents can be applied in the form of powder, granules, flakes, beads or diced cubes.
The amounts of additive (b), such as pentasl ~lhritol or PPS to be used in the invention is about 0.0% to 50%, preferably from 0.5% to about 5 40%. It will be evident to those skilled in the art of polyrner compounding and flame Fetardancy that the exact amount will depend on the polymeric system and on the degree of flame retardancy required. The ~mount of (b) is to be adapted to the amount of (a).
The metal colllpoullds for use as additive (c) in the invention 10 co..-l..; e oxides and salts of alkali, ~lk~line earth, divalent and multivalent metals. 04e or several such colll~oullds may be used together in the invention, dependin~ on the nature of the polymeric system and according to the function required. It is believed that there are three major functions which the metal colllpounds may fulfill in the invention:
A. Regnlation of the acidity of the co~ osilion during processing, storage and co~l~u~lion. The additive (a) releases a relatively strong acid which may degrade the polymer ~Ace~sively and bring about a deterioration of its physical l,f~ellies and a decrease in molecular weight, which in~lcas~s its fl~mm~hility. Whereas a limitet3 degree of degradation is 20 needed during the co...b~.~l;on to f~cilit~te the dehydration and the crocclinhne, excessive degr~ tion is detriment~l. It has sul~lisingly been found that zinc oxide as additive (c) can co~lnteract this excessive degr~ tif)n by buffering the system and reg~ tir~ the acidity. The identity of the metal oxide and its concenllation are most illl~ollant and have to be 25 strictly regvl~te~ An excess in the (c) concentration may decrease the effc~livclless of additives (a) and (b). If the concentration is too low, a degr?~l~tio~ is perceived. It has further sul~Jri~ingly been discovered that a similar effect can be obtained by ~drling~ incte~d of (c), a basic nitrogen deli~,ali~c, such as mel~mine, which l,res~ bly pel~lllls the same 30 b~lffçrir~ f~tnction- It can be seen by coln~al ing Examples 14, lS and 16 hereinbelow. Thus it is clear that melamine may be optional ~or the invention, but it is not es.ce.nti~l B. A char stabilizing effect. The integrity and me~nical strength of the char is known to contribute greatly to flame retaldancy. The 35 char has to perform the function of a barrier to the passage of fl~mm~ble gases and rnolten mass out of the polymer and to the transfer of heat from WO g5/18841 2 1 7 8 7 1 8 pCT/U:,~5J'~ 70 the flarne to the polymer. Low melting glasses such as zinc borate have been used as a flarne retard~lt and smoke su~pressant additive in conjunction with h~lo~enc for polyvinyl chloride [see R. E. Meyers et al., J. Fire Sci, (1985) ~, 415~31]. It has also been disclosed as a component in conjunction S with magnesium l~d~Aide for PE (Nakagoma et al., Japan Patent No.
02,150,436) and with triphenyl phosphate for polycall,onate (Watanabi, J.
Eur~ean Patent Application 0520186 A1 (1992). Zinc borate has up to now not been iicclQsed as a collll)ollent in a sulfur-based flame retardant CO1I1~JOS;~ n According to the present invention, zinc borate can serve in a 10 dual r~p~ity: a char-stabilizer and a buffer.
The low meltine glasses according to the invention co~ rise borates o ~ ..gP~-Pse, iron and ~refe,ably zinc, for example Zn;~B402, ZnB2O4 or ZnB4O4. Other low-melting glasses are, for inct~nre, lead borate glass and aLkali phosphate glass with meltine points of 200 - 600C
15 and plefe~ably 300 - 500C. They are cornrnercially available as solder gl~cces~ frits and glazes. Such glasses include those described by R. E.
Meyers (see above) and incol~ol~ted by reference in its entirety herein.
Borophosph~tes are also incl~ ed in these gl~cces.
C. The third flmGtion of the additive (c) is as crosslinkine catalyst.
20 Many m~t~llic co.~oullds are known to catalyze cro~slinkinE, as described by Petersen in Handbook of Fiber Science and Technology, Vol. II, mi~l Procc;s - .~g of Fibers and Fabrics, Part A, Functinn~l Finishes, M.
L~vrin and S. B. Sello, editors, Marcel dekker, Publishers, pages 205 - 210 (1983). The preferred catalysts for the invention are m~g,.e~ .... hydrogen 25 phosphate, ~rCQ~ lll oxide or ~ ... oxide. Whereas the above crosslinki~g agents are a part of the invention, their use is optional.
Additive (c) can be col.")osed of one, two or three of the above-mentione~l materials.
The amounts of additive (c) applied accordi--~ to the invention 30 are 0.0 to 40 wt % of the co.ll~osilion. It will be evident to those skilled in the art that the amount will valy according to the polymer system and to the degree of flame retardance desired, and for a given level of flame retardancy the composition of (c) can be varied and its amount can be lower as the amount of (a) and (b) is higher, and conversely. The amount of the 35 thermoplastic polymer is at a minim~lm 20% by weight of the total col,-posiliQn.
The polyrner mLxtures of the invention may also inrlllde additive (d) such as reinforch~g agents and fillers: glass fibers, rnineral fibers, carbon fibers, ararnide ~lbers, talc, mica, gypsum, wollastonite, etc. They may also in~ de pigmentc~ stabilizers, processing aids, coupling agents, lubricants, 5 mold-release agents, electro-conductive additives and impact modifiers.
The polymer ~ ures may also include, according to the invention, flow modifiers (additive (e)) such as Teflon (polytetrafluoroethylene) p-~wder. The amounts of the powdered Teflon~9 may vary from 0.0 to 3 wt % of the composition.
Other flame retardants such as phosphorus- and halogen-co~ g agents can be present in the composition and they contribute partly to the flarne retardance of the polymers. Ho..~.er, an important advantage of the present invention is that no halogen- or phosphorus-based flarne r~tardant additives are needed for obtaining a very high degree of flame rel~udancy, which are ~ ressed in LOI values above 30 and UL94 rating of VO.
The rnLxing and blen~iing of the ingre-lient~ of the invention can be carried out by any method suitable for obtaining lmi~oll-- dispersions of part~ te solids, such as mixing in the Brabender rmLYer or in an extruder.
EX~MPLES
The present invention is further illustrated, but not lirnited to, the following exarnples.
Varying al--ol-~ls of ingre-lient~ (a), (b) and (c) were ~dmiyed with the powdered polymer in a Brabender mixer of 240 grams capacity for a time and at a temperalure dependent upon the polymer used, at 40 rotations per minnte. Sarnples were prepared by conll)ression molding in a hot press at a temperature dependent on the polymer used, cooled to room temperature and cut to standard test pieces. The mixing and co..,l)ression molding for nylon 6 was 240C and the time of mixing was 4 min~ltes For 30 nylon 66, the tirne of rnixing was 5 minutes, the telll~efalulc; was 270C. The nylon used was commercial-grade powder, produced by Rhone Pou lenc, France.
The fl~mm~bility was tested by the limitin~ oxygen index (LOI) method, accordil~g to ASTM D-2863 and by UL (Underwriters 35 Laboratories) 94 configuration-bottom ignition by a st~nd~rd burner flame for two successive 10-second intervals, with averaging of the after flame WO gS/18841 ~ 1 7 ~ 7 1 8 PCT/US95/00070 time. Ten test pieces were tested and the burning times given in each example are averages of all ten test pieces.
The DIBS used in most examples was ~ mm~nillm imido bi~lllfon~te. It was prepared by vacuum heating at 200C of ~mmonium 5 slllf~m~te. Its formula is NH(SO3NH4)2.
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WO g5/18841 2 1 7 8 7 1 8 PCI~/US95/00070 Some comp~rative materials not within the invention are also in~ (le-l, viz. Examples 6, 7, 8, 9, 13, 20, 26, 28, and 31. It can be seen thatno signific~nt flame retardancy effect is obtained in the absence of additive (a). FY~mpl~ 7 shows that (a) without (b) or (c) is inadequate. Example 8 shows that mel~mine plus ammonium slllf~m~te without (b) is inadequate, although it shows an increased LOI. Comparing Examples 14, 15 and 16 show that the same wt ~o of DIBS yields a similar result in the presence of m~l~mine or when, incte^ 1 of m~!~mine, additive (c), e.g., ZnO, is added.
This shows that the m~l~min~ is not needed for the perro~ ance of the invention, ~lthollgh it may be optionally used. Comparing examples 15 and 16, it can be seen that a high degree of flame retardance can be obtained without additive (e), and its use is optional.
Examples 21, æ and 23 (see Table 3) show that a high degree of F~ is ol)tai~ed when only additives (a) and (c) are ~rescn~ in the case of glass fiber ~ orced nylon 6, while additive (c) alone (Example 26) yields a very mode~ i~up~o.e~llent.
It is clearly evident from the examples that, in order to ~e.roll,-the invention, it is escenti~l to blend the polymer with (a) or with (a) and (b)or (a) and (c) or (a), (b) and (c), depending on the polymer ~ ule.
While only a few exemplary embodiments of this invention have been desc ibed in detail, those skilled in the art will rCco~ 7c that there are many possible variations and modifications possible; many of the novel and advantageous fealures of the invention can be formed. Accordillgly, it is intende-l that the following claims cover all such modifications and 2S v~ri~tion.c,
Claims (23)
1. A thermoplastic flame retardant composition comprising particles of at least one thermoplastic polyamide, a flame retardant effective amount of an additive comprising at least one (a) member selected from the group consisting of sulfamic acid, imido bisulfonic acid of the formula NH(SO3H)2, a mono- or di-ammonium or mono-valent, di-valent or multi-valent metal salt of sulfamic acid or imido bi-sulfonic acid, sulfamide of the formula H2MSO2NH2, aliphatic or aromatic-substituted sulfamide, a sulfate ester of a polyhydric alcohol, an imidosulfonic acid ester of a polyhydric alcohol and a y-sultone, and optionally at least one of (b) a char-forming agent, (c) a metal compound, (d) a filler or reinforcing agent, and (e) a flow modifier
2. A composition according to Claim 1, wherein there is present a char-forming agent (b) comprising polyphenylene oxide.
3. A composition according to Claim 1, wherein there is present a char-forming agent (b) comprising polyphenylene sulfide.
4. A composition according to claim 1, wherein (a) comprises di-ammonium imido bi-sulfonate.
5. A composition according to Claim 1, wherein there is present a char forming agent (b) selected from the group consisting of a polyhydric alcohol, oligomeric polyhydric alcohol, substituted alcohol, esterified polyhydric alcohol, sugar and polysaccharide.
6. A composition according to Claim 5, wherein the char forming agent (b) comprises pentaerythritol.
7. A composition according to Claim 5, wherein there is present as a composite of (a) and (b) a sulfate ester or an imidosulfonic ester of pentaerythritol.
8. A composition according to Claim 1, wherein there is present a char forming agent (b) which is an aromatic polymer having aromatic groups in the backbone selected from the group consisting of a polyphenylene oxide, polyphenylene sulfide, polyphenylene sulfone, polyarylate, polyimide and polyetherimide.
9. A composition according to Claim 8, wherein there is present a char forming agent (b) comprising polyphenylene sulfide.
10. A composition according to Claim 8, wherein there is present a char forming agent (b) comprising polyphenylene oxide.
11. A composition according to Claim 1, wherein there is present a metal compound (c) selected from the group consisting of an oxide borate silicate sulfamate, phosphate, zirconate, and titanate of an alkali, alkaline earth and di- or multi-valent metal.
12. A composition according to Claim 11, wherein the metal compound is selected from the group consisting of zinc oxide, zinc borate, magnesium oxide, magnesium hydroxide, magnesium borate, magnesium hydrogen phosphate, magnesium di-hydrogen phosphate, zirconium oxide, titanium oxide, sodium fluozirconate sodium fluotitanate, manganese oxide, manganese borate, vanadium oxide and vanadium borate.
13. A composition according to Claim 1 1, wherein the metal compound comprises zinc oxide.
14. A composition according to Claim 1 1, wherein the metal compound comprises zinc borate.
15. A composition according to Claim 1, wherein there is present a filler or reinforcing agent (d) selected from the group consisting of glass fibers, carbon fibers, aramide fibers, thermotropic polyester fibers, mineral fibers, wollastonite, mica, gypsum, talc and a low temperature glass.
16. A composition according to Claim 1, wherein there is present polytetrafluoroethylene powder as a flow modifier (e).
17. A composition according to Claim 1, comprising by weight about at least 20% of polymer (a) 0.1 to 40%
(b) 0 to 50%
(c) 0 to 50%
(d) 0 to 50% and (e) 0 to 3%.
(b) 0 to 50%
(c) 0 to 50%
(d) 0 to 50% and (e) 0 to 3%.
18. A composition according to Claim 1, wherein the polyamide comprises at least one member selected from the group consisting of nylon 6, nylon 66, copolymers of nylon 6 and of nylon 66, blends of nylon 6 and 66, nylon 11, nylon 12, nylon 4.4, nylon 6.3, nylon 6.4, nylon 6.10, nylon 6.12 and nylon 4.6.
19. A composition according to Claim 1, wherein the polyamide comprises nylon 66.
20. A composition according to Claim 15, comprising by weight about at least 20% of polyamide, (a) 0.2 to 30%, (b) 0 to 40% of a char forming agent selected from the group consisting of pentaerythritol, polyphenylene oxide and polyphenylene sulfide, (c) 0 to 40% of a metal compound selected from the group consisting of zinc oxide, zinc borate, magnesium hydrogen phosphate, zirconium oxide and titanium oxide, (d) 0 to 40% of a reinforcing agent selected from the group consisting of glass fibers, aramide fibers, inorganic powders and inorganic fibers and (e) 0 to 1 % of polytetrafluoroethylene powder.
21. A composition according to Claim 1, wherein (a) is a cyclic sulfate ester.
22. A composition according to Claim 1, wherein (a) is a y-sultone substituted by at least one of hydroxy and hydroxyalkyl.
23. A thermoplastic flame retardant composition comprising at least one thermoplastic polyamide, a flame retardant effective amount of an additive comprising at least one (a) member selected from the group consisting of sulfamic acid, imido bi-sulfonic acid of the formula NH(SO3H)2, a mono- or di-ammonium or monovalent, di-valent or multi-valent metal salt of sulfamic acid or imido bi-sulfonic acid, sulfamide of the formula H2NSO2HN2, aliphatic or aromatic-substituted sulfamide, a sulfate ester of a polyhydric alcohol, an imidosulfonic acid ester of a polyhydric alcohol and a y-sultone, and at least one of (b) a char forming agent, (c) a metal compound, (d) a filler or reinforcing agent, and (e) a flow modifier
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/177,883 | 1994-01-05 | ||
| US08/177,883 US5424344A (en) | 1994-01-05 | 1994-01-05 | Flame retardant polyamide compositions |
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|---|---|
| CA2178718A1 true CA2178718A1 (en) | 1995-07-13 |
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| CA002178718A Abandoned CA2178718A1 (en) | 1994-01-05 | 1995-01-05 | New flame retardant polymeric compositions |
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| EP (1) | EP0738297B1 (en) |
| JP (1) | JPH09507265A (en) |
| CA (1) | CA2178718A1 (en) |
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| US5691404A (en) * | 1995-06-20 | 1997-11-25 | E. I. Du Pont De Nemours And Company | Fire resistant polyamide compositions |
| US6239219B1 (en) * | 1995-07-21 | 2001-05-29 | Atofina | Thermoplastic compositions with improved fire resistance |
| US5708065A (en) * | 1995-12-22 | 1998-01-13 | E. I. Du Pont De Nemours And Company | Fire resistant resin compositions |
| US5618865A (en) * | 1995-12-22 | 1997-04-08 | E. I. Du Pont De Nemours And Company | Fire resistant resin compositions |
| US6025419A (en) * | 1997-04-07 | 2000-02-15 | E. I. Du Pont De Nemours And Company | Flame retardant resin compositions |
| US6025422A (en) * | 1998-05-29 | 2000-02-15 | Siecor Operations, Llc | Flame retardant polymer compositions |
| JP4284808B2 (en) * | 1999-03-30 | 2009-06-24 | 宇部興産株式会社 | Injection welding material |
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| DE3732907A1 (en) * | 1987-09-30 | 1989-04-13 | Basf Ag | SELF-EXTINGUISHING, THERMOPLASTIC POLYPHENYLENETHER-POLYAMIDE MOLDING MATERIALS AND THEIR USE FOR THE PRODUCTION OF MOLDED BODIES |
| DE3829712A1 (en) * | 1988-09-01 | 1990-03-15 | Basf Ag | TEMPERATURE-RESISTANT THERMOPLASTIC MOLDS |
| US5264474A (en) * | 1989-05-23 | 1993-11-23 | Mtm Americas Inc. | Polymer compositions |
| DE3925791A1 (en) * | 1989-08-04 | 1991-02-07 | Bayer Ag | FLAME-RETARDED, NON-DRIPING POLYAMIDE MOLDS |
| US5071894A (en) * | 1990-08-03 | 1991-12-10 | Stamicarbon B.V. | Flame retardant polyamides |
| US5151462A (en) * | 1991-09-30 | 1992-09-29 | Amoco Corporation | Flame retardant blends of polysulfone and polyalkylene phthalate |
-
1994
- 1994-01-05 US US08/177,883 patent/US5424344A/en not_active Expired - Fee Related
-
1995
- 1995-01-05 EP EP95906752A patent/EP0738297B1/en not_active Expired - Lifetime
- 1995-01-05 WO PCT/US1995/000070 patent/WO1995018841A1/en active IP Right Grant
- 1995-01-05 JP JP7518571A patent/JPH09507265A/en active Pending
- 1995-01-05 CA CA002178718A patent/CA2178718A1/en not_active Abandoned
- 1995-01-05 DE DE69519627T patent/DE69519627D1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| WO1995018841A1 (en) | 1995-07-13 |
| EP0738297B1 (en) | 2000-12-13 |
| JPH09507265A (en) | 1997-07-22 |
| DE69519627D1 (en) | 2001-01-18 |
| EP0738297A1 (en) | 1996-10-23 |
| US5424344A (en) | 1995-06-13 |
| EP0738297A4 (en) | 1997-05-28 |
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