CN104277432A - Flame retardant polymer composition - Google Patents
Flame retardant polymer composition Download PDFInfo
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- CN104277432A CN104277432A CN201310277098.0A CN201310277098A CN104277432A CN 104277432 A CN104277432 A CN 104277432A CN 201310277098 A CN201310277098 A CN 201310277098A CN 104277432 A CN104277432 A CN 104277432A
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- flame retardant
- polymer composition
- phosphorus compound
- retardant polymer
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- 229920000642 polymer Polymers 0.000 title claims abstract description 106
- 239000003063 flame retardant Substances 0.000 title claims abstract description 84
- 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 78
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- -1 aryl phosphonate Chemical compound 0.000 claims abstract description 81
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 46
- 239000011574 phosphorus Substances 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 27
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 6
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims description 33
- 229920000877 Melamine resin Polymers 0.000 claims description 32
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 31
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 239000003365 glass fiber Substances 0.000 claims description 18
- 229920000728 polyester Polymers 0.000 claims description 18
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 11
- 239000004793 Polystyrene Substances 0.000 claims description 10
- 229920002223 polystyrene Polymers 0.000 claims description 10
- 239000012744 reinforcing agent Substances 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 7
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 7
- 229920002215 polytrimethylene terephthalate Polymers 0.000 claims description 7
- 229920001169 thermoplastic Polymers 0.000 claims description 7
- FYXPKOPFEGFWHG-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-phenylphosphoryl]phenol Chemical compound C1=CC(O)=CC=C1P(=O)(C=1C=CC(O)=CC=1)C1=CC=CC=C1 FYXPKOPFEGFWHG-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 6
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229920001577 copolymer Chemical compound 0.000 claims description 6
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000001188 haloalkyl group Chemical group 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 6
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 6
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- 239000004952 Polyamide Substances 0.000 claims description 4
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- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
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- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920002050 silicone resin Polymers 0.000 claims description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 3
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- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
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- 230000000052 comparative effect Effects 0.000 description 4
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- 150000003018 phosphorus compounds Chemical class 0.000 description 4
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
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- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 235000012222 talc Nutrition 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
- KQCDNTFMEXGZKZ-UHFFFAOYSA-N 2-[[oxiran-2-ylmethoxy(phenyl)phosphoryl]oxymethyl]oxirane Chemical compound C1OC1COP(C=1C=CC=CC=1)(=O)OCC1CO1 KQCDNTFMEXGZKZ-UHFFFAOYSA-N 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- XAMQTCWAEFIFRO-UHFFFAOYSA-N 3-diphenoxyphosphorylphenol Chemical compound OC1=CC=CC(P(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)=C1 XAMQTCWAEFIFRO-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- JRCBAJFWUZDKAP-UHFFFAOYSA-N OC(O)=O.OP(O)=O Chemical class OC(O)=O.OP(O)=O JRCBAJFWUZDKAP-UHFFFAOYSA-N 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- DDNCQMVWWZOMLN-IRLDBZIGSA-N Vinpocetine Chemical compound C1=CC=C2C(CCN3CCC4)=C5[C@@H]3[C@]4(CC)C=C(C(=O)OCC)N5C2=C1 DDNCQMVWWZOMLN-IRLDBZIGSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 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
- 230000003321 amplification Effects 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
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- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 150000004985 diamines Chemical class 0.000 description 1
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- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- OGBPILLJZSJJRC-UHFFFAOYSA-N phenoxyphosphonoyloxybenzene Chemical class C=1C=CC=CC=1OP(=O)OC1=CC=CC=C1 OGBPILLJZSJJRC-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
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- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 1
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- 125000003944 tolyl group Chemical group 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a reinforced polymer composition. The composition comprises at least one polymer and about 15-40wt% of at least one flame retardant bag, wherein the flame retardant bag is composed of an aryl phosphonate oligomer or polymer and a coated phosphorus compound according to a weight ratio of about 15:85-45:55. The coated phosphorus compound has a core formed by a phosphorus compound, and the core is coated by about 15-35wt% of at least one cross-linked polymer coating material. The invention also discloses products formed by using the composition, such as molded products.
Description
Technical Field
The present disclosure relates to a flame retardant polymer composition comprising a flame retardant of high thermal stability.
Background
Thermoplastic polymers, such as polyesters or polyamides, have excellent mechanical properties, moldability and chemical resistance, and thus have been used for automobile parts, electric/electronic components and many other applications. In some applications, it is desirable that these polymers also be flame retardant. This can be achieved by adding various types of additives as flame retardants. In the past, halogenated organic compounds (e.g., brominated polystyrene) have been used in polymeric materials as effective flame retardants with antimony compounds. However, in recent years, due to environmental concerns, various halogen-free flame retardants are being developed to replace halogenated flame retardants.
For example, in U.S. patent publication No. 2013/0046036, oligomers, co-oligomers, polymers or copolymers containing an aryl phosphonate component are disclosed for use in thermoplastic polyurethanes as flame retardants. Phosphorus compounds such as triphenylphosphine oxide (TPPO) and similar compounds have been proposed to improve flame retardant properties in polymeric materials, see for example us patent No. 4,115,345 or PCT patent publication No. WO 2003042303. However, it is stated that when an aryl phosphonate group containing oligomer or polymer, or a phosphorus compound of the TPPO type, is used alone in a thermoplastic polymer (such as a polyester), the flame retardant properties of the polymer composition are still not optimal for some applications. Thus, there is still a need to develop flame retardant packages that can further improve the flame retardant properties of polymeric materials.
Disclosure of Invention
It is an object of the present disclosure to provide a flame retardant polymer composition comprising: (a) at least one polymer; and (b) 15 to 40 wt% of at least one flame retardant package, wherein the total wt% of all components comprised in the flame retardant polymer composition adds up to 100 wt%,
wherein,
the flame retardant package consists essentially of an aryl phosphonate oligomer or polymer and a coated phosphorus compound in a weight ratio of 15:85 to 45: 55;
the coated phosphorus compound has a core formed from a phosphorus compound of formula (I) and coated with 15 to 35 wt% of at least one crosslinked polymeric coating material, based on the total weight of the coated phosphorus compound;
and wherein the one or more of the one,
R1is straight-chain or branched C1-C4Alkyl, haloalkyl or C3-C6A cycloalkyl group; r2And R3Each of which is a straight or branched C1-C4Alkyl, haloalkyl, C3-C6Cycloalkyl or aryl.
In one embodiment of the flame retardant polymer composition, the volatilization temperature (T) of the phosphorus compound of formula (I)v) Or decomposition temperature (T)d) At a temperature of 180-.
In another embodiment of the flame retardant polymer composition, the phosphorus compound of formula (I) is selected from the group consisting of triphenylphosphine oxide (TPPO), bis (4-hydroxyphenyl) phenylphosphine oxide (BOHPPO), bis 4-carboxyphenylphenylphosphine oxide (BCPPO), phosphine oxide containing poly (amide-imide) s and combinations of two or more thereof, or the phosphorus compound of formula (I) is triphenylphosphine oxide (TPPO).
In yet another embodiment of the flame retardant polymer composition, the at least one cross-linked polymer coating material is selected from melamine-formaldehyde (MF) resin, cross-linked polystyrene (CPS), urea-formaldehyde (UF) resin, phenol-formaldehyde (PF) resin, silicone resin, and combinations of two or more thereof, or the at least one cross-linked polymer coating material is selected from melamine-formaldehyde (MF) resin and cross-linked polystyrene (CPS).
In yet another embodiment of the flame retardant polymer composition, the coated phosphorus compound comprises 17 to 30 wt%, alternatively 17 to 25 wt%, of the crosslinked polymeric coating material, based on the total weight of the coated phosphorus compound.
In yet another embodiment of the flame retardant polymer composition, the aryl phosphonate oligomer or polymer is a linear or branched polyphosphonate or copolyphosphonate containing one or more structural units of formula (II):
wherein R is4Is methyl or phenyl and n is an integer not exceeding about 90.
In yet another embodiment of the flame retardant polymer composition, the at least one polymer is selected from thermoplastic polymers, or the at least one polymer is selected from polyamides, polyesters, polycarbonates, Acrylonitrile Butadiene Styrene (ABS), polyurethanes, polyphenylene oxide (PPO), Liquid Crystal Polymers (LCP) and blends of two or more thereof, or the at least one polymer is a polyester selected from polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polycyclohexanedimethanol terephthalate (PCT), polyester elastomers and combinations of two or more thereof.
In yet another embodiment of the flame retardant polymer composition, the flame retardant polymer composition comprises 30 to 85 wt%, alternatively 40 to 75 wt%, alternatively 45 to 60 wt% of the at least one polymer, based on the total weight of the flame retardant polymer composition.
In yet another embodiment of the flame retardant polymer composition, the flame retardant polymer composition comprises 15 to 40 wt%, alternatively 16 to 30 wt%, alternatively 18 to 25 wt%, of the at least one flame retardant package, based on the total weight of the flame retardant polymer composition.
In yet another embodiment of the flame retardant polymer composition, the weight ratio between the aryl phosphonate oligomer or polymer and the coated phosphorus compound is from 15:85 to 45:55, or from 18:82 to 40: 60.
In yet another embodiment of the flame retardant polymer composition, the flame retardant polymer composition further comprises 10 to 60 wt.%, alternatively 18 to 40 wt.%, alternatively 20 to 30 wt.%, based on the total weight of the composition, of at least one reinforcing agent.
In yet another embodiment of the flame retardant polymer composition, the at least one reinforcing agent is selected from glass fibers, carbon fibers, whiskers of wollastonite and potassium titanate, montmorillonite, talc, mica, calcium carbonate, silica, clay, kaolin, glass powder, glass beads, polymer powder, and mixtures of two or more thereof, or the at least one reinforcing agent is selected from glass fibers.
Also provided herein are articles formed from the flame retardant polymer compositions as described above.
In accordance with this disclosure, when a range is given by two specific endpoints, it is understood that the range includes any value within the two specific endpoints and any value equal to or about equal to any one of the two endpoints.
Detailed Description
Disclosed herein is a flame retardant polymer composition comprising: (a) at least one polymer; and (b) about 15 to 40 weight percent of at least one flame retardant package, wherein the total weight percent of all components included in the flame retardant polymer composition totals 100 weight percent, wherein the flame retardant package consists essentially of the aryl phosphonate oligomer or polymer and the coated phosphorus compound in a weight ratio of about 15:85 to about 45: 55. The coated phosphorus compounds used herein have a core formed from a phosphorus compound of formula (I) and coated with about 15 to 35 wt% of at least one crosslinked polymeric coating material, based on the total weight of the coated phosphorus compound,
wherein R is1Is straight-chain or branched C1-C4Alkyl, haloalkyl or C3-C6A cycloalkyl group; r2And R3Each of which is a straight or branched C1-C4Alkyl, haloalkyl, C3-C6Cycloalkyl or aryl (i.e., phenyl, halophenyl, hydroxyphenyl, tolyl, alkylphenyl, benzyl, biphenyl, polycyclic aromatic hydrocarbon) and the like and derivatives thereof.
The polymer used herein can be any suitable polymeric material. Alternatively, the polymer used herein is a thermoplastic polymer or a blend of two or more suitable thermoplastic polymers. Exemplary thermoplastic polymers suitable for use herein include, but are not limited to: polyamides, polyesters (including unsaturated polyesters), polycarbonates, Acrylonitrile Butadiene Styrene (ABS), polyurethanes, polyphenylene oxide (PPO), Liquid Crystal Polymers (LCP) and blends of two or more thereof. Suitable polyesters in accordance with the present disclosure include, but are not limited to: polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polycyclohexanedimethanol terephthalate (PCT), polyester elastomers (such asCopolyether ester). The polyesters used herein may also be purchased from various suppliers. For example, suitable PET may be available under the trade namePurchased from e.i. intra moore dupont (e.i. du Pont de Nemours and Company (u.s.a.) (hereinafter "dupont")); suitable PBT may be referred to by the trade namePurchased from dupont; suitable PTT may be given the trade namePurchased from dupont; suitable PCT may be available under the trade name ThermxTMPurchased from Ticona, The Netherland, netherlands; and suitable copolyetheresters are available under the trade namePurchased from dupont.
The at least one polymer may be present in an amount of about 30 to 85 weight percent, or about 40 to 75 weight percent, or about 45 to 60 weight percent, based on the total weight of the flame retardant polymer composition disclosed herein.
The aryl phosphonate oligomers or polymers used in the at least one flame retardant package include aryl phosphonate oligomers, oligomeric aryl phosphonate copolymers, aryl phosphonate polymers, and aryl phosphonate copolymers (i.e., copolymers including an aryl phosphonate component). The aryl phosphonate oligomers or polymers used herein can be linear, branched, or hyperbranched, and in some embodiments, the aryl phosphonate oligomers or polymers can comprise functional end groups, such as phenols, phosphonates, esters, carbonates, epoxy groups, vinyl groups, and the like. In some embodiments, the aryl phosphonate oligomers or polymers used herein may be predominantly hydroxyl terminated polyphosphonates or oligomeric phosphonates, random or block co-oligo (phosphonates), and co-oligo (phosphonate carbonates). Further, the aryl phosphonate oligomer or polymer used herein may be a linear or branched polyphosphonate or copolyphosphonate containing one or more structural units of formula (II):
wherein R is4Is methyl or phenyl and n is an integer not exceeding about 90. In certain embodiments, such linear or branched polyphosphonates or copolyphosphonates may also include one or more carbonate structural units. Also, such linear or branched polyphosphonates or copolyphosphonates may be prepared by any method known in the art. For example, in some embodiments, the polyphosphonate component may be prepared by polymerization of one or more diphenyl phosphonates (DPPs) and one or more aromatic dihydroxy compounds such as bisphenol a (bpa). The DPP and aromatic dihydroxy compound used may be prepared by any method and combined by any method to form a polyphosphonate. Alternatively, other components, such as branching agents and catalysts, may be used in such processes.
The aryl phosphonate oligomer or polymer used herein may have a weight average molecular weight of greater than 500g/mol, or about 1,000-140,000g/mol, or about 1,500-90,000g/mol, or about 10,000-80,000 g/mol.
Aryl phosphonate oligomers or polymers for use herein are disclosed in U.S. patent publication No. 2013/0046036, the disclosure of which is incorporated herein by reference. The aryl phosphonate oligomers or polymers used herein may also be sold under the tradename NofiaTM HM1100、NofiaTM CO3000、NofiaTM CO6000、NofiaTM OL3000、NofiaTM OL5000、NofiaTMOL1001 or NofiaTMOL3001 is purchased from FRX Polymers (u.s.a.) of america.
Preferably, it is used hereinThe volatilization temperature (T) of the phosphorus compound of formula (I)v) Or decomposition temperature (T)d) About 180 ℃ or about 190 ℃ or about 260 ℃ or about 200 ℃ or about 250 ℃. Temperature of volatilization (T) of a substancev) Is the temperature at which the material has a 1% weight loss; and the decomposition temperature (T) of the substanced) Is the temperature at which the substance chemically decomposes. T isvAnd TdBoth can be measured by thermogravimetric analysis (TGA). Exemplary phosphorus compounds of formula (I) for use herein include, but are not limited to:
·triphenylphosphine oxide (TPPO)（Tv=210 ℃, as measured by thermogravimetric analysis (TGA);
·bis-phenoxy (3-hydroxy) phenylphosphine oxide (BPHPPO)（Tv=220 ℃, see, e.g., Figure5, Polymer Degradation and Stability, 2007, 92, 956-type 961 in "Synthesis and properties of anticancer based on bound bis-phenyl (3-hydroxy) phenyl oxide" of H.ren et al;
·bis (4-hydroxyphenyl) phenylphosphine oxide (BOHPPO)（Tv=239 ℃, see e.g. Table2 in "Synthesis, characterization and thermal amplification of functional benzoxazine monomers and polymeric linking phenylsilane oxides", Polymer differentiation and Stability, 2006, 91, 1166-;
·bis 4-carboxyphenylphenylphosphine oxide (BCPPO)（Tv=210 ℃ see, e.g., Figure3 in "Triarylphosphine Oxide containment Nylon6,6 polymers" of I-YuanWan et al, Figure and Polymer II, 1995, Charp II, 29-40);
·bis- (glycidyloxy) phenylphosphine oxide (BGPPO)（Td=225 ℃ C, see, e.g., phosphor-Containing Epoxy for Flame Retardant. III, U.S. Liu et al, Figure5 in Using phosphor modified Diamines as Current Agents, journal of Applied Polymer Science, 1998，63，895-901）；
·Poly (amide-imides) containing phosphine oxides（Td=245 ℃, see, e.g., Figure4 in "Synthesis and Properties of Novel Flame-Retardant Polymer in MainChain by Microwave Irradation", Journal of applied Polymer Science, 2006, 101, 4263-;
and combinations of two or more thereof.
In accordance with the present disclosure, the coated phosphorus compound used herein has a core formed from the phosphorus compound of formula (I), and the phosphorus compound of formula (I) is coated with a crosslinked polymeric coating material.
The term "coated" means having a covering, e.g., a coated surface, and includes degrees of coverage ranging from partial coverage to complete encapsulation. The coating may be intermittent or continuous. "coating" means forming a covering on a surface, such as the surface of a particle, and includes partial covering and integral covering. The term "at least partially coated" means that there is a coating material on the surface but it need not completely cover the surface. For example, the coating material can intermittently or continuously cover about 10% or more of the surface, or up to about 98% of the surface. In some embodiments, the coating covers from about 20% to about 60% of the surface.
The term "substantially encapsulated," as used herein with respect to particles covered by a coating material, means that the surface of the microparticle is primarily covered by the coating material. For example, in some embodiments, the surface is at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 99% covered. In some embodiments, the microparticles are about 100% covered by the coating material.
Alternatively, in accordance with the present disclosure, the coated phosphorus compound comprises from about 15 wt% to about 35 wt%, or from about 17 wt% to about 30 wt%, or from about 17 wt% to about 25 wt% of the crosslinked polymeric coating material, based on the total weight of the coated phosphorus compound. In those embodiments comprising about 20 wt% or more of the crosslinked polymeric capping material, the phosphorus compound is substantially encapsulated.
In accordance with the present disclosure, crosslinked polymeric coating materials for use herein include, but are not limited to: melamine-formaldehyde (MF) resins, Crosslinked Polystyrene (CPS), urea-formaldehyde (UF) resins, phenol-formaldehyde (PF) resins, silicone resins, and the like. In certain embodiments, the crosslinked polymeric coating material used herein is a melamine-formaldehyde resin.
And, by coating the phosphorus compound of formula (I) with a cross-linking coating material, the T of the coated phosphorus compoundvOr TdTo about 300 c or higher. Without being bound by or to any particular theory, it is believed that the T of the coated phosphorus compoundvOr TdThe increase in (b) increases the thermal stability of the compound and thus also its flame retardant efficacy.
The coated phosphorus compounds used herein can be prepared by any suitable process. For example, the coated phosphorus compound can be prepared in such a way that: the phosphorus-containing particles are mixed with a suitable monomer or monomers or prepolymer or prepolymers and then subjected to a polymerization process. Alternatively, the coated phosphorus compound may be prepared by: the phosphorus-containing microparticles are mixed with a suitable crosslinkable polymer and then subjected to a curing process. Alternatively, the coated phosphorus compound can be prepared by dry particle coating techniques using, for example, a hybridization machine (hybridizer), a nano-coater, or a cyclone mixer.
According to the present disclosure, the weight ratio between the aryl phosphonate oligomer or polymer and the coated phosphorus compound within the flame retardant package ranges from about 15:85 to 45:55, or from about 18:82 to 40: 60.
Also in accordance with the present disclosure, the at least one flame retardant package may be present in an amount of about 15 to 40 weight percent, alternatively about 16 to 30 weight percent, alternatively about 18 to 25 weight percent, based on the total weight of the flame retardant polymer composition.
The flame retardant polymer compositions disclosed herein may also comprise from about 10 to about 60 wt%, alternatively from about 18 to about 40 wt%, alternatively from about 20 to about 30 wt%, of a reinforcing agent, based on the total weight of the composition.
Reinforcing agents for use herein may be selected from fibrous inorganic materials (such as glass fibers, carbon fibers, and whiskers of wollastonite and potassium titanate), inorganic fillers (such as various montmorillonites, talcs, micas, calcium carbonates, silicas, clays, kaolins, glass powders, and glass beads), organic fillers (such as powders of various organics or polymers), and mixtures of two or more thereof. In one embodiment, the reinforcing agent used herein is selected from glass fibers. In yet another embodiment, the glass fibers used herein have a non-circular cross-section.
Glass fibers having a non-circular cross-section are those that: the glass fiber has a long axis perpendicular to the longitudinal direction of the fiber and corresponding to the longest straight distance in the cross-section. The non-circular cross-section also has a minor axis corresponding to the longest straight-line distance in cross-section in a direction perpendicular to the major axis. The non-circular cross-section of the fiber may have a variety of shapes including cocoon-like, rectangular, oval, semi-oval, triangular-like, polygonal, rectangular, etc. The cross-section may have other shapes, as will be appreciated by those skilled in the art. The ratio of the length of the major axis to the length of the minor axis is preferably between about 1.5:1 and about 6: 1. More preferably, the ratio is between about 2:1 and 5:1, and still more preferably between about 3:1 and about 4: 1. Suitable glass fibers having a non-circular cross-section are disclosed in EP0190001 and EP 0196194. The glass fibers may be in the form of long glass fibers, chopped short glass fibers, or other suitable forms known to those skilled in the art.
Other suitable additives may also be included in the flame retardant polymer composition. Such other additives may include, but are not limited to: impact modifiers, ultraviolet light stabilizers, heat stabilizers, antioxidants, flow enhancers, processing aids, lubricants, colorants (including dyes, pigments, carbon black, and the like), and combinations of two or more thereof.
The flame retardant polymer compositions disclosed herein can be prepared by melt blending the components using any known method. The component materials may be mixed uniformly using a melt mixer such as a single-screw or twin-screw extruder, a blender, a kneader, a Banbury mixer, or the like, to produce a resin composition. Alternatively, portions of the materials may be mixed in a melt mixer, then the remaining materials may be added and further melt mixed until homogeneous.
The flame retardant polymer compositions disclosed herein can be formed into articles using any known melt processing method such as injection molding, blow molding, extrusion, or thermoforming. Articles molded using injection molding are most preferred.
As illustrated by the examples below, molded articles formed from the reinforced polymer compositions disclosed herein (e.g., glass fiber reinforced polyester resins containing a flame retardant package formed from a weight ratio of aryl phosphonate oligomer or polymer to the coated phosphorus compound (as described above)) exhibit improved flame retardant properties when compared to those molded articles formed from the same reinforced polymer compositions containing only aryl phosphonate oligomer or polymer or only the coated phosphorus compound.
Further disclosed herein are articles formed from the reinforced polymer compositions disclosed herein. Suitable articles include, but are not limited to: components of electronic devices (e.g., desktop computers, laptop computers, tablet devices, mobile phones, handheld game consoles, etc.), manufacturing equipment (e.g., appliances, furniture, industrial equipment, office supplies, sporting goods, etc.), transportation vehicles (e.g., aircraft, automobiles, railroads, recreational sports vehicles, etc.), and health care appliances.
Examples
Materials:
PBT: polybutylene terephthalate, available from Taiwan vinpocetine Artificial RESINs, under the trade name PBT RESIN 1100-211D;
PTFE: polytetrafluoroethylene, anti-dripping agent, trade nameAvailable from dupont.
AO: pentaerythritol tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), antioxidant, Irganox (R) brandTM1100 was purchased from basf (germany).
PTS: pentaerythritol tetrastearate, mold release agent, commercially available under the trade name PTS from american TCIAMERICA corporation (TCI AMERICA (u.s.a.).
GF: glass fibers available from Nippon Electric Glass co.ltd. (Japan) under the trade name Glass NDG 187H;
AP-1 (aryl phosphonate oligomer or polymer-1): polyphosphonates under the trade name NofiaTMHM1100 is commercially available from FRX Polymers (u.s.a.)) in the united states.
AP-2 (aryl phosphonate oligomer or polymer-2): polycarbonate/polyphosphonate copolymer, available under the trade name NofiaTMHM CO6000 is available from FRX Polymers;
TPPO: triphenylphosphine oxide, commercially available (T.S.A.) from Sigma Aldrich, USAv=210℃）；
MF-C-TPPO-1: the preparation method of the TPPO particles coated with melamine-formaldehyde (MF) comprises the following steps: (a) 5g MF prepolymer, 40g TPPO and 150ml deionized water were mixed in a 500ml round bottom flask; (b) the flask was kept in an oil bath set at 80 ℃ for 2 hours, stirring at 500 r/min; (c) washing with deionized waterWashing the reaction product three times, followed by drying to obtain melamine-formaldehyde coated TPPO, wherein the melamine-formaldehyde coated TPPO has a T of 225 ℃ as measured by TGAvAnd a melamine-formaldehyde concentration of 11.27 wt%.
MF-C-TPPO-2: the preparation method of the melamine-formaldehyde coated TPPO particles comprises the following steps: (a) in a 500ml round bottom flask, 11g MF prepolymer, 40g TPPO and 150ml deionized water were mixed; (b) the flask was kept in an oil bath set at 80 ℃ for 2 hours, stirring at 500 r/min; (c) washing the reaction product three times with deionized water, followed by drying to obtain melamine-formaldehyde coated TPPO, wherein the melamine-formaldehyde coated TPPO has a T of 320 ℃ as measured by TGAvAnd a melamine-formaldehyde concentration of 20.34 wt%.
MF-C-TPPO-3: the preparation method of the melamine-formaldehyde coated TPPO particles comprises the following steps: (a) in a 500ml round bottom flask, 27g MF prepolymer, 40g TPPO and 150ml deionized water were mixed; (b) the flask was kept in an oil bath set at 80 ℃ for 2 hours, stirring at 500 r/min; (c) washing the reaction product three times with deionized water, followed by drying to obtain melamine-formaldehyde coated TPPO, wherein the melamine-formaldehyde coated TPPO has a T of 326 ℃ as measured by TGAvAnd a melamine-formaldehyde concentration of 39.19 wt%.
CPS-C-TPPO: TPPO particles coated with crosslinked polystyrene were prepared as follows: (a) 0.12g NaOH and 0.1g NaNO2Dissolved in 80g of deionized water and 1% H was used2SO4Adjusting the solution to pH 6.4; (b) adding 4g of styrene, 16g of TPPO, 0.3g of divinylbenzene to the solution from step (a) and mixing the solution with ultrasound for 10 min; (d) the solution was transferred to a 250ml flask and the flask was kept at a temperature of 70 ℃ for 8 hours; and (e) washing the product by deionized water, followed by drying in a vacuum state at 75 ℃ for 3 hours to obtain TPPO coated with crosslinked polystyrene, wherein the coated crosslinked polystyrene is measured by TGATPPO of alkenes has a T of 305 ℃vAnd a crosslinked polystyrene concentration of 22.89 wt%.
TPP: purchased from Sigma-AldrichvTriphenyl phosphate at 158 ℃;
MF-C-TPP: the preparation method of the melamine-formaldehyde coated TPP particles comprises the following steps: (a) in a 500ml round bottom flask, 11g MF prepolymer, 40g TPP and 150ml deionized water were mixed; (b) placing the flask in an oil bath at 80 ℃, and stirring for 2 hours at 500 r/min; (c) washing the reaction product three times with deionized water, followed by drying to obtain melamine-formaldehyde coated TPP, wherein said melamine-formaldehyde coated TPP has a T of 308 ℃ as measured by TGAvAnd a melamine-formaldehyde concentration of 18.44 wt%;
FR: under the trade name ExolitTMOP1230 is a halogen-free flame retardant based on aluminum diethylphosphinate purchased from clariant (switzerland).
Comparative examples CE1-CE10 and examples E1-E3
In each of comparative examples CE1-CE10 and examples E1-E3, a polyester composition resin was prepared as follows: appropriate amounts of PBT, GF, AP-1 or AP-2, TPPO (coated or uncoated) and other additives (as listed in Table 1) were dried, pre-mixed and melt blended in a ZSK26 twin screw extruder (purchased from Coperion Werner Pfleiderer GmbH Co., Germany) set at 250 ℃, an extrusion speed of 300rpm and an output of 20 kg/hr.
The resin thus obtained was then injection molded into a sample plate of type 1A (4 mm thick) with the barrel temperature set at 250 ℃ and the mold temperature at 80 ℃. Using such a sample plate, the test piece was tested according to ISO 527-2: 1993 measures the tensile modulus, tensile strength and elongation at break for each composition, charpy-notched-impact strength (notched-charpy) for each composition according to ISO179 and the results are listed in table 1. In addition, the resin in each of CE1-CE9 and E1-E4 was also injection molded into UL test pieces-127 x12.7x1.5mm for flame retardancy measurements. The results are shown in Table 1.
The results show that when AP-1 or AP-2 or MF-C-TPPO-2 is added to the glass fiber reinforced polyester (CE1 or CE7), respectively, the flame retardant rating of the composition is recorded as NVC or V1. However, by adding AP-1 or AP-2 together with MF-C-TPPO-2 (in weight ratios of 20: 80, 25:75 or 35: 65) to the glass fiber reinforced polyester, the flame retardant rating of the composition (UL 94) was improved V0 (see E1-E3). Further, when AP-1 and MF-C-TPPO-2 were added at a low weight ratio of 10:90 (CE 8) or AP-1 was added to the polyester with TPPO, the flame retardant rating of the composition ranged from NVC to V1.
Comparative examples CE11-CE23 and example E4
In each of comparative examples CE11-CE23 and example E4, a polyester composition resin was prepared as described above (all components are listed in Table 2).
Thereafter, the resin was injection-molded into test specimens (following the same procedures as described above), tensile properties (including tensile modulus, tensile strength and elongation at break) and charpy notch impact strength were measured for each composition, and the results are listed in table 2. In addition, the resin in each of CE11-CE23 and E4 was also injection molded into UL test pieces-127 x12.7x1.5mm for flame retardancy measurement. The results are shown in Table 2.
Again, it was demonstrated that by adding AP-1 together with CPS-C-TPPO to glass fiber reinforced polyester, the flame retardant rating of the composition was improved to V0 (E4) compared to those where either AP-1 or CPS-C-TPPO was added alone (CE1 and CE 15). It has also been demonstrated that the degree of coating of the coated TPPO is important to its flame retardant effectiveness. In particular, as illustrated by CE12 and CE14, when the degree of coating is too low (e.g., about 12 wt% or less in MF-C-TPPO-1) or too high (e.g., about 40 wt% or more in MF-C-TPPO-2), the synergistic effect between the aryl phosphonate oligomer or polymer and the coated phosphorus compound is not maximized.
Claims (13)
1. A flame retardant polymer composition comprising: (a) at least one polymer; and (b) 15 to 40 wt% of at least one flame retardant package, wherein the total wt% of all components comprised in the flame retardant polymer composition adds up to 100 wt%,
wherein,
the flame retardant package consists essentially of an aryl phosphonate oligomer or polymer and a coated phosphorus compound in a weight ratio of 15:85 to 45: 55;
the coated phosphorus compound has a core formed from a phosphorus compound of formula (I) and the core is coated with 15 to 35 wt% of at least one crosslinked polymeric coating material, based on the total weight of the coated phosphorus compound;
and wherein the one or more of the one,
R1is straight-chain or branched C1-C4Alkyl, haloalkyl or C3-C6A cycloalkyl group; r2And R3Each of which is a straight or branched C1-C4Alkyl, haloalkyl, C3-C6Cycloalkyl or aryl.
2. The flame retardant polymer composition according to claim 1, wherein the phosphorus compound of formula (I) has a volatilization temperature (T:)v) Or decomposition temperature (T)d) At a temperature of 180-.
3. The flame retardant polymer composition according to claim 2, wherein the phosphorus compound of formula (I) is selected from triphenylphosphine oxide (TPPO), bis (4-hydroxyphenyl) phenylphosphine oxide (BOHPPO), bis 4-carboxyphenylphenylphosphine oxide (BCPPO), phosphine oxide containing poly (amide-imide) and combinations of two or more thereof, or the phosphorus compound of formula (I) is triphenylphosphine oxide (TPPO).
4. The flame retardant polymer composition according to any one of claims 1-3 wherein the at least one cross-linked polymer coating material is selected from melamine-formaldehyde (MF) resins, cross-linked polystyrene (CPS), urea-formaldehyde (UF) resins, phenol-formaldehyde (PF) resins, silicone resins, and combinations of two or more thereof, or the at least one cross-linked polymer coating material is selected from melamine-formaldehyde (MF) resins and cross-linked polystyrene (CPS).
5. The flame retardant polymer composition of any of claims 1-3, wherein the coated phosphorus compound comprises 17-30 wt%, or 17-25 wt% of the crosslinked polymer coating material, based on the total weight of the coated phosphorus compound.
6. The flame retardant polymer composition of any of claims 1-3 wherein the aryl phosphonate oligomer or polymer is a linear or branched polyphosphonate or copoly phosphonate containing one or more structural units of formula (II):
wherein R is4Is methyl or phenyl and n is an integer not exceeding about 90.
7. The flame retardant polymer composition according to any one of claims 1-3 wherein the at least one polymer is selected from thermoplastic polymers, or the at least one polymer is selected from polyamides, polyesters, polycarbonates, Acrylonitrile Butadiene Styrene (ABS), polyurethanes, polyphenylene oxide (PPO), Liquid Crystal Polymers (LCP), and blends of two or more thereof, or the at least one polymer is a polyester selected from polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polycyclohexanedimethylene terephthalate (PCT), polyester elastomers, and combinations of two or more thereof.
8. The flame retardant polymer composition according to claim 7 wherein the flame retardant polymer composition comprises 30 to 85 wt.%, or 40 to 75 wt.%, or 45 to 60 wt.% of the at least one polymer, based on the total weight of the flame retardant polymer composition.
9. The flame retardant polymer composition according to any one of claims 1-3, wherein the flame retardant polymer composition comprises 15-40 wt%, alternatively 16-30 wt%, alternatively 18-25 wt%, of the at least one flame retardant package, based on the total weight of the flame retardant polymer composition.
10. A flame retardant polymer composition according to any of claims 1-3 wherein the weight ratio between the aryl phosphonate oligomer or polymer and the coated phosphorus compound is: 15:85-45:55, or 18:82-40: 60.
11. The flame retardant polymer composition according to any of claims 1-3 wherein the flame retardant polymer composition further comprises 10 to 60 wt.%, alternatively 18 to 40 wt.%, alternatively 20 to 30 wt.%, based on the total weight of the composition, of at least one reinforcing agent.
12. The flame retardant polymer composition according to claim 11 wherein the at least one reinforcing agent is selected from glass fibers, carbon fibers, whiskers of wollastonite and potassium titanate, montmorillonite, talc, mica, calcium carbonate, silica, clay, kaolin, glass powder, glass beads, polymer powder, and mixtures of two or more thereof, or the at least one reinforcing agent is selected from glass fibers.
13. An article formed from the flame retardant polymer composition of any of claims 1-12.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705563A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Flame-proof thermoplastic polyurethane composition and its expanded bead |
| CN114258415A (en) * | 2018-08-15 | 2022-03-29 | 化学制造布敦海姆两合公司 | Polymer Compounds Containing Phosphonate Flame Retardants |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998008898A1 (en) * | 1996-08-29 | 1998-03-05 | E.I. Du Pont De Nemours And Company | Flame retardant composition |
| CN1743336A (en) * | 2001-02-15 | 2006-03-08 | 帕布服务公司 | Novel hydroxyaryl phosphine oxides,diglycidyl ethers and epoxy compositions, composites and laminates derived therefrom |
| CN102229712A (en) * | 2011-04-25 | 2011-11-02 | 同济大学 | Preparation method of melamine/formaldehyde resin cladded melamine phosphatic microcapsules for fire retardant |
| CN103003344A (en) * | 2010-07-19 | 2013-03-27 | 帝斯曼知识产权资产管理有限公司 | Flame Retardant Insulated Electrical Conductors |
-
2013
- 2013-07-03 CN CN201310277098.0A patent/CN104277432A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998008898A1 (en) * | 1996-08-29 | 1998-03-05 | E.I. Du Pont De Nemours And Company | Flame retardant composition |
| CN1743336A (en) * | 2001-02-15 | 2006-03-08 | 帕布服务公司 | Novel hydroxyaryl phosphine oxides,diglycidyl ethers and epoxy compositions, composites and laminates derived therefrom |
| CN103003344A (en) * | 2010-07-19 | 2013-03-27 | 帝斯曼知识产权资产管理有限公司 | Flame Retardant Insulated Electrical Conductors |
| CN102229712A (en) * | 2011-04-25 | 2011-11-02 | 同济大学 | Preparation method of melamine/formaldehyde resin cladded melamine phosphatic microcapsules for fire retardant |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705563A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Flame-proof thermoplastic polyurethane composition and its expanded bead |
| CN109705563B (en) * | 2017-10-26 | 2021-03-16 | 中国石油化工股份有限公司 | Flame retardant thermoplastic polyurethane composition and expanded beads thereof |
| CN114258415A (en) * | 2018-08-15 | 2022-03-29 | 化学制造布敦海姆两合公司 | Polymer Compounds Containing Phosphonate Flame Retardants |
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