CA1315449C - Flame-retardant polymer compositions - Google Patents
Flame-retardant polymer compositionsInfo
- Publication number
- CA1315449C CA1315449C CA000544285A CA544285A CA1315449C CA 1315449 C CA1315449 C CA 1315449C CA 000544285 A CA000544285 A CA 000544285A CA 544285 A CA544285 A CA 544285A CA 1315449 C CA1315449 C CA 1315449C
- Authority
- CA
- Canada
- Prior art keywords
- flame
- ammonium polyphosphate
- polyolefin composition
- weight
- retardant polyolefin
- 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.)
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
FLAME-RETARDANT POLYMER COMPOSITIONS
ABSTRACT OF THE DISCLOSURE
Flame-retardant polymer compositions contain an intumes-cent flame-retardant system substantially comprised of a phosphorus component and an organic nitrogen component. The flame-retardant system is more particularly comprised of am-monium polyphosphate and tris-(2-hydroxyethyl)-isocyanurate.
ABSTRACT OF THE DISCLOSURE
Flame-retardant polymer compositions contain an intumes-cent flame-retardant system substantially comprised of a phosphorus component and an organic nitrogen component. The flame-retardant system is more particularly comprised of am-monium polyphosphate and tris-(2-hydroxyethyl)-isocyanurate.
Description
~31S~9 This invention relates to flame-retardant polymer compo-sitions containing an intumescent flame-retardant system com-prised substantially of a phosphorus component and an organic nitrogen component.
In U.S. Patent No. 4,140,66a it has been suggested that phosphonic acid derivatives of isocyanuric acid are useful for imparting flame-retardant properties to polyurethanes.
U.S. Patent No. 4,001,177 also describes a combination of me-lamine and isocyanuric acid derivatives for imparting flame-lû retardant properties to polyamides.
U.S. Patent No. 3,810,862 appears to be the first refe-rence to disclose the use of an intumescent mixture for im-parting flame-retardant properties to polyolefins; this mix-ture consists of ammonium polyphosph~ate, melamine and dipen-taerythrltol or melamine pyrophosphate and dipentaerythritol.In U.S. Patent No. 4,312,805 (DE-OS 28 Oû 891), a three-com-ponent mixture of ammonium polyphosphate, melamine and poly-amide 6 (cf. Example 6) is suggested, and in U.S. Patent No.
4,198,493~(~E-OS 28 39 710) a further series of three-compo-nent mixtures are suggested consisting of ammonium polyphos-phatej melamine and tris-(2-hydroxyethyl)-isocyanurate (cf.
; Examples 2, 5, 6, 7, 8) or ammonium polyphosphate, pentaery-thritol or tripentaerythritol and tris-(2-hydroxyethyl)-iso-cyanurate (cf. Examples 4, 9) or ammonium polyphosphate, cyanuric acid and tris-(2-hyroxyethyl)-isocyanurate (cf.
~ Examples 13, 14) as intumescent agents imparting flame-retar-; dant properties to polyolefins. It has also been disclosed (cf. U.S. Patent No. 4,461,862) that a combination ~f ammo-~1 3 1 ~ ~ ~ 9 23343-826 nium polyphosphate and the reaction product of an oxygen acid of phosphorus with a hyclroxy-alkyl deriva~ive o i60cyanuric acid can conveniently be used for this purpose.
We have now unexpectedly found that a two component system, consisting of ammonium polyphosphate and tri~-(2~hy-droxyethyl)-isocyanurate also imparts very good flame-retar-dant properties to polyolefins. This was more particularly an unexpected result as the other components of the three-compo-nent system specified hereinabove when used in a two-component system with ammonium polyphosphate did not have any flame-retardant activlty whatever ~cf comparative Examples 1-12 herein).
The present invention now provides a flame retardant polyolefin composition, containing an intu~escent flame-retardant system consisting essentially o~ a phosphorus component and an organic nitrogen component, wherein the lame-retardant system iæ a two component mixture of ammonium polyphosphate and tris-(2-hydroxyethyl~-isocyanurate.
Further preferred and optional features of the flame-: retardant polymer composltion of this invention provide:
a) for the ammonium polyphosphate to contain Q.5 to 25 ~eight % of a water-insoluble artificial, preferably cured, resin enoapsulating the individual ammonium ~: polyphosphate particles;
b) for the ammonium polyphosphate to contain O.S to 25 weight % of a reaction product of a polyisocyanate with a carbodiimidizatlon catalyst, the polycarbodi-lmlde formecl encapsulating ~he individual a~monium polyphosphate particles;
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~31~9 c) for the ammonium polyphosphate to contain 0.5 to 25 weight % of a reaction product of a polyisocyanate and a polyhydroxy compound, the polyurethane formed encapsu-lating the individual ammoniurn polyphosphate particles;
d) for the ammonium polyphosphate to contain 0.5 to 25 weight % of a reaction product of a polyisocyanate with a trimerization catalyst, the polyisocyanurate formed encapsulating the individual ammonium polyphosphate particles;
e) for the ammonium polyphosphate to contain 0.5 to 25 weight % of a reaction product of a polyisocyanate:and water, the ?olyurea formed encapsulating the individual : ammonium polyphosphate particles;
f) for the ammonium polyphosphate to contain 0.5 to 25 weight % o a cured melamine/formaldehyde-resin, the me-lamine/formaldehyde resin encapsulating the indivldual ~: ~ ammonium polyphosphate particles;
g) for the ammonium polyphosphate to contain 0.5 to 25 : weight % of a cured epoxlde resin, the epoxide resin en-capsulating the individual ammonium polyphosphate par-~ ticles;
: h) for the flame-retardant system to contain from:80 to 50 :
: weight % ammonium polyphosphate and 20 to 50 weight %
; ~ tris-(2-hydroxyethyl)-isocyanurate;
i) or the ammonium polyphosphate used to be a free-flow-: ing, pulverulent, sparingly water~soluble ammonium poly-phosphate of the formula (NH4P03)n, in which n is an integer from 200 to 1000, preferably about 700;
~ 3 ~
j) for more than 99 % of the ammoniurn polyphosphate to have a particle size of less than 45 ~rn;
k) for the flame-retardant polymer composition to contain the flame-retardant system in an amount from 15 to 40 weight %;
l) for the flame-retardant polymer composition to be a thermoplast;
m) for the flame-retardant polymer composition to be an olefin.
The following Examples and Tables are intended to il-lustrate the invention which is na-turally not limited there-to.
Example 1 (Comparative Example) ;~ 5000 9 of ~HOSTALEN PPU 0180 P~(a registered Trade Mark : 15 of HOECHST AKTIENGESELLSCHAFT, Frankfurt) - a polypropylene powder having a melt index: MFI 230/5 of about 55 9/10 minu-tes;
;1500 9 of ~EXOLIT 422 (a registe:red Trade Mark of HOECHST AKTIENGESELLSCHAFT, Frankfurt) - a fine particulate, sparingly water-soluble ammonium polyphosphate of the formula : : (NH4P03)n, in which:n is about 700 and more than 99 % of the particles have a size of less than 45 ,um;
500 9 of melamine;
ao 9 of ~ RONOS CL Z20 (a registered Trade Mark of Kronos Titan GmbH, Leverkusen) - a titanium dioxlde pigment (rutile grade);
10 9 calcium stearate;
lû g of ~HOSTANOX û3 (a registered Trade Mark of HOECHST
AKTIENGESEILSCHAFT, Frankfurt) - an antioxidan~ based on ~L 3 ~ 9 polynuclear phenols;
10 9 of ~HOSTANOX SE 10 (a registered Trade Mark of HOECHST AKTIENGESELLSCHAFT, frankfurt) - an antioxidant based on dialkyl sulfides, and 10 9 of QHOSTANOX PA~ 24 (a registered Trade Mark of HûECHST AKTIENGESELLSCHAFT, Frankfurt) - an aromatic phos-phite(tris-(2,4-ditert.-butylphenol)-phosphite) were mixed in a SPANGENBERG intensive mixer (20 1 capa-city), extruded at 180-200C in a WEBER small extruder (20 mm screw diameter) and granulated in a DREHER laboratory granu-lator.
The dried, granulated material was introduced into a steam-heated BECKER-VAN-HULLEN molding press and molded at a temperature of 195C and under a pressure of 2-3 bars (5-10 .
15 mlnutes) or 30û bars (2 minutes) into test plates 1.6 mm thick and 3.2 mm thick.
The flammability of the composition was tested in accor-dance with the Underwriters Laboratories procedure "Test for Flammability of Plastic Material - UL 94" dated as of May 2, 2û ~975, on specimens 127 mm long, 12.7 mm wide and 1.6 and 3.2 mm thick, and the oxygen lndex was determined substantially in accordance with ASTM-D ~2863 in a modified apparatus.
The results of the flammability tests are reported in Table 1.
Example 2 (Comparative Example) The procedure of Example l was repeated but 1000 9 of ~3EXOLIT 422 and 1000 g of melamine were used. Tha results of the flammability tests are listed in Table 1.
..
~31 5~
Example 3 (Comparative Example) The procedure of Example 1 was repeated but 50û 9 of ~EXOLIT 422 and 1500 9 of melamine were used. The results of the flammability tests are listed in Table 1.
Example 4 (Comparative Example) The procedure of Example 1 was repeated but the mela-mine was replaced by 500 g of cyanuric acid. The results of the flammability tests are listed in Table 1.
Example 5 (Comparative Example) lû The procedure of Example 2 was repeated but the mela-mine was replaced by 1000 9 of cyanuric acid. The results of the flammability tests are listed in Table 1.
Example 6 (Comparative Example) The procedure of Example 3 was repeated but the mela-mine was replaced by 1500 9 of cyanuric acid. The results of the fl~ammabillty tests are listed in Table 1.
Example 7 (Comparative Example) The procedure of Exàmple 1 was repeated but the mela-mine was replaced by 500 9 of melamine cyanurate. The re-sults of the flammability tests are listed in Table 2.
Example 8 (Comparative Example) The procedure ~of Example 2 was repeated but the mela-mine was replaced by 1000 9 of melamine cyanurate. The re-sults of the flammability tests are listed in Table 2.
~: :
25. Example 9 (Comparative Example) The procedure of Example 3 was repeated but the mela-mine was replaced by 1500 9 of melamine cyanurate. The re-sults of the flammability tests are listed in Table 2.
13~5~
Example 10 (Comparative Exampla) The procedure of Example 1 was repeated but the mela-mine was replaced by 500 9 of ~ ADURIT MW 909 (a registered Trade Mark of HOECHST AKTIENGESELLSCHAFT, Frankfurt) which was used in the form of a melamine/formaldehyde-resin cured for 2 hours at 180C prior to use. ~ AOURIT MW gO9 is an un-plastlcized melamine/formaldehyde-resin commercially avail-able in the form of a white powder. A 50 weight % percent solution has a dynamic viscosity of about 30 mPa.s, a pH of 9.0-10.0 and a density (at 20C) of 1.21-1.225 gjml. The results of the flammability tests are listed in Table 2.
Example 11 (Comparative Example) The procedure of Example 2 was repeated but the mela-mine was replaced by 1000 9 of 6MADURIT MW 909, which was in the form of a melamine/formaldehyde-resin which had been cured for 2 hours at 180C prior to use. The results of the flammability tests are listed in Table 2.
Example 12 (Comparative Example) The procedure of Example 3 was repeated but the mela-20 mine was replaced by 1500 9 ~MADURIT MW 909, which was used in the form~of a me1amine/formaldehyde-resin cured for 2 hours at 180C. The results of the flammability tests are listed in Table 2.
Example 13 (inventionj The procedure of Example 1 was repeated but the mela-mine was replaced by 500 9 of tris-(2-hydroxyethyl)-iso-cyanurate (THEIC). The results of the flammability tests are listed in Table 3.
~3~5~
Example 14 (invention) The procedure of Example 2 was repeated but the mela-mine was replaced by lOûO g of tris-(2-hydroxyethyl)-iso-cyanurate (THEIC). The results of the flammability tests are listed in Table 3.
Example 15 (invention) The procedure of Example 3 was repeated but the mela-mine was replaced by 1500 g of tris-(2-hydroxyethyl)-iso-cyanurate ~THEIC). The results of the flammability tests are listed in Table 3.
Example 16 (invention) The procedure of Example 1 was repeated but 1312.5 9 of ~EXOLIT 422 and (instead of 500 9 of melamine) 437.5 9 of THEIC were used. The results of the flammability -tests are lS listed in Table 3.
Example 17 (invention) The procedure of Example 2 was repeated but 875 g of ~EXOLIT 422 and (instead of 500 9 melamlne) 875 9 of THEIC
were used. The results of the flammability tests are listed in Table 3.
Example 18 (invention) ; ~ :
The procedure~ of Example 1 was ~repeated but 1~125 9 of EXOLIT 422 and (lnstead of 500 9 of melamine) 375 9 of THEIC were use.d. The results of the flammability tests are :
listed in Table 3.
Example 19 (invention) The procedure of Example 1 was repeated but 75C g of ~EXOLIT 422 and (instead of 500 9 of melamine) 750 9 of THEIC wera used. The results of the flammability tests are indicated in Table 3.
~31~
Example 20 (invention) The procedure of Example 16 was repeated but ~EXOLIT
.422 was replaced by 1312.5 9 of ~EXOLIT 462.
The ~-~EXOLIT 462 is a microencapsulated ammonium poly-phosphate made by the process described in German Specifica-tion DE-OS 35 31 50û, containing about 10 weight % of en-capsulating material consisting of a cured melamine/formal-dehyde resin.
The results of the flammability tests are indicated in Table 4.
Example 21 (invention) The procedure of Example 18 was repeated but the `~EXOLIT 422 was replaced by 1125 9 of EXOLIT 462.
The results of the flammability tests are indicated in Table 4.
Example 22 (inventlon) ~: The procedure of Example 16 was repeated but the : ~ XOLIT 422 was replac;ed by 1312.5 9 of ~EXOLIT 470.
~, The ~EXOLIT 470 is a microencapsulated ammonium poly-phos,ohate made by the process described in German Specifica-: tion DE-OS 35 26 006, containing about 10 weight % of encap-suIating material:cons:isting of the reaction product of a :: ~ polyisocyanate and a carbodiimldization catalyst.
The reaults of the flammability tests are indicated in ~; ~ 25 Table 4.
Example 23 (invention) The procedure of Example 18 was repeated but the G~EXOLIT 422 was replaced by 1125 9 of ~EXOLIT 470.
: 9 ~ 3 ~ 9 The results of the flammability tests are indicated in Table 4.
The comparative materials melamine, cyanuric acid, me-lamine cyanurate and melamine/formaldehyde-resin (~MADUnIT
MW 909) were found in the flammability tests to be definite-ly unsuitable for use in a two-component system with ammo-nium polyphosphate as a flame-retardant composition for thermoplastic materials; tcf. Tables 1 and 2).
In clear contrast therewith, the ammonium polyphospha-te/tris-(2-hydroxyethyl)-isocyanurate composition was very - effectiva (cf. Tables 3 and 4). Specimens 3.2 mm thick made from material in which 35 parts of this composition were used per 100 parts of polypropylene could be classified in class UL g4 V-0.
15 ~ Comparison physical properties for APP/THEIC (inve~n-tion), typical halogen and 3-component non-halogen flame re-:~ ~: tardant formulations are presented in Table 5. An excellent trade-off in property balance is demonstrated for APP/THEIC
formulations (1, 2, 3). Compared with commercial halogen ;20 formulations (5, 6) strengths in tensile, flexural, impact, : :and low smoke properties, and specific gravity are note-worthy. The non-halogen 3-component formulations (7, 8, 93 :: show inferior performance in tensile, flexural, elongation and impact properties.
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In U.S. Patent No. 4,140,66a it has been suggested that phosphonic acid derivatives of isocyanuric acid are useful for imparting flame-retardant properties to polyurethanes.
U.S. Patent No. 4,001,177 also describes a combination of me-lamine and isocyanuric acid derivatives for imparting flame-lû retardant properties to polyamides.
U.S. Patent No. 3,810,862 appears to be the first refe-rence to disclose the use of an intumescent mixture for im-parting flame-retardant properties to polyolefins; this mix-ture consists of ammonium polyphosph~ate, melamine and dipen-taerythrltol or melamine pyrophosphate and dipentaerythritol.In U.S. Patent No. 4,312,805 (DE-OS 28 Oû 891), a three-com-ponent mixture of ammonium polyphosphate, melamine and poly-amide 6 (cf. Example 6) is suggested, and in U.S. Patent No.
4,198,493~(~E-OS 28 39 710) a further series of three-compo-nent mixtures are suggested consisting of ammonium polyphos-phatej melamine and tris-(2-hydroxyethyl)-isocyanurate (cf.
; Examples 2, 5, 6, 7, 8) or ammonium polyphosphate, pentaery-thritol or tripentaerythritol and tris-(2-hydroxyethyl)-iso-cyanurate (cf. Examples 4, 9) or ammonium polyphosphate, cyanuric acid and tris-(2-hyroxyethyl)-isocyanurate (cf.
~ Examples 13, 14) as intumescent agents imparting flame-retar-; dant properties to polyolefins. It has also been disclosed (cf. U.S. Patent No. 4,461,862) that a combination ~f ammo-~1 3 1 ~ ~ ~ 9 23343-826 nium polyphosphate and the reaction product of an oxygen acid of phosphorus with a hyclroxy-alkyl deriva~ive o i60cyanuric acid can conveniently be used for this purpose.
We have now unexpectedly found that a two component system, consisting of ammonium polyphosphate and tri~-(2~hy-droxyethyl)-isocyanurate also imparts very good flame-retar-dant properties to polyolefins. This was more particularly an unexpected result as the other components of the three-compo-nent system specified hereinabove when used in a two-component system with ammonium polyphosphate did not have any flame-retardant activlty whatever ~cf comparative Examples 1-12 herein).
The present invention now provides a flame retardant polyolefin composition, containing an intu~escent flame-retardant system consisting essentially o~ a phosphorus component and an organic nitrogen component, wherein the lame-retardant system iæ a two component mixture of ammonium polyphosphate and tris-(2-hydroxyethyl~-isocyanurate.
Further preferred and optional features of the flame-: retardant polymer composltion of this invention provide:
a) for the ammonium polyphosphate to contain Q.5 to 25 ~eight % of a water-insoluble artificial, preferably cured, resin enoapsulating the individual ammonium ~: polyphosphate particles;
b) for the ammonium polyphosphate to contain O.S to 25 weight % of a reaction product of a polyisocyanate with a carbodiimidizatlon catalyst, the polycarbodi-lmlde formecl encapsulating ~he individual a~monium polyphosphate particles;
~ ',.
5~ I
~31~9 c) for the ammonium polyphosphate to contain 0.5 to 25 weight % of a reaction product of a polyisocyanate and a polyhydroxy compound, the polyurethane formed encapsu-lating the individual ammoniurn polyphosphate particles;
d) for the ammonium polyphosphate to contain 0.5 to 25 weight % of a reaction product of a polyisocyanate with a trimerization catalyst, the polyisocyanurate formed encapsulating the individual ammonium polyphosphate particles;
e) for the ammonium polyphosphate to contain 0.5 to 25 weight % of a reaction product of a polyisocyanate:and water, the ?olyurea formed encapsulating the individual : ammonium polyphosphate particles;
f) for the ammonium polyphosphate to contain 0.5 to 25 weight % o a cured melamine/formaldehyde-resin, the me-lamine/formaldehyde resin encapsulating the indivldual ~: ~ ammonium polyphosphate particles;
g) for the ammonium polyphosphate to contain 0.5 to 25 : weight % of a cured epoxlde resin, the epoxide resin en-capsulating the individual ammonium polyphosphate par-~ ticles;
: h) for the flame-retardant system to contain from:80 to 50 :
: weight % ammonium polyphosphate and 20 to 50 weight %
; ~ tris-(2-hydroxyethyl)-isocyanurate;
i) or the ammonium polyphosphate used to be a free-flow-: ing, pulverulent, sparingly water~soluble ammonium poly-phosphate of the formula (NH4P03)n, in which n is an integer from 200 to 1000, preferably about 700;
~ 3 ~
j) for more than 99 % of the ammoniurn polyphosphate to have a particle size of less than 45 ~rn;
k) for the flame-retardant polymer composition to contain the flame-retardant system in an amount from 15 to 40 weight %;
l) for the flame-retardant polymer composition to be a thermoplast;
m) for the flame-retardant polymer composition to be an olefin.
The following Examples and Tables are intended to il-lustrate the invention which is na-turally not limited there-to.
Example 1 (Comparative Example) ;~ 5000 9 of ~HOSTALEN PPU 0180 P~(a registered Trade Mark : 15 of HOECHST AKTIENGESELLSCHAFT, Frankfurt) - a polypropylene powder having a melt index: MFI 230/5 of about 55 9/10 minu-tes;
;1500 9 of ~EXOLIT 422 (a registe:red Trade Mark of HOECHST AKTIENGESELLSCHAFT, Frankfurt) - a fine particulate, sparingly water-soluble ammonium polyphosphate of the formula : : (NH4P03)n, in which:n is about 700 and more than 99 % of the particles have a size of less than 45 ,um;
500 9 of melamine;
ao 9 of ~ RONOS CL Z20 (a registered Trade Mark of Kronos Titan GmbH, Leverkusen) - a titanium dioxlde pigment (rutile grade);
10 9 calcium stearate;
lû g of ~HOSTANOX û3 (a registered Trade Mark of HOECHST
AKTIENGESEILSCHAFT, Frankfurt) - an antioxidan~ based on ~L 3 ~ 9 polynuclear phenols;
10 9 of ~HOSTANOX SE 10 (a registered Trade Mark of HOECHST AKTIENGESELLSCHAFT, frankfurt) - an antioxidant based on dialkyl sulfides, and 10 9 of QHOSTANOX PA~ 24 (a registered Trade Mark of HûECHST AKTIENGESELLSCHAFT, Frankfurt) - an aromatic phos-phite(tris-(2,4-ditert.-butylphenol)-phosphite) were mixed in a SPANGENBERG intensive mixer (20 1 capa-city), extruded at 180-200C in a WEBER small extruder (20 mm screw diameter) and granulated in a DREHER laboratory granu-lator.
The dried, granulated material was introduced into a steam-heated BECKER-VAN-HULLEN molding press and molded at a temperature of 195C and under a pressure of 2-3 bars (5-10 .
15 mlnutes) or 30û bars (2 minutes) into test plates 1.6 mm thick and 3.2 mm thick.
The flammability of the composition was tested in accor-dance with the Underwriters Laboratories procedure "Test for Flammability of Plastic Material - UL 94" dated as of May 2, 2û ~975, on specimens 127 mm long, 12.7 mm wide and 1.6 and 3.2 mm thick, and the oxygen lndex was determined substantially in accordance with ASTM-D ~2863 in a modified apparatus.
The results of the flammability tests are reported in Table 1.
Example 2 (Comparative Example) The procedure of Example l was repeated but 1000 9 of ~3EXOLIT 422 and 1000 g of melamine were used. Tha results of the flammability tests are listed in Table 1.
..
~31 5~
Example 3 (Comparative Example) The procedure of Example 1 was repeated but 50û 9 of ~EXOLIT 422 and 1500 9 of melamine were used. The results of the flammability tests are listed in Table 1.
Example 4 (Comparative Example) The procedure of Example 1 was repeated but the mela-mine was replaced by 500 g of cyanuric acid. The results of the flammability tests are listed in Table 1.
Example 5 (Comparative Example) lû The procedure of Example 2 was repeated but the mela-mine was replaced by 1000 9 of cyanuric acid. The results of the flammability tests are listed in Table 1.
Example 6 (Comparative Example) The procedure of Example 3 was repeated but the mela-mine was replaced by 1500 9 of cyanuric acid. The results of the fl~ammabillty tests are listed in Table 1.
Example 7 (Comparative Example) The procedure of Exàmple 1 was repeated but the mela-mine was replaced by 500 9 of melamine cyanurate. The re-sults of the flammability tests are listed in Table 2.
Example 8 (Comparative Example) The procedure ~of Example 2 was repeated but the mela-mine was replaced by 1000 9 of melamine cyanurate. The re-sults of the flammability tests are listed in Table 2.
~: :
25. Example 9 (Comparative Example) The procedure of Example 3 was repeated but the mela-mine was replaced by 1500 9 of melamine cyanurate. The re-sults of the flammability tests are listed in Table 2.
13~5~
Example 10 (Comparative Exampla) The procedure of Example 1 was repeated but the mela-mine was replaced by 500 9 of ~ ADURIT MW 909 (a registered Trade Mark of HOECHST AKTIENGESELLSCHAFT, Frankfurt) which was used in the form of a melamine/formaldehyde-resin cured for 2 hours at 180C prior to use. ~ AOURIT MW gO9 is an un-plastlcized melamine/formaldehyde-resin commercially avail-able in the form of a white powder. A 50 weight % percent solution has a dynamic viscosity of about 30 mPa.s, a pH of 9.0-10.0 and a density (at 20C) of 1.21-1.225 gjml. The results of the flammability tests are listed in Table 2.
Example 11 (Comparative Example) The procedure of Example 2 was repeated but the mela-mine was replaced by 1000 9 of 6MADURIT MW 909, which was in the form of a melamine/formaldehyde-resin which had been cured for 2 hours at 180C prior to use. The results of the flammability tests are listed in Table 2.
Example 12 (Comparative Example) The procedure of Example 3 was repeated but the mela-20 mine was replaced by 1500 9 ~MADURIT MW 909, which was used in the form~of a me1amine/formaldehyde-resin cured for 2 hours at 180C. The results of the flammability tests are listed in Table 2.
Example 13 (inventionj The procedure of Example 1 was repeated but the mela-mine was replaced by 500 9 of tris-(2-hydroxyethyl)-iso-cyanurate (THEIC). The results of the flammability tests are listed in Table 3.
~3~5~
Example 14 (invention) The procedure of Example 2 was repeated but the mela-mine was replaced by lOûO g of tris-(2-hydroxyethyl)-iso-cyanurate (THEIC). The results of the flammability tests are listed in Table 3.
Example 15 (invention) The procedure of Example 3 was repeated but the mela-mine was replaced by 1500 g of tris-(2-hydroxyethyl)-iso-cyanurate ~THEIC). The results of the flammability tests are listed in Table 3.
Example 16 (invention) The procedure of Example 1 was repeated but 1312.5 9 of ~EXOLIT 422 and (instead of 500 9 of melamine) 437.5 9 of THEIC were used. The results of the flammability -tests are lS listed in Table 3.
Example 17 (invention) The procedure of Example 2 was repeated but 875 g of ~EXOLIT 422 and (instead of 500 9 melamlne) 875 9 of THEIC
were used. The results of the flammability tests are listed in Table 3.
Example 18 (invention) ; ~ :
The procedure~ of Example 1 was ~repeated but 1~125 9 of EXOLIT 422 and (lnstead of 500 9 of melamine) 375 9 of THEIC were use.d. The results of the flammability tests are :
listed in Table 3.
Example 19 (invention) The procedure of Example 1 was repeated but 75C g of ~EXOLIT 422 and (instead of 500 9 of melamine) 750 9 of THEIC wera used. The results of the flammability tests are indicated in Table 3.
~31~
Example 20 (invention) The procedure of Example 16 was repeated but ~EXOLIT
.422 was replaced by 1312.5 9 of ~EXOLIT 462.
The ~-~EXOLIT 462 is a microencapsulated ammonium poly-phosphate made by the process described in German Specifica-tion DE-OS 35 31 50û, containing about 10 weight % of en-capsulating material consisting of a cured melamine/formal-dehyde resin.
The results of the flammability tests are indicated in Table 4.
Example 21 (invention) The procedure of Example 18 was repeated but the `~EXOLIT 422 was replaced by 1125 9 of EXOLIT 462.
The results of the flammability tests are indicated in Table 4.
Example 22 (inventlon) ~: The procedure of Example 16 was repeated but the : ~ XOLIT 422 was replac;ed by 1312.5 9 of ~EXOLIT 470.
~, The ~EXOLIT 470 is a microencapsulated ammonium poly-phos,ohate made by the process described in German Specifica-: tion DE-OS 35 26 006, containing about 10 weight % of encap-suIating material:cons:isting of the reaction product of a :: ~ polyisocyanate and a carbodiimldization catalyst.
The reaults of the flammability tests are indicated in ~; ~ 25 Table 4.
Example 23 (invention) The procedure of Example 18 was repeated but the G~EXOLIT 422 was replaced by 1125 9 of ~EXOLIT 470.
: 9 ~ 3 ~ 9 The results of the flammability tests are indicated in Table 4.
The comparative materials melamine, cyanuric acid, me-lamine cyanurate and melamine/formaldehyde-resin (~MADUnIT
MW 909) were found in the flammability tests to be definite-ly unsuitable for use in a two-component system with ammo-nium polyphosphate as a flame-retardant composition for thermoplastic materials; tcf. Tables 1 and 2).
In clear contrast therewith, the ammonium polyphospha-te/tris-(2-hydroxyethyl)-isocyanurate composition was very - effectiva (cf. Tables 3 and 4). Specimens 3.2 mm thick made from material in which 35 parts of this composition were used per 100 parts of polypropylene could be classified in class UL g4 V-0.
15 ~ Comparison physical properties for APP/THEIC (inve~n-tion), typical halogen and 3-component non-halogen flame re-:~ ~: tardant formulations are presented in Table 5. An excellent trade-off in property balance is demonstrated for APP/THEIC
formulations (1, 2, 3). Compared with commercial halogen ;20 formulations (5, 6) strengths in tensile, flexural, impact, : :and low smoke properties, and specific gravity are note-worthy. The non-halogen 3-component formulations (7, 8, 93 :: show inferior performance in tensile, flexural, elongation and impact properties.
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Claims (14)
1. A flame retardant polyolefin composition, containing an intumescent flame-retardant system consisting essentially of a phosphorus component and an organic nitrogen component, wherein the flame-retardant system is a two component mixture of ammonium polyphosphate and tris-(2-hydroxyethyl)-isocyanurate.
2. A flame-retardant polyolefin composition as claimed in claim 1, wherein the said ammonium polyphosphate contains 0.5 to 25 weight % of a water-insoluble artificial resin encapsulating the individual ammonium polyphosphate particles.
3. A flame-retardant polyolefin composition as claimed in claim 1, wherein the said ammonium polyphosphate contains 0.5 to 25 weight % of a reactlon product of a polyisocyanate with a carbodiimidization catalyst, the polycarbodiimide formed encapsulating the individual ammonium polyphosphate particles.
4. A flame-retardant polyolefin composition as claimed 1n claim 1, wherein the sald ammonium polyphosphate contains 0.5 to 25 weight % of a reaction product of a polyisocyanate and a polyhydroxy compound, the polyurethane formed encapsulating the individual ammonium polyphosphate particles.
5. A flame-retardant polyolefin composition as claimed in claim 1, wherein the said ammonium polyphosphate contains 0.5 to 25 weight % of a reaction product of a polyisocyanate with a trimerization catalyst, the polyisocyanurate formed encapsulating the individual ammonium polyphosphate particles.
6. A flame-retardant polyolefin composition as claimed in claim 1, wherein the said ammonium polyphosphate contains 0.5 to 25 weight % of a reaction product of a polyisocyanate and water, the polyurea formed encapsulating the individual ammonium polyphosphate particles.
7. A flame-retardant polyolefin composition as claimed in claim 1, wherein the said ammonium polyphosphate contains 0.5 to 25 weight % of a cured melamine/formaldehyde-resin, the melamine/formaldehyde resin encapsulating the individual ammonium polyphosphate particles.
8. A flame-retardant polyolefin composition as claimed in claim 1, wherein the said ammonium polyphosphate contains 0.5 to 25 weight % of a cured epoxide resin, the epoxide resin encapsulating the individual ammonium polyphosphate particles.
9. A flame-retardant polyolefin composition as claimed in claim 1, wherein said flame-retardant system contains from 80 to 50 weight % ammonium polyphosphate and 20 to 50 weight %
tris-(2-hydroxyethyl)-isocyanurate.
tris-(2-hydroxyethyl)-isocyanurate.
10. A flame-retardant polyolefin composition as claimed in claim 1, containing a free flowing pulverulent, sparingly water-soluble ammonium polyphosphate of the formula (NH4PO3)n, in which n is an integer from about 200 to about 1000.
11. A flame-retardant polyolefin composition as claimed in claim 1, wherein more than 99 percent by weight of said ammonium polyphosphate has a particle size of less than about 45 µm.
12. A flame-retardant polyolefin composition as claimed in claim 1, wherein said flame-retardant system is present in an amount from 15 to 40 weight percent.
13. A flame-retardant polyolefin composition as claimed in claim 2, wherein the said water-insoluble artificial resin is cured.
14. A flame-retardant polyolefin composition as claimed in claim 10, wherein n is an integer of about 700.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3628797.0 | 1986-08-25 | ||
| DE3628797 | 1986-08-25 | ||
| DE19873720094 DE3720094A1 (en) | 1986-08-25 | 1987-06-16 | FLAME-RESISTANT POLYMERS |
| DEP3720094.1 | 1987-06-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1315449C true CA1315449C (en) | 1993-03-30 |
Family
ID=25846854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000544285A Expired - Fee Related CA1315449C (en) | 1986-08-25 | 1987-08-12 | Flame-retardant polymer compositions |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0258685A3 (en) |
| JP (1) | JPH0668038B2 (en) |
| AU (1) | AU592219B2 (en) |
| BR (1) | BR8704350A (en) |
| CA (1) | CA1315449C (en) |
| DE (1) | DE3720094A1 (en) |
| ES (1) | ES2004811A6 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1228923B (en) * | 1987-08-04 | 1991-07-10 | Vamp Srl | FLAME RETARDANT COMPOSITION FOR POLYMERS AND SELF-EXTINGUISHING POLYMER PRODUCTS SO OBTAINED. |
| AU627615B2 (en) * | 1989-08-28 | 1992-08-27 | Ministero Dell Universita E Della Ricerca Scientifica E Tecnologica | Self-extinguishing polymeric compositions |
| DE3930722A1 (en) * | 1989-09-14 | 1991-03-28 | Gruenau Gmbh Chem Fab | TUBE BOTTOM |
| DE4003230A1 (en) * | 1990-02-03 | 1991-08-08 | Hoechst Ag | Self-extinguishing polyurethane prods. partic. foams - contain mixt. of ammonium poly:phosphate with bis-triazinyl-piperazine or hydroxyalkyl isocyanurate or amino-triazine-aldehyde |
| US5204392A (en) * | 1991-09-05 | 1993-04-20 | Hoechst Celanese Corporation | Two-component intumescent flame retardant |
| GB2267498B (en) * | 1992-04-24 | 1996-05-29 | Minnesota Mining & Mfg | Flame retardants for polymers |
| TW252135B (en) * | 1992-08-01 | 1995-07-21 | Hoechst Ag | |
| DE4300390A1 (en) * | 1992-08-22 | 1993-07-01 | Tech Wissenschaftliche Ges Thi | Preventing burning of plastics materials or plastics composites - by incorporating conventional flame retardant as microcapsules |
| US5414031A (en) * | 1993-11-19 | 1995-05-09 | Polymer Product Company, Inc. | Intumescent nonhalogenated flame retardant polystyrene composition |
| DE19546834A1 (en) * | 1995-12-15 | 1997-06-19 | Hoechst Ag | Flame-retardant polymeric masses |
| DE10321286B4 (en) * | 2003-05-13 | 2005-04-14 | Clariant Gmbh | Flame retardant additive for polymer compositions with improved hydrothermal stability |
| JP2005228546A (en) * | 2004-02-12 | 2005-08-25 | Matsushita Electric Ind Co Ltd | Heating element |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US400177A (en) * | 1889-03-26 | Gas and air mixer | ||
| IT1076204B (en) * | 1977-01-12 | 1985-04-27 | Montedison Spa | SELF-EXTINGUISHING POLYMERIC COMPOSITIONS |
| IT1087517B (en) * | 1977-09-14 | 1985-06-04 | Montedison Spa | POLYMERIC COMPOSITIONS |
| IT1110266B (en) * | 1979-02-05 | 1985-12-23 | Montedison Spa | SELF-EXTINGUISHING POLYOLEFINIC COMPOSITIONS WITH IMPROVED HEAT AND THERMO-OXIDATION RESISTANCE |
| US4461862A (en) * | 1980-06-02 | 1984-07-24 | Ludwig Eigenmann | Self extinguishing polymeric compositions, which upon contacting a flame provide a nondropping char-forming incandescent crust, and which do not produce flame neither toxic fumes |
| DE3100626C2 (en) * | 1981-01-12 | 1985-05-15 | Schmittmann, Hans-Bernd, Dipl.-Chem. Dr.Rer.Nat., 5620 Velbert | Flame-retardant plastics, especially those which can be used as building materials or the like, processes for their production and their use as components |
| IT1183626B (en) * | 1985-05-14 | 1987-10-22 | Vamp Srl | POLYOLEFINE SELF-EXTINGUISHING POLYMER PRODUCTS |
-
1987
- 1987-06-16 DE DE19873720094 patent/DE3720094A1/en not_active Withdrawn
- 1987-08-08 EP EP87111504A patent/EP0258685A3/en not_active Ceased
- 1987-08-12 CA CA000544285A patent/CA1315449C/en not_active Expired - Fee Related
- 1987-08-24 AU AU77342/87A patent/AU592219B2/en not_active Ceased
- 1987-08-25 BR BR8704350A patent/BR8704350A/en unknown
- 1987-08-25 JP JP62209432A patent/JPH0668038B2/en not_active Expired - Lifetime
- 1987-08-25 ES ES8702468A patent/ES2004811A6/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| BR8704350A (en) | 1988-04-19 |
| ES2004811A6 (en) | 1989-02-01 |
| JPS6361055A (en) | 1988-03-17 |
| JPH0668038B2 (en) | 1994-08-31 |
| DE3720094A1 (en) | 1988-03-03 |
| AU592219B2 (en) | 1990-01-04 |
| EP0258685A3 (en) | 1989-03-29 |
| AU7734287A (en) | 1988-02-25 |
| EP0258685A2 (en) | 1988-03-09 |
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| MKLA | Lapsed |