WO2010112375A1 - Polymer composition containing polybutylene terephthalate and flame retardant additives - Google Patents
Polymer composition containing polybutylene terephthalate and flame retardant additives Download PDFInfo
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- WO2010112375A1 WO2010112375A1 PCT/EP2010/053804 EP2010053804W WO2010112375A1 WO 2010112375 A1 WO2010112375 A1 WO 2010112375A1 EP 2010053804 W EP2010053804 W EP 2010053804W WO 2010112375 A1 WO2010112375 A1 WO 2010112375A1
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- Prior art keywords
- composition
- weight
- composition according
- flame retardant
- nitrogen
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 229920001707 polybutylene terephthalate Polymers 0.000 title claims abstract description 24
- 239000003063 flame retardant Substances 0.000 title claims abstract description 23
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 19
- -1 polybutylene terephthalate Polymers 0.000 title claims abstract description 17
- 229920000642 polymer Polymers 0.000 title claims abstract description 11
- 239000000654 additive Substances 0.000 title claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 19
- 150000007513 acids Chemical class 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 16
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000470 constituent Substances 0.000 claims abstract description 10
- 239000003365 glass fiber Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 13
- 229920000388 Polyphosphate Polymers 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 239000001205 polyphosphate Substances 0.000 description 8
- 235000011176 polyphosphates Nutrition 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000007859 condensation product Substances 0.000 description 4
- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-n-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-UHFFFAOYSA-N 0.000 description 3
- 241000219112 Cucumis Species 0.000 description 3
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 3
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- ICBHRIMOANFLDA-UHFFFAOYSA-J [PH2]([O-])=O.[Zn+2].[Ca+2].[PH2]([O-])=O.[PH2]([O-])=O.[PH2]([O-])=O Chemical class [PH2]([O-])=O.[Zn+2].[Ca+2].[PH2]([O-])=O.[PH2]([O-])=O.[PH2]([O-])=O ICBHRIMOANFLDA-UHFFFAOYSA-J 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- AIXMJTYHQHQJLU-UHFFFAOYSA-N chembl210858 Chemical compound O1C(CC(=O)OC)CC(C=2C=CC(O)=CC=2)=N1 AIXMJTYHQHQJLU-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 229920001198 elastomeric copolymer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- YZPOQCQXOSEMAZ-UHFFFAOYSA-N pbt2 Chemical compound ClC1=CC(Cl)=C(O)C2=NC(CN(C)C)=CC=C21 YZPOQCQXOSEMAZ-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 1
- CZQYVJUCYIRDFR-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O CZQYVJUCYIRDFR-UHFFFAOYSA-N 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- QVJYHZQHDMNONA-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1 QVJYHZQHDMNONA-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy 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
- 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
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Definitions
- the invention relates to a polymer composition containing polybutylene terephthalate and flame retardant additives.
- Such polymer compositions are frequently used in parts for electrical and electronic equipment, for example in connectors, housings of relays and bobbins, lamp sockets etc.
- a halogen free flame retardant polymer composition containing a thermoplastic polyester, for example polybutylene terephthalate, an organic phosphorous compound and a compound derived from triazine.
- the composition of WO 99/02606 shows a high level of flame retardancy at a moderate level of flame retardants in the composition.
- Object of the invention is to provide such a further improved composition.
- polystyrene resin A. 90 - 50 wt. % polybutylene terephthalate (PBT) B. 10 - 50 wt. % polyethylene terephthalate (PET), the polymeric constituents add up to 100 %, at 100 part by weight of the sum of the polymeric constituents:
- PBT Polybutylene terephthalate
- PBT may be produced from the polycondensation reaction of butane diol and terephthalic acid and/or the methyl ester of terephthalic acid.
- PET Polyethylene terephthalate PET may be produced from the polycondensation reaction of ethylene diol and terephthalic acid and/or the methyl ester of terephthalic acid.
- PBT and PET may comprise minor amounts, for example up to 5 wt. % of further monomer units, for example monomeric units of further alkylene diols and aromatic dicarboxylic acids.
- the composition contains 80 -52 wt. PBT and 20 - 48 wt.
- the composition contains 70 - 54 wt. % of PBT and 30 - 46 wt. % of PET, this all under the condition that A and B up to 100 wt. %.
- the polymer composition contains only PET and PBT as the polymeric constituents and the composition does not contain any further polymer.
- the component C in the flame retardant elastomeric composition consists of metal salts of phosphinic acids and/or diphosphinic acids or polymeric derivatives thereof, which compounds are also denoted as metal phosphinates. This term will also be used further herein to indicate the same compounds.
- Test samples for testing the mechanical properties and the flame retardancy properties according to UL-94-V were prepared on an injection-moulding machine of type Engel 80 A. For the injection moulding set temperatures of 250-265 0 C were used. The mould temperature was 90 0 C.
- the samples according to the invention show improved burning times and higher gloss. Also the GWIT shows improved values.
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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)
Abstract
Polymer composition containing: as the polymeric constituents A. 90 - 50 wt. % polybutylene terephthalate (PBT) B. 10 - 50 wt. % polyethylene terephthalate (PET), the polymeric constituents add up to 100 wt. %, at 100 part by weight of the sum of the polymeric constituents: C. 10 - 40 part by weight of metal salts of phosphinic acids and/or diphosphinic acids or polymeric derivatives thereof. D. 3 - 30 part by weight of a nitrogen or nitrogen and phosphor containing flame retardant synergist for metal salts of phosphinic acids and/or diphosphinic acids or polymeric derivatives thereof, E. 0 - 80 part of glass fibers.
Description
POLYMER COMPOSITION CONTAINING POLYBUTYLENE TEREPHTHALATE AND
FLAME RETARDANT ADDITIVES
The invention relates to a polymer composition containing polybutylene terephthalate and flame retardant additives. Such polymer compositions are frequently used in parts for electrical and electronic equipment, for example in connectors, housings of relays and bobbins, lamp sockets etc.
It is important for such compositions to have a high level of flame- retardancy, while maintaining their further properties at an acceptable level. Another important demand in the last years, due to increased attention to environmental problems, is the use of halogen free flame retardants. This puts restrictions on the freedom to formulate new compositions and makes it therefore difficult to develop further improved compositions.
From WO 99/02606 a halogen free flame retardant polymer composition is known containing a thermoplastic polyester, for example polybutylene terephthalate, an organic phosphorous compound and a compound derived from triazine. The composition of WO 99/02606 shows a high level of flame retardancy at a moderate level of flame retardants in the composition. However there still exists a need for a further improved composition. Object of the invention is to provide such a further improved composition.
Surprisingly this object is obtained by a polymer composition containing: as the polymeric constituents
A. 90 - 50 wt. % polybutylene terephthalate (PBT) B. 10 - 50 wt. % polyethylene terephthalate (PET), the polymeric constituents add up to 100 %, at 100 part by weight of the sum of the polymeric constituents:
C. 10 - 40 parts by weight of metal salts of phosphinic acids and/or diphosphinic acids or polymeric derivatives thereof. D. 3 - 30 parts by weight of a nitrogen or nitrogen and phosphor containing flame retardant synergist for metal salts of phosphinic acids and/or diphosphinic acids or polymeric derivatives thereof.
E. 0 - 80 parts of glass fibers.
Surprisingly this composition shows a high level of flame retardancy. It is even possible to produce objects with a low wall thickness from the composition
that shows an UL VO classification, which indicates a high level of flame retardancy. The compositions according to the invention especially show short burning times at low wall thicknesses. Furthermore the surface of objects made from the composition show a relatively high level of gloss. Preferably a composition according to the invention is provided having a burning time of less than 25 sec, more preferably less than 22 sec. measured at a sample of 0.4 mm thickness, preferably of 0.3 mm thickness.
A. PBT Polybutylene terephthalate (PBT) may be produced from the polycondensation reaction of butane diol and terephthalic acid and/or the methyl ester of terephthalic acid.
B. PET Polyethylene terephthalate PET may be produced from the polycondensation reaction of ethylene diol and terephthalic acid and/or the methyl ester of terephthalic acid. PBT and PET may comprise minor amounts, for example up to 5 wt. % of further monomer units, for example monomeric units of further alkylene diols and aromatic dicarboxylic acids. Preferably the composition contains 80 -52 wt. PBT and 20 - 48 wt.
% PET, more preferably the composition contains 70 - 54 wt. % of PBT and 30 - 46 wt. % of PET, this all under the condition that A and B up to 100 wt. %. This means that the polymer composition contains only PET and PBT as the polymeric constituents and the composition does not contain any further polymer.
C. Metal phosphinates
The component C in the flame retardant elastomeric composition consists of metal salts of phosphinic acids and/or diphosphinic acids or polymeric derivatives thereof, which compounds are also denoted as metal phosphinates. This term will also be used further herein to indicate the same compounds.
Suitably, the metal phosphinate is a metal of a phosphinic acid of the formula [R1R2P(O)O] mMm+ (formula I) and/or a diphosphinic acid of the formula [O(O)PR1-R3-PR2(O)O]2 nMx m+ (formula II), and /or a polymer thereof, wherein
R1 and R2 are equal or different substituents chosen from the group consisting of hydrogen, linear, branched and cyclic C1 -C6 aliphatic groups, and aromatic groups,
R3 is chosen from the group consisting of linear, branched and cyclic C1 -C10 aliphatic groups and C6-C10 aromatic and aliphatic-aromatic groups,
M is a metal chosen from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti,
Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, and K, and m, n and x are equal or different integers in the range of 1 -4.
Suitable metal phosphinates that can be used as component C in the present invention are described for example in DE-A 2 252 258, DE-A 2 447 727, PCT/W-097/39053 and EP-0932643-B1 . Preferred phosphinates are aluminium-, calcium- and zinc-phosphinates, i.e. metal phosphinates wherein the metal M = Al, Ca, Zn respectively, and combinations thereof. Also preferred are metal phosphinates wherein R1 and R2 are the same or different and are equal to H, linear or branched C1- C6-alkyl groups, and/or phenyl. Particular preferably, R1, R2 are the same or different and are chosen from the group consisting of hydrogen (H), methyl, ethyl, n-propyl, iso- propyl, n-butyl, tert. -butyl, n-pentyl and phenyl. More preferably, R1 and R2 are the same or different and are chosen from the group of substituents consisting of H, methyl and ethyl. Also preferably R3 is chosen from the group consisting of methylene, ethylene, n-propylene, iso-propylene, n-butylene, tert.-butylene, n-pentylene, n- octylene, n-dodecylene, phenylene and naphthylene.
Highly preferably, the metal phosphinate comprises a hypophosphate and/or a CrC2 dialkylphosphinate, more preferably Ca- hypophosphate and/or an Al- CrC2 dialkylphosphinate, i.e. Al-dimethylphosphinate, Al-methylethylphosphinate and/or Al-diethylphosphinate. The best results are obtained if Al-diethylphosphinate is used.
D. nitrogen containing and nitrogen/phosphor containing flame retardant The nitrogen containing and nitrogen/phosphor containing component
D in the flame retardant elastomeric copolymer composition can be any nitrogen or nitrogen and phosphor containing compound that itself is a flame retardant and/or is a flame retardant synergist for phosphinate flame retardants. Suitable nitrogen containing and nitrogen/phosphor containing compounds that can be used as component D are
- A -
described, for example in PCT/EP97/01664, DE-A-197 34 437, DE-A-197 37 72, and DE-A-196 14 424.
Preferably, the nitrogen containing synergist is chosen from the group consisting of benzoguanamine, tris(hydroxyethyl)isocyanurate, allantoine, glycouril, melamine, melamine cyanurate, dicyandiamide, guanidine and carbodiimide, and derivatives thereof.
More preferably, the nitrogen containing synergist comprises a condensations product of melamine. Condensation products of melamine are, for example, melem, melam and melon, as well as higher derivatives and mixtures thereof. Condensations products of melamine can be produced by a method as described, for example, in PCT/WO 96/16948.
Preferably, the nitrogen/phosphor containing flame retardant is a reaction product of melamine with phosphoric acid and/or a condensation product thereof. With the reaction product of melamine with phosphoric acid and/or a condensation product thereof are herein understood compounds, which result from the reaction of melamine or a condensation product of melamine, for example, melem, melam and melon, with a phosphoric acid.
Examples include dimelaminephosphate, dimelamine pyrophosphate, melamine phosphate, melamine polyphosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melon polyphosphate and melem polyphosphate, as are described for example in PCT/WO 98/39306. More preferably the nitrogen/phosphor containing flame retardant is melamine polyphosphate.
Preferably the flame retardant component D is melamine cyanurate or melamine polyphosphate. Most preferably the flame retardant component D is melamine cyanurate.
Most preferably the composition according to the invention contains Al-diethylphosphinate as flame retardant component C and melamine cyanurate as flame retardant component D.
E. Glass fibers
The composition according to the invention contains preferably 40 - 80 parts by weight of glass fibers, more preferably 45 - 75 parts by weight, even more preferably 50 - 70 parts by weight.
F. Further additives
The composition according to the invention, may further contain usual additives, like for example processing aids, pigments, colorants, stabilizers, fillers etc. The composition according to the invention comprises preferably less than 10 parts by weight of further organic additives, more preferably less than 5 parts by weight, more preferably less than 2 parts by weight, most preferably less than 1 part by weight.
Preferably the composition according to the invention exists of components A - F.
The invention is further explained by hands of the examples, without being restricted thereto.
Materials
PBT1 : PBT 1060, a PBT delivered by DSM in the Netherlands.
PBT2: PBT 5007, a PBT delivered by DSM in the Netherlands. PET: BAGA 5018, PET delivered by DSM in the Netherlands.
Glass fibers: CPIC ECS 303A glass fibers delivered by CPIC in China.
DEPAL: Exolit OP 1230, Aluminium Diethylphosphinate, delivered by Clariant, in
Germany.
Mecy: Sechuan Mecy powder, melamine cyanurate powder delivered by Sechuan in China.
Melapur 200/70: melamine polyphosphate, delivered by Ciba in Switzerland.
Compounding
Moulding compositions were prepared by melt-blending the PBT and PBT/PET with the flame retardant components, glass fibers and a usual package of stabilisers on a ZSK 25/33 twin-screw extruder with screw speed 400 rpm, throughput of 25 kg/hr, and melt temperature regulated at 2700C. The glass fibers were added at a side feed opening about half way the extruder barrel. The melt from the extruder is transported through a granulation die. The granules obtained by compounding in the extruder were dried for 24 hours at 900C, prior to further use.
Moulding of test samples
Test samples for testing the mechanical properties and the flame retardancy properties according to UL-94-V were prepared on an injection-moulding
machine of type Engel 80 A. For the injection moulding set temperatures of 250-2650C were used. The mould temperature was 900C.
Properties measured on the samples: -MVR (280eC/2.16kg): Melt Volume Rate at a temperature of 280eC, under a weight of
2.16kg according to ISO 1 133.
-TM, TS, E.a.b.: tensile modulus, tensile strength and elongation at break according to
ISO 527-1 A.
-CharpyN: impact resistance by notched Charpy according to ISO 179/1 eA. -CharpyUN: impact resistance by unnotched Charpy according to ISO 179/1 ell.
-UL94V (0.4mm ;48h): flame retardancy according to UL94V test, at a sample thickness of 0.4 mm and a precondition of the sample during 48 hours at 23 °C and 50% relative humidity. Measured was the burning time (total afterflame times t1 + t2 of 5 specimen), the time that the sample kept burning after ignition. GWIT-Glow wire ignition temperature according to IEC 60695-2-13.
Gloss: the gloss was determined visually.
Examples 1 , 2 and comparative experiment A, B
Compounds with the compositions of Examples 1 and 2 and according to the invention and Comparative Experiments A and B were prepared and tested as described above. The compositions and test results are presented in Tables 1 and 2.
Table 1.
The samples according to the invention show improved burning times and higher gloss. Also the GWIT shows improved values.
Claims
1. Polymer composition containing: as the polymeric constituents A. 90 - 50 wt. % polybutylene terephthalate (PBT)
B. 10 - 50 wt. % polyethylene terephthalate (PET), the polymeric constituents add up to 100 wt. %, at 100 part by weight of the sum of the polymeric constituents:
C. 10 - 40 part by weight of metal salts of phosphinic acids and/or diphosphinic acids or polymeric derivatives thereof.
D. 3 - 30 part by weight of a nitrogen or nitrogen and phosphor containing flame retardant synergist for metal salts of phosphinic acids and/or diphosphinic acids or polymeric derivatives thereof,
E. 0 - 80 part of glass fibers.
2. Composition according to claim 1 , the composition shows a burning time of less than 25 sec for a sample having a thickness of 0.4 mm.
3. Composition according to claim 1 or 2, wherein the composition contains 80 - 52 wt. % PBT and 20 - 48 wt. % PET.
4. Composition according to claim 1 or 2, wherein the composition contains 40- 80 wt. % of glass fibers.
5. Composition according to any one of claim 1 - 4, wherein the composition contains 20 - 30 parts by weight of metal salts of phosphinic acids and/or diphosphinic acids or polymeric derivatives thereof.
6. Composition according to any one of claim 1 - 5, wherein the composition contains 8 - 20 part by weight of a nitrogen or nitrogen and phosphor containing flame retardant synergist for metal salts of phosphinic acids and/or diphosphinic acids or polymeric derivatives thereof.
7. Composition according to any one of claim 1 - 6, wherein component C is Al- diethylphosphinate.
8. Composition according to any one of claims 1 - 7, wherein component D is melamine cyanurate.
9. Composition according to any one of claims 1 - 8, which composition consists of components A, B, C, D, E and F, where component F is one or more of the usual additives.
10. Objects produced from the composition according to any one of claims 1 - 9.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012502574A JP2012522083A (en) | 2009-03-31 | 2010-03-24 | Polymer composition containing polybutylene terephthalate and a flame retardant additive |
| EP10710038A EP2414454A1 (en) | 2009-03-31 | 2010-03-24 | Polymer composition containing polybutylene terephthalate and flame retardant additives |
| US13/202,167 US20120101197A1 (en) | 2009-03-31 | 2010-03-24 | Polymer composition containing polybutylene terephthalate and flame retardant additives |
| CN2010800143541A CN102369241A (en) | 2009-03-31 | 2010-03-24 | Polymer composition containing polybutylene terephthalate and flame retardant additives |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09156825 | 2009-03-31 | ||
| EP09156825.3 | 2009-03-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2010112375A1 true WO2010112375A1 (en) | 2010-10-07 |
Family
ID=40906537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2010/053804 WO2010112375A1 (en) | 2009-03-31 | 2010-03-24 | Polymer composition containing polybutylene terephthalate and flame retardant additives |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20120101197A1 (en) |
| EP (1) | EP2414454A1 (en) |
| JP (1) | JP2012522083A (en) |
| CN (1) | CN102369241A (en) |
| WO (1) | WO2010112375A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012083626A (en) * | 2010-10-13 | 2012-04-26 | Gunze Ltd | Conductive elastic member for electrophotography having flame retardancy, and method for manufacturing the same |
| EP3290475A1 (en) * | 2016-09-01 | 2018-03-07 | LANXESS Deutschland GmbH | Thermoplastic moulding materials |
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| CN103450642A (en) * | 2013-08-07 | 2013-12-18 | 上海日之升新技术发展有限公司 | High-strength carbon-fiber-reinforced halogen-free flame-retardant PBT (polybutylene terephthalate) composite material and preparation method thereof |
| CN104744901A (en) * | 2015-04-09 | 2015-07-01 | 南通市东方塑胶有限公司 | Halogen-free flame retardant PBT composite material with high glowing filament initiation temperature and preparation method thereof |
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| JPWO2021166851A1 (en) * | 2020-02-19 | 2021-08-26 | ||
| CN115516034A (en) * | 2020-03-05 | 2022-12-23 | 株式会社三养社 | Polybutylene terephthalate resin composition having excellent flame retardancy and hydrolysis resistance, and molded article produced therefrom |
| CN114133708B (en) * | 2021-11-08 | 2023-08-04 | 会通新材料(上海)有限公司 | Thermoplastic polyester elastomer and preparation method and application thereof |
| CN114605787A (en) * | 2022-02-24 | 2022-06-10 | 金发科技股份有限公司 | PBT/PET composite material, and preparation method and application thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN102369241A (en) | 2012-03-07 |
| JP2012522083A (en) | 2012-09-20 |
| US20120101197A1 (en) | 2012-04-26 |
| EP2414454A1 (en) | 2012-02-08 |
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