WO2024121540A1 - Flame retardant polymers and blends - Google Patents
Flame retardant polymers and blends Download PDFInfo
- Publication number
- WO2024121540A1 WO2024121540A1 PCT/GB2023/053126 GB2023053126W WO2024121540A1 WO 2024121540 A1 WO2024121540 A1 WO 2024121540A1 GB 2023053126 W GB2023053126 W GB 2023053126W WO 2024121540 A1 WO2024121540 A1 WO 2024121540A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- repeating units
- phosphonated
- ethylene repeating
- polymer blend
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 320
- 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 52
- 239000003063 flame retardant Substances 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 224
- 239000005977 Ethylene Substances 0.000 claims abstract description 219
- 229920002959 polymer blend Polymers 0.000 claims abstract description 170
- -1 polyethylene Polymers 0.000 claims abstract description 151
- 239000004698 Polyethylene Substances 0.000 claims abstract description 130
- 229920000573 polyethylene Polymers 0.000 claims abstract description 124
- 229920001684 low density polyethylene Polymers 0.000 claims description 56
- 239000004702 low-density polyethylene Substances 0.000 claims description 56
- 239000000654 additive Substances 0.000 claims description 35
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical group [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 34
- 230000000996 additive effect Effects 0.000 claims description 31
- 229920000098 polyolefin Polymers 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 239000004700 high-density polyethylene Substances 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 19
- 229920001903 high density polyethylene Polymers 0.000 claims description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 14
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 125000005647 linker group Chemical group 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 claims description 5
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims description 5
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 96
- 230000008569 process Effects 0.000 description 84
- 230000004580 weight loss Effects 0.000 description 80
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 64
- 239000002243 precursor Substances 0.000 description 64
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 33
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- 125000004429 atom Chemical group 0.000 description 25
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- 238000010348 incorporation Methods 0.000 description 22
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- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 17
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- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 12
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- 230000000875 corresponding effect Effects 0.000 description 10
- 238000005227 gel permeation chromatography Methods 0.000 description 10
- 125000001072 heteroaryl group Chemical group 0.000 description 10
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
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- 238000003873 derivative thermogravimetry Methods 0.000 description 9
- 125000005843 halogen group Chemical group 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 229910052794 bromium Inorganic materials 0.000 description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 7
- 125000004450 alkenylene group Chemical group 0.000 description 7
- 125000004419 alkynylene group Chemical group 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 7
- 239000013256 coordination polymer Substances 0.000 description 7
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 7
- 229940069096 dodecene Drugs 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- SJHCUXCOGGKFAI-UHFFFAOYSA-N tripropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC(C)C SJHCUXCOGGKFAI-UHFFFAOYSA-N 0.000 description 7
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 125000000304 alkynyl group Chemical group 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 125000005842 heteroatom Chemical group 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 description 6
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 description 5
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 5
- YPLVPFUSXYSHJD-UHFFFAOYSA-N 11-bromoundec-1-ene Chemical compound BrCCCCCCCCCC=C YPLVPFUSXYSHJD-UHFFFAOYSA-N 0.000 description 5
- 239000004114 Ammonium polyphosphate Substances 0.000 description 5
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- 239000012190 activator Substances 0.000 description 5
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 5
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 4
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- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000011174 green composite Substances 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000005980 hexynyl group Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000002808 molecular sieve 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000010963 scalable process Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/016—Flame-proofing or flame-retarding additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Definitions
- the invention relates to a polymer comprising ethylene repeating units and phosphonated ethylene repeating units.
- the invention also relates to polymer blends comprising a phosphonated polymer and polyethylene.
- the invention also relates to the use of the polymer or polymer blends as a flame retardant, as well as to a process for preparing a phosphonated polymer and a polymer blend.
- Polyethylene is known to be the most widely used plastic in the world.
- Phosphorus flame retardants are considered as alternatives for halogenated flame retardants due to their chemical versatility, multiple flame retardant mechanisms and high flame retardancy, even at low loadings.
- Most PFRs have mechanisms of action in the solid or condensed phase, or in the gas phase. 4b, 4c, 5, 6, 7 [0004]
- strategies for integrating the desirable flame retardant properties of PFRs into polyolefins have faced a number of challenges.
- a polymer obtained, directly obtained or obtainable by the process of the second aspect of the invention is provided.
- a polymer blend comprising: a polymer of the first or third aspect of the invention; and polyethylene.
- a polymer blend comprising: phosphonated polyethylene; a polyolefin; and a hydroxylated flame retardant additive.
- alkynylene refers to a divalent equivalent of an alkynyl group as described above.
- alkoxy refers to -O-alkyl, wherein alkyl is a straight or branched chain and comprises 1, 2, 3, 4, 5 or 6 carbon atoms. In one class of embodiments, alkoxy has 1, 2, 3 or 4 carbon atoms. This term includes reference to groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentoxy, hexoxy and the like.
- Carbocyclyl means a non-aromatic saturated or partially saturated monocyclic, or a fused, bridged, or spiro bicyclic carbocyclic ring system(s).
- Monocyclic carbocyclic rings contain from about 3 to 12 (suitably from 3 to 7) ring atoms.
- Bicyclic carbocycles contain from 7 to 17 carbon atoms in the rings, suitably 7 to 12 carbon atoms, in the rings.
- Bicyclic carbocyclic rings may be fused, spiro, or bridged ring systems.
- the polymer comprises 2-8 mol% of phosphonated ethylene repeating units, B. Even more suitably, the polymer comprises 2.25-7 mol% of phosphonated ethylene repeating units, B. In embodiments, the polymer comprises 4-6.5 mol% of phosphonated ethylene repeating units, B. [0042] In embodiments, the polymer comprises: (i) 86-99 mol% of ethylene repeating units, A, and (ii) 1-14 mol% of phosphonated ethylene repeating units, B. [0043] In embodiments, the polymer comprises: (i) 90-98.25 mol% of ethylene repeating units, A, and (ii) 1.75-10 mol% of phosphonated ethylene repeating units, B.
- Y is a (5-18C)alkylene group, a (5-18C)alkenylene group, or a (5-18C)alkynylene group linking C 1 to X. More suitably, Y is a (5-12C)alkylene group, a (5-12C)alkenylene group, or a (5- 12C)alkynylene group linking C 1 to X. Yet more suitably, Y is a (5-9C)alkylene group linking C 1 to X. [0050] In embodiments, Y is selected from: wherein denotes the point of attachment to C1; and denotes the point of attachment to X.
- the polymer may have a temperature at maximum weight loss rate (Tmax) in air of 480- 510 0C.
- the polymer has a temperature at maximum weight loss rate (Tmax) in air of 483- 507 0C.
- the polymer has a melting temperature (T m ) of 115-130 0C, a temperature at maximum weight loss rate (T max ) in nitrogen of 500-515 0C and a temperature at maximum weight loss rate (T max ) in air of 480-510 0C.
- the polymer has: a temperature of 10% weight loss (T 10% ) in nitrogen of 300-500 0C; a temperature of 50% weight loss (T 50% ) in nitrogen of 500-520 0C; and a temperature at maximum weight loss rate (T max ) in nitrogen of 500-515 0C.
- the polymer has: a temperature of 10% weight loss (T 10% ) in nitrogen of 305-475 0C; a temperature of 50% weight loss (T 50% ) in nitrogen of 503-510 0C; and a temperature at maximum weight loss rate (T max ) in nitrogen of 505-510 0C.
- the polymer has: a temperature of 10% weight loss (T10%) in air of 250-500 0C; a temperature of 50% weight loss (T50%) in air of 450-550 0C; and a temperature at maximum weight loss rate (T max ) in air of 480-510 0C.
- the polymer has: a temperature of 10% weight loss (T10%) in air of 270-460 0C; a temperature of 50% weight loss (T50%) in air of 480-510 0C; and a temperature at maximum weight loss rate (Tmax) in air of 483-507 0C.
- the polymer has: a heat release capacity (HRC) of 200-300 J g -1 K; a peak heat release rate (pHRR) of 150-250 W g -1 ; a total heat release (THR) of 5-15 kJ g -1 ; and a temperature at peak heat release rate of (T pHRR ) of 485-500 0C.
- HRC heat release capacity
- pHRR peak heat release rate
- THR total heat release
- T pHRR temperature at peak heat release rate
- the polymer has: a heat release capacity (HRC) of 215-275 J g -1 K; a peak heat release rate (pHRR) of 180-230 W g -1 ; a total heat release (THR) of 7-12 kJ g -1 ; and a temperature at peak heat release rate of (TpHRR) of 488-497 0C.
- HRC heat release capacity
- pHRR peak heat release rate
- THRR total heat release
- TpHRR temperature at peak heat release rate
- the phosphonate group decomposes before the remainder of the polymer to form a carbonaceous char layer.
- the carbonaceous char layer shields the polymer from oxygen and prevents the formation of flammable gases.
- the polymer is such that, when heated to 700 0C in nitrogen, a carbonaceous char layer is formed accounting for 0.5-2.0 wt% of the resulting material. More suitably, the polymer is such that, when heated to 700 0C in nitrogen, a carbonaceous char layer is formed accounting for 0.8-1.7 wt% of the resulting material.
- the phosphonated ethylene repeating units, B are randomly distributed along the length of the polymer and the polymer end groups are ethylene repeating units, A.
- the polymer may have a -C-C- backbone (i.e., the polymer backbone consists of / consists essentially of carbon atoms).
- the polymer may consist of / consist essentially of ethylene repeating units, A, and phosphonated ethylene repeating units, B.
- the polymer may also be linear (e.g., units of the polymer are arranged in a straight line) or branched (e.g., linear polymer chain substituted with one or more polymer chains along its length).
- the polymer blend comprises 1-20 wt% of the polymer. More suitably, the polymer blend comprises 1-10 wt% of the polymer.
- the polyethylene in the polymer blend may be selected from high density polyethylene (HDPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE).
- the polyethylene is LDPE.
- the polymer blend may comprise 70-99.9 wt% polyethylene.
- the polymer blend comprises 80-99 wt% polyethylene. More suitably, the polymer blend comprises 90-99 wt% polyethylene. In embodiments, the polymer blend comprises 80-99 wt% HDPE, LDPE or LLDPE.
- the polymer blend comprises 90-99 wt% LDPE.
- the polymer blend may comprise 0.1-30 wt% of the polymer and 70-99.9 wt% polyethylene.
- the polymer blend comprises 1-20 wt% of the polymer and 80-99 wt% polyethylene.
- the polymer blend comprises 1-10 wt% of the polymer and 90-99 wt% polyethylene.
- the polyethylene may be HDPE, LDPE or LLDPE.
- the polymer blend comprises: a) 10 wt% of the polymer and 90 wt% LDPE; b) 5 wt% of the polymer and 95 wt% LDPE; or c) 1 wt% of the polymer and 99 wt% LDPE.
- the melting temperature (T m ), temperature of 10% weight loss (T 10% ), temperature of 50% weight loss (T50%) and temperature at maximum weight loss rate (Tmax) of the polymer blend can be determined according to the protocols defined hereinbefore.
- the polymer blend may have a melting temperature (Tm) of 109-112 0C.
- the polymer blend has a melting temperature (T m ) of 109-112 0C, a temperature of 10% weight loss (T 10% ) in air of 340-420 0C, and a temperature of 50% weight loss (T 50% ) in air of 375-500 0C.
- T m melting temperature
- T 10% 10% weight loss
- T 50% 50% weight loss
- the polymer blend may have a temperature at maximum weight loss rate (T max ) in air of 390-470 0C.
- the flame retardant is selected from a layered double hydroxide (LDH), aluminium trihydroxide (i.e., Al(OH) 3 ) (ATH), Mg(OH) 2 (MDH), Sb 2 O 3 , resorcinol bis(diphenyl phosphate) (RDP), a triaryl phosphate, a metal phosphinate, 9,10-Dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide (DOPO), trischloropropyl phosphate (TCCP), ammonium polyphosphate (APP) and red phosphorus. More suitably, the flame retardant is selected from a LDH, ATH and MDH.
- LDH aluminium trihydroxide
- MDH Mg(OH) 2
- Sb 2 O 3 resorcinol bis(diphenyl phosphate)
- DOPO 9,10-Dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide
- TCCP tri
- the char layer inhibits the transmission of oxygen and heat, thereby preventing the formation of flammable gases.
- the phosphonated polyethylene is able to serve as an amphiphilic compatibilizer for the hydrophilic hydroxylated flame retardant additive and the hydrophobic polyolefin (e.g., polyethylene, resulting in a more uniform polymer blend having improved mechanical integrity.
- the phrase “phosphonated polyethylene” refers to a polymer comprising ethylene repeating units and a plurality of phosphonate-containing groups.
- the phosphonate- containing groups may be provided as substituents on some or all of the ethylene repeating units.
- the phosphonated polyethylene may comprise 0.5-20 mol% mol% of phosphonate groups. The quantity of phosphonate groups present within the polymer may be determined by integration of peaks recorded by 1 H NMR in C 2 D 2 Cl 4 at 130 °C.
- the polymer blend comprises 76-84 wt% of the polyolefin. Yet more suitably, the polymer blend comprises 80 wt% of the polyolefin. Even more suitably, the polymer blend comprises 80 wt% polyethylene. In embodiments, the polymer blend comprises 70-90 wt% HDPE, LDPE or LLDPE. In embodiments, the polymer blend comprises 76-84 wt% LDPE. In embodiments, the polymer blend comprises 80 wt% LDPE. [00116]
- the hydroxylated flame retardant additive may be selected from a LDH, ATH and MDH. Suitably, the hydroxylated flame retardant additive is ATH.
- the polymer blend may comprise 5-15 wt% of the hydroxylated flame retardant additive.
- the polymer blend comprises 8-12 wt% of the hydroxylated flame retardant additive. More suitably, the polymer blend comprises 10 wt% of the hydroxylated flame retardant additive.
- the polymer blend comprises: a) 70-90 wt% polyethylene, 5-15 wt% of the phosphonated polyethylene, and 5-15 wt% of the hydroxylated flame retardant additive; b) 76-84 wt% polyethylene, 8-12 wt% of the phosphonated polyethylene, and 8-12 wt% of the hydroxylated flame retardant additive; or c) 80 wt% polyethylene, 10 wt% of the phosphonated polyethylene, and 10 wt% of the hydroxylated flame retardant additive.
- the melting temperature (T m ), temperature of 10% weight loss (T 10% ), temperature of 50% weight loss (T 50% ) and temperature at maximum weight loss rate (T max ) of the polymer blend can be determined according to the protocols defined hereinbefore.
- the polymer blend may have a melting temperature (T m ) of 110-115 0C.
- the polymer blend has a melting temperature (T m ) of 111-113 0C.
- the polymer blend may have a temperature of 10% weight loss (T 10% ) in air of 360-380 0C.
- the polymer blend has a temperature of 10% weight loss (T 10% ) in air of 362-372 0C.
- the polymer blend has a melting temperature (T m ) of 110-115 0C and a temperature of 10% weight loss (T10%) in air of 360-380 0C.
- the polymer blend may have a temperature of 50% weight loss (T50%) in air of 470-480 0C.
- the polymer blend has a temperature of 50% weight loss (T 50% ) in air of 472-475 0C.
- the polymer blend has a melting temperature (Tm) of 110-115 0C and a temperature of 50% weight loss (T50%) in air of 470-480 0C.
- the polymer blend has a temperature of 10% weight loss (T10%) in air of 360-380 0C, a temperature of 50% weight loss (T50%) in air of 470-480 0C and a temperature at maximum weight loss rate (Tmax) in air of 460-470 0C.
- the polymer blend has a temperature of 10% weight loss (T10%) in air of 362-372 0C, a temperature of 50% weight loss (T50%) in air of 472-475 0C and a temperature at maximum weight loss rate (Tmax) in air of 475- 478 0C.
- the invention provides a use of a polymer as defined herein or a polymer blend as defined herein as a flame retardant.
- Process for the preparation of a polymer and a polymer blend [00130]
- a process for the preparation of a polymer comprising the steps of: a) providing a precursor polymer comprising: (i) ethylene repeating units, A; and (ii) LG-functionalised ethylene repeating units, C, wherein LG is a leaving group; and b) phosphonating the precursor polymer provided in step a), such that the LG-functionalised repeating units, C, are converted into phosphonated ethylene repeating units, B.
- a process for the preparation of a polymer blend comprising the steps of: a) providing a precursor polymer comprising: (i) ethylene repeating units, A; and (ii) LG-functionalised ethylene repeating units, C, wherein LG is a leaving group; b) phosphonating the precursor polymer provided in step a), such that the LG-functionalised repeating units, C, are converted into phosphonated ethylene repeating units, B; and c) mixing the polymer resulting from step b) with one or more polyolefins.
- ethylene repeating units, A may have any of the definitions discussed herein in relation to the first aspect.
- the phosphonated ethylene repeating units, B, formed in step b) may have any of the definitions discussed herein in relation to the first aspect.
- Each LG-functionalised ethylene repeating unit, C may independently have the structural formula C1: wherein Y is linking group connecting C1 to LG; and LG is a leaving group.
- Y links C 1 to LG by 5-18 bridging atoms.
- bridging atoms as defined herein will be understood to mean the fewest number of atoms directly connecting C 1 to LG.
- Y links C 1 to LG by 5-12 bridging atoms. Yet more suitably, Y links C 1 to LG by 5-9 bridging atoms. In embodiments, Y links C 1 to LG by 5 bridging atoms. In embodiments, Y links C 1 to LG by 9 bridging atoms.
- Y may be an alkylene, an alkenylene or an alkynylene group linking C 1 to LG.
- Y is a (5-18C)alkylene group, a (5-18C)alkenylene group, or a (5-18C)alkynylene group linking C 1 to LG.
- the precursor polymer comprises 90-98.25 mol% of ethylene repeating units, A. More suitably, the precursor polymer comprises 92-98 mol% of ethylene repeating units, A. Even more suitably, the precursor polymer comprises 93-97.75 mol% of ethylene repeating units, A. In embodiments, the precursor polymer comprises 93.5-96 mol% of ethylene repeating units, A. [00140]
- the precursor polymer provided in step a) may comprise 1-14 mol% of LG- functionalised ethylene repeating units, C. Suitably, the precursor polymer comprises 1.75-10 mol% of LG-functionalised ethylene repeating units, C.
- the polymer has a molecular weight (Mw) of 25-65 kg mol -1 .
- the precursor polymer may have a melting temperature (T m ) of 115-130 0C.
- the melting temperature (T m ) of the precursor polymer can be determined according to the protocol defined hereinbefore.
- the precursor polymer has a melting temperature (Tm) of 116-127 0C.
- the precursor polymer may be prepared by polymerising ethylene monomers, A’, and LG-functionalised ethylene monomers, C’.
- each ethylene monomer, A’ has the structural formula: [00148]
- Each LG-functionalised ethylene monomer, C’ may independently have the structural formula C’1: wherein Y and LG are as defined herein.
- each LG-functionalised ethylene monomer, C’ independently has the structural formula: wherein LG is as defined herein.
- each LG-functionalised ethylene monomer, C’ is a bromoalkene. More suitably, each LG-functionalised ethylene monomer, C’, is an ⁇ -bromo- ⁇ -alkene.
- each LG-functionalised ethylene monomer, C’ is 11-bromo-1-undecene or 7- bromo-1-heptene.
- the precursor polymer provided in step a) may be polyethylene- co-11-bromo-1-undecene or polyethylene-co-7-bromo-1-heptene.
- said polymerisation may be conducted in the presence of an olefin polymerisation catalyst.
- the olefin polymerisation catalyst may have a structure according to formula (D1): (L 1 )(L 2 )M 1 (Y 1 )(Y 2 ) (D1) wherein M 1 is zirconium, hafnium or titanium; L 1 and L 2 are each independently a ligand comprising a cyclopentadienyl moiety, said cyclopentadienyl moiety being ⁇ 5 bound to M 1 , wherein L 1 and L 2 are optionally linked to one another; and Y 1 and Y 2 are each independently a ligand selected from hydride, halo and (1-3C)alkyl.
- D1 formula (D1): (L 1 )(L 2 )M 1 (Y 1 )(Y 2 ) (D1) wherein M 1 is zirconium, hafnium or titanium; L 1 and L 2 are each independently a ligand comprising a cyclopentadienyl moiety, said cyclopentadienyl
- M 1 is zirconium.
- Y 1 and Y 2 are each independently selected from hydride, chloro and methyl. In embodiments, Y 1 and Y 2 are each chloro.
- the optional substituents present in L 1 and L 2 may be selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl (e.g., phenyl), aryl(1-2C)alkyl (e.g., benzyl), aryloxy (e.g., phenoxy) and heteroaryl.
- the olefin polymerisation catalyst is a bis-indenyl zirconocene compound.
- the olefin polymerisation catalyst is: [00160]
- the olefin polymerisation catalyst may be used together with one or more suitable activators. Suitable activators are well known in the art and include organo aluminium compounds (e.g., alkyl aluminium compounds).
- the activators include aluminoxanes (e.g., methylaluminoxane (MAO)), triisobutylaluminium (TIBA), diethylaluminium (DEAC) and triethylaluminium (TEA).
- the olefin polymerisation catalyst is used together with MAO, TIBA, DEAC and/or TEA.
- the precursor polymer may be phosphonated by contacting the precursor polymer with a phosphonating reagent, B’.
- phosphonating reagent, B’ has the structural formula B’1.
- the flame retardant additive is selected from a LDH, ATH, MDH, Sb 2 O 3 , RDP, a triaryl phosphate, a metal phosphinate, DOPO, TCCP, APP and red phosphorus. More suitably, the flame retardant additive is ATH.
- the present invention provides a polymer obtained, directly obtained or obtainable by a process of the second aspect of the invention.
- the present invention provides a polymer blend obtained, directly obtained or obtainable by a process of the sixth aspect of the invention.
- the following numbered statements 1 to 144 are not claims, but instead describe particular aspects and embodiments of the invention: .
- the polymer of statement 13 wherein Y links C1 to X by 5-18 bridging atoms.
- the polymer of statement 12 or 13 wherein Y links C1 to X by 5-9 bridging atoms.
- each LG-functionalised ethylene repeating unit, C is independently a halogenated ethylene repeating unit.
- the process of any one of statements 43-53, wherein the precursor polymer provided in step a) comprises 86-99 mol% of ethylene repeating units, A.
- the process of any one of statements 43-54, wherein the precursor polymer comprises 90- 98.25 mol% of ethylene repeating units, A.
- TGA and DTG curves of PE-PO(O i Pr) 2 , PE-PO(OPh) 2 , and LDPE demonstrate comparable T 50% and T max (500–510 °C).
- T 10% , T 50% and T max obtained from LDPE were lower when performed under air atmosphere than nitrogen atmosphere.
- a single-decomposition step was observed from testing LDPE under both atmospheres evidenced by a single DTG peak ( Figures 15b and 15d). The residue of the LDPE at 700 °C is at 0.16–0.22%.
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Abstract
The invention relates to a polymer comprising ethylene repeating units and phosphonated ethylene repeating units. The invention also relates to polymer blends comprising a phosphonated polymer and polyethylene. The invention also relates to the use of the polymer or polymer blends as a flame retardant, as well as to a process for preparing a phosphonated polymer and a polymer blend.
Description
FLAME RETARDANT POLYMERS AND BLENDS INTRODUCTION [0001] The invention relates to a polymer comprising ethylene repeating units and phosphonated ethylene repeating units. The invention also relates to polymer blends comprising a phosphonated polymer and polyethylene. The invention also relates to the use of the polymer or polymer blends as a flame retardant, as well as to a process for preparing a phosphonated polymer and a polymer blend. BACKGROUND OF THE INVENTION [0002] Polyethylene is known to be the most widely used plastic in the world. However, despite its use in an array of fields, its low limiting oxygen index (LOI) and poor fire resistance mean that its use is restricted in many applications requiring fire safety standards.1 Traditionally, the flame retardancy of polyolefins has been improved by using flame-retardant additives such as chlorinated or brominated compounds, often used in combination with antimony trioxide.2 However, many halogenated chemicals which are used for this purpose have proven to be highly persistent, bioaccumulative and toxic in the environment and to animals and humans.3 [0003] Phosphorus flame retardants (PFRs) are considered as alternatives for halogenated flame retardants due to their chemical versatility, multiple flame retardant mechanisms and high flame retardancy, even at low loadings.4 Three different general structures of these PFRs can be recognised: phosphite esters (O=P(OR)3), phosphonates (O=P(OR)2R), and phosphinates (O=P(OR)R2). Most PFRs have mechanisms of action in the solid or condensed phase, or in the gas phase.4b, 4c, 5, 6, 7 [0004] In spite of this, strategies for integrating the desirable flame retardant properties of PFRs into polyolefins have faced a number of challenges. In particular, when using electrophilic early transition metal (groups 3 and 4) catalysts to integrate PFRs, which has been widely used in conventional olefin polymerisation, the strong interactions between Lewis-acidic cationic metal centres and Lewis-basic polar functional groups prevent olefin coordination and insertion, as well as suffering from catalyst deactivation. Moreover, coordination of the Lewis basic group on the inserted comonomer at the metal centre forms a chelate structure. This effect is severe in early transition metal catalysed copolymerisation with short-chain comonomers, since a stable 5– to 7–membered chelating ring can be formed. [0005] Accordingly, there remains a need for a non-toxic and non-bioaccumulative polyolefin with enhanced thermal stability and improved flame retardant properties, as well as a scalable process of preparing the same.
[0006] The invention was devised with the foregoing in mind. SUMMARY OF THE INVENTION [0007] According to a first aspect of the invention there is provided a polymer comprising: ethylene repeating units, A; and phosphonated ethylene repeating units, B. [0008] According to a second aspect of the invention there is provided a process for the preparation of a polymer, the process comprising the steps of: a) providing a precursor polymer comprising: (i) ethylene repeating units, A; and (ii) LG-functionalised ethylene repeating units, C, wherein LG is a leaving group; and b) phosphonating the precursor polymer provided in step a), such that the LG-functionalised repeating units, C, are converted into phosphonated ethylene repeating units, B. Suitably, the process of the second aspect of the invention is a process for the preparation of a polymer of the first aspect of the invention. [0009] According to a third aspect of the invention there is provided a polymer obtained, directly obtained or obtainable by the process of the second aspect of the invention. [0010] According to a fourth aspect of the invention there is provided a polymer blend comprising: a polymer of the first or third aspect of the invention; and polyethylene. [0011] According to a fifth aspect of the invention there is provided a polymer blend comprising: phosphonated polyethylene; a polyolefin; and a hydroxylated flame retardant additive. [0012] According to a sixth aspect of the invention there is a provided a process for the preparation of a polymer blend, the process comprising the steps of: a) providing a precursor polymer comprising: (i) ethylene repeating units, A; and (ii) LG-functionalised ethylene repeating units, C, wherein LG is a leaving group; b) phosphonating the precursor polymer provided in step a), such that the LG-functionalised repeating units, C, are converted into phosphonated ethylene repeating units, B; and c) mixing the polymer resulting from step b) with one or more polyolefins. Suitably, the process of the sixth aspect of the invention is a process for the preparation of a polymer blend of the fourth or fifth aspect of the invention.
[0013] According to a seventh aspect of the invention there is provided a polymer blend obtained, directly obtained or obtainable by the process of the sixth aspect of the invention. [0014] According to an eighth aspect of the invention there is provided a use of a polymer of the first or third aspect of the invention, or a polymer blend of the fourth, fifth or seventh aspect of the invention as a flame retardant or a fire retardant. DETAILED DESCRIPTION OF THE INVENTION Definitions [0015] The term "(m-nC)" or "(m-nC) group" used alone or as a prefix, refers to any group having m to n carbon atoms. [0016] The term “alkyl” as used herein refers to straight or branched chain alkyl moieties, typically having 1, 2, 3, 4, 5 or 6 carbon atoms. This term includes reference to groups such as methyl, ethyl, propyl (n-propyl or isopropyl), butyl (n-butyl, sec-butyl or tert-butyl), pentyl, hexyl and the like. Most suitably, an alkyl may have 1, 2, 3 or 4 carbon atoms. [0017] The term “alkylene” as used herein refers to a divalent equivalent of an alkyl group as described above. [0018] The term “alkenyl” as used herein refers to straight or branched chain alkenyl moieties, typically having 1, 2, 3, 4, 5 or 6 carbon atoms. The term includes reference to alkenyl moieties containing 1, 2 or 3 carbon-carbon double bonds (C=C). This term includes reference to groups such as ethenyl (vinyl), propenyl (allyl), butenyl, pentenyl and hexenyl, as well as both the cis and trans isomers thereof. [0019] The term “alkenylene” as used herein refers to a divalent equivalent of an alkenyl group as described above. [0020] The term “alkynyl” as used herein refers to straight or branched chain alkynyl moieties, typically having 1, 2, 3, 4, 5 or 6 carbon atoms. The term includes reference to alkynyl moieties containing 1, 2 or 3 carbon-carbon triple bonds (C≡C). This term includes reference to groups such as ethynyl, propynyl, butynyl, pentynyl and hexynyl. [0021] The term “alkynylene” as used herein refers to a divalent equivalent of an alkynyl group as described above. [0022] The term “alkoxy” as used herein refers to -O-alkyl, wherein alkyl is a straight or branched chain and comprises 1, 2, 3, 4, 5 or 6 carbon atoms. In one class of embodiments, alkoxy has 1, 2, 3 or 4 carbon atoms. This term includes reference to groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentoxy, hexoxy and the like.
[0023] The term "aryl" or “aromatic” as used herein means an aromatic ring system comprising 6, 7, 8, 9 or 10 ring carbon atoms. Aryl is often phenyl but may be a polycyclic ring system, having two or more rings, at least one of which is aromatic. This term includes reference to groups such as phenyl, naphthyl and the like. [0024] The term “heteroaryl” or “heteroaromatic” means an aromatic mono-, bi-, or polycyclic ring incorporating one or more (for example 1-4, particularly 1, 2 or 3) heteroatoms selected from nitrogen, oxygen or sulfur. Examples of heteroaryl groups are monocyclic and bicyclic groups containing from five to twelve ring members, and more usually from five to ten ring members. The heteroaryl group can be, for example, a 5- or 6-membered monocyclic ring or a 9- or 10- membered bicyclic ring, for example a bicyclic structure formed from fused five and six membered rings or two fused six membered rings. Each ring may contain up to about four heteroatoms typically selected from nitrogen, sulfur and oxygen. Typically, the heteroaryl ring will contain up to 3 heteroatoms, more usually up to 2, for example a single heteroatom. [0025] The term “carbocyclyl”, “carbocyclic” or “carbocycle” means a non-aromatic saturated or partially saturated monocyclic, or a fused, bridged, or spiro bicyclic carbocyclic ring system(s). Monocyclic carbocyclic rings contain from about 3 to 12 (suitably from 3 to 7) ring atoms. Bicyclic carbocycles contain from 7 to 17 carbon atoms in the rings, suitably 7 to 12 carbon atoms, in the rings. Bicyclic carbocyclic rings may be fused, spiro, or bridged ring systems. [0026] The term “heterocyclyl”, “heterocyclic” or “heterocycle” means a non-aromatic saturated or partially saturated monocyclic, fused, bridged, or spiro bicyclic heterocyclic ring system(s). Monocyclic heterocyclic rings contain from about 3 to 12 (suitably from 3 to 7) ring atoms, with from 1 to 5 (suitably 1, 2 or 3) heteroatoms selected from nitrogen, oxygen or sulfur in the ring. Bicyclic heterocycles contain from 7 to 17 member atoms, suitably 7 to 12 member atoms, in the ring. Bicyclic heterocyclic(s) rings may be fused, spiro, or bridged ring systems. [0027] The term "halogen" or “halo” as used herein refers to F, Cl, Br or I. In particular, halogen may be F or Cl, of which Cl is more common. [0028] The term “haloalkyl” is used herein to refer to an alkyl group in which one or more hydrogen atoms have been replaced by halogen (e.g., fluorine) atoms. Often, haloalkyl is fluoroalkyl. Examples of haloalkyl groups include -CH2F, -CHF2 and -CF3. [0029] The term “substituted” as used herein in reference to a moiety means that one or more, especially up to 5 of the hydrogen atoms in said moiety are replaced independently of each other by the corresponding number of the described substituents. Preferably, “substituted” as used herein in reference to a moiety means that 1, 2 or 3, of the hydrogen atoms in said moiety are replaced independently of each other by the corresponding number of the described substituents. Even more preferred, “substituted” as used herein in reference to a moiety means that 1 or 2, of
the hydrogen atoms in said moiety are replaced independently of each other by the corresponding number of the described substituents. The term “optionally substituted” as used herein means substituted or unsubstituted. [0030] It will, of course, be understood that substituents are only at positions where they are chemically possible, the person skilled in the art being able to decide (either experimentally or theoretically) without inappropriate effort whether a particular substitution is possible. [0031] As used herein, references to flame retardancy will be understood to embrace fire retardancy, and vice versa. [0032] Throughout the entirety of the description and claims of this specification, where subject matter is described herein using the term “comprise” (or “comprises” or “comprising”), the same subject matter instead described using the term “consist of” (or “consists of” or “consisting of”) or “consist essentially of” (or “consists essentially of” or “consisting essentially of”) is also contemplated. [0033] Throughout the description and claims of this specification, the singular encompasses the plural unless the context otherwise requires. In particular, where the indefinite article is used, the specification is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise. [0034] Features described in conjunction with a particular aspect, embodiment or example of the invention are to be understood to be applicable to any other aspect, embodiment or example described herein unless incompatible therewith. All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. The invention is not restricted to the details of any of the specific embodiments recited herein. The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings) and/or all of the steps of any method or process so disclosed. [0035] Unless otherwise specified, where the quantity or concentration of a particular component of a given product is specified as a weight percentage (wt% or %w/w), said weight percentage refers to the percentage of said component by weight relative to the total weight of the product as a whole. It will be understood by those skilled in the art that the sum of weight percentages of all components of a product will total 100 wt%. However, where not all components are listed (e.g., where a product is said to “comprise” one or more particular components), the weight percentage balance may optionally be made up to 100 wt% by unspecified ingredients.
Polymers [0036] In a first aspect, the invention provides a polymer comprising: ethylene repeating units, A; and phosphonated ethylene repeating units, B. [0037] Through extensive investigations, the inventors have devised new polymers with enhanced flame retardancy and thermal stability, making them ideally suited for use in a number of flame retardant applications. In particular, the presence of phosphonated ethylene repeating units, B, has the effect of markedly improving the thermal degradation properties of the polymer. Advantageously, the polymers are devoid of the drawbacks associated with halogenated flame retardant polyolefins (e.g., high persistence and toxicity), and can be straightforwardly prepared using a two-step synthetic process. [0038] The term “ethylene repeating unit” refers to an ethylenic (i.e., -CH2-CH2-) unit of the polymer. Thus, each ethylene repeating unit, A, has the structural formula: .
[0039] The polymer may comprise 86-99 mol% of ethylene repeating units, A. The quantity of ethylene repeating units, A in the polymer can be calculated by integration of peaks recorded by 1H NMR in C2D2Cl4 at 130 °C. Suitably, the polymer comprises 90-98.25 mol% of ethylene repeating units, A. More suitably, the polymer comprises 92-98 mol% of ethylene repeating units, A. Even more suitably, the polymer comprises 93-97.75 mol% of ethylene repeating units, A. In embodiments, the polymer comprises 93.5-96 mol% of ethylene repeating units, A. [0040] The phrase “phosphonated ethylene repeating unit” refers to an ethylenic (e.g., -CH2- CH2-) unit of the polymer substituted with a phosphonate containing group. Suitably, each phosphonated ethylene repeating unit, B, comprises one phosphonate containing group. It will be understood that each phosphonate containing group may independently be a phosphonate ester (e.g., -C-P=O(OR)2, where R is as defined herein) or phosphonic acid (e.g., -C-P=O(OH)2). [0041] The polymer may comprise 1-14 mol% of phosphonated ethylene repeating units, B. The quantity of phosphonated ethylene repeating units, B in the polymer can be calculated by integration of peaks recorded by 1H NMR in C2D2Cl4 at 130 °C. Suitably, the polymer comprises 1.75-10 mol% of phosphonated ethylene repeating units, B. More suitably, the polymer comprises 2-8 mol% of phosphonated ethylene repeating units, B. Even more suitably, the polymer comprises 2.25-7 mol% of phosphonated ethylene repeating units, B. In embodiments, the polymer comprises 4-6.5 mol% of phosphonated ethylene repeating units, B.
[0042] In embodiments, the polymer comprises: (i) 86-99 mol% of ethylene repeating units, A, and (ii) 1-14 mol% of phosphonated ethylene repeating units, B. [0043] In embodiments, the polymer comprises: (i) 90-98.25 mol% of ethylene repeating units, A, and (ii) 1.75-10 mol% of phosphonated ethylene repeating units, B. [0044] In embodiments, the polymer comprises: (i) 92-98 mol% of ethylene repeating units, A, and (ii) 2-8 mol% of phosphonated ethylene repeating units, B. [0045] In embodiments, the polymer comprises: (i) 93-97.75 mol% of ethylene repeating units, A, and (ii) 2.25-7 mol% of phosphonated ethylene repeating units, B. [0046] In embodiments, the polymer comprises: (i) 93.5-96 mol% of ethylene repeating units, A, and (ii) 4-6.5 mol% of phosphonated ethylene repeating units, B. [0047] Each phosphonated ethylene repeating unit, B, may independently have the structural formula B1:
wherein Y is linking group connecting C1 to X; and X is a phosphonate containing group. [0048] Y may link C1 to X by 5-18 bridging atoms. The term “bridging atoms” refers to the fewest number of atoms directly connecting C1 to X. For example, when Y links C1 to X by 5 bridging atoms, this could mean that Y is a pentylene group (i.e., 5 carbons atoms directly connecting C1 to X). In this case, all other atoms not directly connecting C1 to X (e.g., H atoms) are not bridging
atoms. Suitably, Y links C1 to X by 5-12 bridging atoms. More suitably, Y links C1 to X by 5-9 bridging atoms. In embodiments, Y links C1 to X by 5 bridging atoms. In embodiments, Y links C1 to X by 9 bridging atoms. [0049] Y may be an alkylene, an alkenylene or an alkynylene group linking C1 to X. Suitably, Y is a (5-18C)alkylene group, a (5-18C)alkenylene group, or a (5-18C)alkynylene group linking C1 to X. More suitably, Y is a (5-12C)alkylene group, a (5-12C)alkenylene group, or a (5- 12C)alkynylene group linking C1 to X. Yet more suitably, Y is a (5-9C)alkylene group linking C1 to X. [0050] In embodiments, Y is selected from:
wherein denotes the point of attachment to C1; and denotes the point of attachment to X. [0051] Accordingly, each phosphonated ethylene repeating unit, B, may independently have the structural formula:
, wherein X is as defined herein.
[0052] X may have the structural formula B1a:
wherein: denotes the point of attachment to Y; and each R is independently selected from (1-6C)alkyl and aryl, wherein each R is optionally substituted. [0053] Suitably, each R is independently selected from (1-6C)alkyl and phenyl, wherein each R is optionally substituted. More suitably, each R is independently selected from methyl, propyl, butyl, pentyl, hexyl and phenyl, wherein each R is optionally substituted. Yet more suitably, each R is independently selected from iso-propyl and phenyl, wherein each R is optionally substituted. [0054] In embodiments wherein R is (1-6C)alkyl (or a subset thereof), each R may be substituted with one or more groups R’ independently selected from aryl, heteroaryl, carbocyclyl, heterocyclyl, halo, hydroxy, cyano and nitro. Suitably, each R’ is independently selected from phenyl, heteroaryl, halo and hydroxy. [0055] In embodiments wherein R is aryl (or a subset thereof), each R may be substituted with one or more groups R’’ independently selected from (1-6C)alkyl, (1-6C)haloalkyl, (1-6C)alkoxy,
(1-6C)alkenyl, (1-6C)alkynyl, aryl, heteroaryl, carbocyclyl, heterocyclyl, halo, hydroxy, cyano and nitro. Suitably, each R’’ is independently selected from (1-3C)alkyl, (1-3C)haloalkyl, (1-3C)alkoxy, phenyl, heteroaryl, halo and hydroxy. [0056] Each R may be unsubstituted. In embodiments, each R is independently selected from methyl, propyl, butyl, pentyl, hexyl and phenyl. In embodiments, each R is independently selected from iso-propyl and phenyl. Each R may be identical. In embodiments, each R is iso-propyl. In embodiments, each R is phenyl. [0057] Suitably, each phosphonated ethylene repeating unit, B, is independently selected from:
[0058] More suitably, each phosphonated ethylene repeating unit, B, is independently selected from:
[0059] The polymer may have a molecular weight (Mw) of 10-100 kg mol-1. Suitably, the polymer has a molecular weight (Mw) of 12-75 kg mol-1. More suitably, the polymer has a molecular weight (Mw) of 15-65 kg mol-1. [0060] The polymer may have a melting temperature (Tm) of 115-130 ⁰C. The melting temperature (Tm) of the polymer can be determined by differential scanning calorimetry (DSC) within a temperature range of 30–180 °C at a rate of 20 °C min–1. Suitably, the polymer has a melting temperature (Tm) of 116-127 ⁰C. More suitably, the polymer has a melting temperature (Tm) of 117-124 ⁰C. [0061] Thermal studies of the polymer were conducted using thermogravimetric analysis. T10%, T50%, and Tmax were determined under a nitrogen atmosphere or a synthetic air (O2:N2 = 20:80) atmosphere. Weight change is recorded from 50 to 800 °C at a rate of 20 °C min-1. T10%, T50%, and Tmax refer to the temperatures at which the mass of the polymer has decreased by 10%, 50% and the temperature at which weight loss rate is greatest, respectively. [0062] The polymer may have a temperature of 10% weight loss (T10%) in nitrogen of 300-500 ⁰C. Suitably, the polymer has a temperature of 10% weight loss (T10%) in nitrogen of 305-475 ⁰C. [0063] The polymer may have a temperature of 10% weight loss (T10%) in air of 250-500 ⁰C. Suitably, the polymer has a temperature of 10% weight loss (T10%) in air of 270-460 ⁰C. [0064] In embodiments, the polymer has a melting temperature (Tm) of 115-130 ⁰C and a temperature of 10% weight loss (T10%) in nitrogen of 300-500 ⁰C. In embodiments, the polymer has a melting temperature (Tm) of 115-130 ⁰C and a temperature of 10% weight loss (T10%) in air of 250-500 ⁰C. [0065] The polymer may have a temperature of 50% weight loss (T50%) in nitrogen of 500-520 ⁰C. Suitably, the polymer has a temperature of 50% weight loss (T50%) in nitrogen of 503-510 ⁰C. [0066] The polymer may have a temperature of 50% weight loss (T50%) in air of 450-550 ⁰C. Suitably, the polymer has a temperature of 50% weight loss (T50%) in air of 480-510 ⁰C. [0067] The polymer may have a temperature at maximum weight loss rate (Tmax) in nitrogen of 500-515 ⁰C. Suitably, the polymer has a temperature at maximum weight loss rate (Tmax) in nitrogen of 505-510 ⁰C. [0068] The polymer may have a temperature at maximum weight loss rate (Tmax) in air of 480- 510 ⁰C. Suitably, the polymer has a temperature at maximum weight loss rate (Tmax) in air of 483- 507 ⁰C.
[0069] In embodiments, the polymer has a melting temperature (Tm) of 115-130 ⁰C, a temperature at maximum weight loss rate (Tmax) in nitrogen of 500-515 ⁰C and a temperature at maximum weight loss rate (Tmax) in air of 480-510 ⁰C. [0070] In embodiments, the polymer has: a temperature of 10% weight loss (T10%) in nitrogen of 300-500 ⁰C; a temperature of 50% weight loss (T50%) in nitrogen of 500-520 ⁰C; and a temperature at maximum weight loss rate (Tmax) in nitrogen of 500-515 ⁰C. [0071] In embodiments, the polymer has: a temperature of 10% weight loss (T10%) in nitrogen of 305-475 ⁰C; a temperature of 50% weight loss (T50%) in nitrogen of 503-510 ⁰C; and a temperature at maximum weight loss rate (Tmax) in nitrogen of 505-510 ⁰C. [0072] In embodiments, the polymer has: a temperature of 10% weight loss (T10%) in air of 250-500 ⁰C; a temperature of 50% weight loss (T50%) in air of 450-550 ⁰C; and a temperature at maximum weight loss rate (Tmax) in air of 480-510 ⁰C. [0073] In embodiments, the polymer has: a temperature of 10% weight loss (T10%) in air of 270-460 ⁰C; a temperature of 50% weight loss (T50%) in air of 480-510 ⁰C; and a temperature at maximum weight loss rate (Tmax) in air of 483-507 ⁰C. [0074] Flammability studies were also carried out to determine heat release capacity (Tmax/heating rate), peak heat release rate (max release rate of heat during combustion), total heat release (total amount of heat evolved during combustion) and the temperature at peak heat release rate (temperature of greatest heat release rate during combustion). The flammability studies were investigated using microscale combustion calorimetry following the procedure specified in ASTM D 7309-19 standard test method for “Determining Flammability Characteristics of Plastics and Other Solid Materials Using Microscale Combustion Calorimetry”. [0075] The polymer may have a heat release capacity (HRC) of 200-300 J g-1 K. Suitably, the polymer has a heat release capacity (HRC) of 215-275 J g-1 K. [0076] The polymer may have a peak heat release rate (pHRR) of 150-250 W g-1. Suitably, the polymer has a peak heat release rate (pHRR) of 180-230 W g-1.
[0077] The polymer may have a total heat release (THR) of 5-15 kJ g-1. Suitably, the polymer has a total heat release (THR) of 7-12 kJ g-1. [0078] The polymer may have a temperature at peak heat release rate of (TpHRR) of 485-500 ⁰C. Suitably, the polymer has a temperature at peak heat release rate of (TpHRR) of 488-497 ⁰C. [0079] In embodiments, the polymer has: a heat release capacity (HRC) of 200-300 J g-1 K; a peak heat release rate (pHRR) of 150-250 W g-1; a total heat release (THR) of 5-15 kJ g-1; and a temperature at peak heat release rate of (TpHRR) of 485-500 ⁰C. [0080] In embodiments, the polymer has: a heat release capacity (HRC) of 215-275 J g-1 K; a peak heat release rate (pHRR) of 180-230 W g-1; a total heat release (THR) of 7-12 kJ g-1; and a temperature at peak heat release rate of (TpHRR) of 488-497 ⁰C. [0081] The inventors have surprisingly found that polymers of the invention comprising phosphonated ethylene repeating units, B, exhibit much higher thermal stability when compared with analogous unphosphonated polyolefins. Without wishing to be bound by theory, it is thought that the phosphonate group decomposes before the remainder of the polymer to form a carbonaceous char layer. The carbonaceous char layer shields the polymer from oxygen and prevents the formation of flammable gases. Suitably, the polymer is such that, when heated to 700 ⁰C in nitrogen, a carbonaceous char layer is formed accounting for 0.5-2.0 wt% of the resulting material. More suitably, the polymer is such that, when heated to 700 ⁰C in nitrogen, a carbonaceous char layer is formed accounting for 0.8-1.7 wt% of the resulting material. Suitably, the polymer is such that, when heated to 700 ⁰C in air, a carbonaceous char layer is formed accounting for 2-5 wt% of the resulting material. More suitably, the polymer is such that, when heated to 700 ⁰C in air, a carbonaceous char layer is formed accounting for 2.5-4.5 wt% of the resulting material. [0082] The distribution of repeating units A and B within the polymer may be random (e.g., ethylene repeating units, A, and phosphonated ethylene repeating units, B, are present in any order in the polymer). The phosphonated ethylene repeating units, B, may be randomly distributed along the length of the polymer. It may be that the polymer end groups are ethylene repeating units, A. Suitably, the phosphonated ethylene repeating units, B, are randomly
distributed along the length of the polymer and the polymer end groups are ethylene repeating units, A. [0083] The polymer may have a -C-C- backbone (i.e., the polymer backbone consists of / consists essentially of carbon atoms). In embodiments of the invention defined herein, the polymer may consist of / consist essentially of ethylene repeating units, A, and phosphonated ethylene repeating units, B. [0084] The polymer may also be linear (e.g., units of the polymer are arranged in a straight line) or branched (e.g., linear polymer chain substituted with one or more polymer chains along its length). Polymer blends [0085] In an aspect, the invention provides a polymer blend comprising: a polymer of the first aspect of the invention; and polyethylene. [0086] Through extensive investigations, the inventors have found that compounding the polymer of the first aspect of the invention with polyethylene results in a significant increase in thermal stability, as shown by higher T10%, T50% and Tmax values, when compared to virgin polyethylene. [0087] The polymer blend may comprise 0.1-30 wt% of the polymer. The amount of polymer and polyethylene in the polymer blend can be determined by chromatographic methods, such as gel permeation chromatography (GPC), wherein the polymer and polyethylene can be distinguished by size and/or polarity. Suitably, the polymer blend comprises 1-20 wt% of the polymer. More suitably, the polymer blend comprises 1-10 wt% of the polymer. [0088] The polyethylene in the polymer blend may be selected from high density polyethylene (HDPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE). Suitably, the polyethylene is LDPE. [0089] The polymer blend may comprise 70-99.9 wt% polyethylene. Suitably, the polymer blend comprises 80-99 wt% polyethylene. More suitably, the polymer blend comprises 90-99 wt% polyethylene. In embodiments, the polymer blend comprises 80-99 wt% HDPE, LDPE or LLDPE. In embodiments, the polymer blend comprises 90-99 wt% LDPE. [0090] The polymer blend may comprise 0.1-30 wt% of the polymer and 70-99.9 wt% polyethylene. Suitably, the polymer blend comprises 1-20 wt% of the polymer and 80-99 wt%
polyethylene. Suitably, the polymer blend comprises 1-10 wt% of the polymer and 90-99 wt% polyethylene. The polyethylene may be HDPE, LDPE or LLDPE. [0091] In embodiments, the polymer blend comprises: a) 10 wt% of the polymer and 90 wt% polyethylene; b) 5 wt% of the polymer and 95 wt% polyethylene; or c) 1 wt% of the polymer and 99 wt% polyethylene. [0092] In embodiments, the polymer blend comprises: a) 10 wt% of the polymer and 90 wt% HDPE, LDPE or LLDPE; b) 5 wt% of the polymer and 95 wt% HDPE, LDPE or LLDPE; or c) 1 wt% of the polymer and 99 wt% HDPE, LDPE or LLDPE. [0093] In embodiments, the polymer blend comprises: a) 10 wt% of the polymer and 90 wt% LDPE; b) 5 wt% of the polymer and 95 wt% LDPE; or c) 1 wt% of the polymer and 99 wt% LDPE. [0094] The melting temperature (Tm), temperature of 10% weight loss (T10%), temperature of 50% weight loss (T50%) and temperature at maximum weight loss rate (Tmax) of the polymer blend can be determined according to the protocols defined hereinbefore. [0095] The polymer blend may have a melting temperature (Tm) of 109-112 ⁰C. [0096] The polymer blend may have a temperature of 10% weight loss (T10%) in air of 340-420 ⁰C. Suitably, the polymer blend has a temperature of 10% weight loss (T10%) in air of 355-405 ⁰C. [0097] In embodiments, the polymer blend has a melting temperature (Tm) of 109-112 ⁰C and a temperature of 10% weight loss (T10%) in air of 340-420 ⁰C. [0098] The polymer blend may have a temperature of 50% weight loss (T50%) in air of 375-500 ⁰C. Suitably, the polymer blend has a temperature of 50% weight loss (T50%) in air of 400-470 ⁰C. [0099] In embodiments, the polymer blend has a temperature of 10% weight loss (T10%) in air of 340-420 ⁰C and a temperature of 50% weight loss (T50%) in air of 375-500 ⁰C. In embodiments, the polymer blend has a temperature of 10% weight loss (T10%) in air of 355-405 ⁰C and a temperature of 50% weight loss (T50%) in air of 400-470 ⁰C. [00100] In embodiments, the polymer blend has a melting temperature (Tm) of 109-112 ⁰C and a temperature of 50% weight loss (T50%) in air of 375-500 ⁰C.
[00101] In embodiments, the polymer blend has a melting temperature (Tm) of 109-112 ⁰C, a temperature of 10% weight loss (T10%) in air of 340-420 ⁰C, and a temperature of 50% weight loss (T50%) in air of 375-500 ⁰C. [00102] The polymer blend may have a temperature at maximum weight loss rate (Tmax) in air of 390-470 ⁰C. [00103] In embodiments, the polymer blend has a temperature of 10% weight loss (T10%) in air of 340-420 ⁰C, a temperature of 50% weight loss (T50%) in air of 375-500 ⁰C and a temperature at maximum weight loss rate (Tmax) in air of 390-470 ⁰C. [00104] The polymer blend may further comprise one or more flame retardant additives. Suitably, the flame retardant is selected from a layered double hydroxide (LDH), aluminium trihydroxide (i.e., Al(OH)3) (ATH), Mg(OH)2 (MDH), Sb2O3, resorcinol bis(diphenyl phosphate) (RDP), a triaryl phosphate, a metal phosphinate, 9,10-Dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide (DOPO), trischloropropyl phosphate (TCCP), ammonium polyphosphate (APP) and red phosphorus. More suitably, the flame retardant is selected from a LDH, ATH and MDH. Yet more suitably, the flame retardant is ATH. [00105] In an aspect, the invention provides a polymer blend comprising: phosphonated polyethylene; a polyolefin; and a hydroxylated flame retardant additive. [00106] The inventors have surprisingly found that the components present within the blends interact synergistically to improve the blend’s thermal and mechanical properties. Insofar as thermal properties are concerned, the inventors have determined that, during heating, the phosphonate containing group on the phosphonated polyethylene forms polyphosphoric acid, whilst the hydroxylated flame retardant additive simultaneously releases water to form an oxide. The liberated water is able to react with the polyphosphoric acid to form a char layer having increased density. The char layer inhibits the transmission of oxygen and heat, thereby preventing the formation of flammable gases. Insofar as mechanical properties are concerned, the inventors have determined that the phosphonated polyethylene is able to serve as an amphiphilic compatibilizer for the hydrophilic hydroxylated flame retardant additive and the hydrophobic polyolefin (e.g., polyethylene, resulting in a more uniform polymer blend having improved mechanical integrity.
[00107] The phrase “phosphonated polyethylene” refers to a polymer comprising ethylene repeating units and a plurality of phosphonate-containing groups. It will be understood that each phosphonate containing group may independently be a phosphonate ester (e.g., -C-P=O(OR)2, where R is as defined herein) or phosphonic acid (e.g., -C-P=O(OH)2). The phosphonate- containing groups may be provided as substituents on some or all of the ethylene repeating units. [00108] The phosphonated polyethylene may comprise 0.5-20 mol% mol% of phosphonate groups. The quantity of phosphonate groups present within the polymer may be determined by integration of peaks recorded by 1H NMR in C2D2Cl4 at 130 °C. Suitably, the phosphonated polyethylene comprises 1.75-14 mol% of phosphonate groups. More suitably, the phosphonated polyethylene comprises 2-8 mol% of phosphonate groups. Yet more suitably, the phosphonate polyethylene comprises 2.25-7 mol% of phosphonate groups. Most suitably, the phosphonated polyethylene comprises 4-6.5 mol% mol% of phosphonate groups. [00109] The phosphonated polyethylene may comprise 0.5-20 mol% ethylene repeating units (i.e., -CH2-CH2-) substituted with a phosphonate containing group. The quantity of ethylene repeating units substituted with a phosphonate containing group and ethylene repeating units in the phosphonated polyethylene may be determined by integration of peaks recorded by 1H NMR in C2D2Cl4 at 130 °C. Suitably, the phosphonated polyethylene comprises 1.75-14 mol% ethylene repeating units substituted with a phosphonate containing group. More suitably, the phosphonated polyethylene comprises 2-8 mol% ethylene repeating units substituted with a phosphonate containing group. Even more suitably, the phosphonated polyethylene comprises 2.25-7 mol% ethylene repeating units substituted with a phosphonate containing group. In embodiments, the phosphonated polyethylene comprises 4-6.5 mol% ethylene repeating units substituted with a phosphonate containing group. The phosphonated polyethylene may also comprise 80-99.5 mol% ethylene repeating units (i.e., -CH2-CH2-). Suitably, the phosphonated polyethylene comprises 86-98.25 mol% ethylene repeating units. More suitably, the phosphonated polyethylene comprises 92-98 mol% of ethylene repeating units. Even more suitably, the phosphonated polyethylene comprises 93-97.75 mol% ethylene repeating units. In embodiments, the phosphonated polyethylene comprises 93.5-96 mol% ethylene repeating units. [00110] In embodiments, the phosphonated polyethylene consists of / consists essentially of ethylene repeating units substituted with a phosphonate containing group and ethylene repeating units. [00111] The phosphonated polyethylene may have a random distribution of repeating units. The phosphonated polyethylene may comprise phosphonate containing groups randomly distributed along the length of the polymer. More suitably, the phosphonated polyethylene comprises
ethylene repeating units substituted with a phosphonate containing group randomly distributed along the length of the polymer. [00112] In embodiments, the phosphonated polyethylene is a polymer as defined in the first aspect of the invention. [00113] The polymer blend may comprise 5-15 wt% of the phosphonated polyethylene. Suitably, the polymer blend comprises 8-12 wt% of the phosphonated polyethylene. More suitably, the polymer blend comprises 10 wt% of the phosphonated polyethylene. [00114] The polyolefin in the polymer blend may be selected from polyethylene, polypropylene, polybutylene and a copolymer of two or more thereof. Suitably, the polyolefin is polyethylene. More suitably, the polyethylene is HDPE, LDPE or LLDPE. Most suitably, the polyethylene is LDPE. [00115] The polymer blend may comprise 70-90 wt% of the polyolefin (e.g., polyethylene). Suitably, the polymer blend comprises 76-84 wt% of the polyolefin. Yet more suitably, the polymer blend comprises 80 wt% of the polyolefin. Even more suitably, the polymer blend comprises 80 wt% polyethylene. In embodiments, the polymer blend comprises 70-90 wt% HDPE, LDPE or LLDPE. In embodiments, the polymer blend comprises 76-84 wt% LDPE. In embodiments, the polymer blend comprises 80 wt% LDPE. [00116] The hydroxylated flame retardant additive may be selected from a LDH, ATH and MDH. Suitably, the hydroxylated flame retardant additive is ATH. [00117] The polymer blend may comprise 5-15 wt% of the hydroxylated flame retardant additive. Suitably, the polymer blend comprises 8-12 wt% of the hydroxylated flame retardant additive. More suitably, the polymer blend comprises 10 wt% of the hydroxylated flame retardant additive. [00118] In embodiments, the polymer blend comprises: a) 70-90 wt% polyethylene, 5-15 wt% of the phosphonated polyethylene, and 5-15 wt% of the hydroxylated flame retardant additive; b) 76-84 wt% polyethylene, 8-12 wt% of the phosphonated polyethylene, and 8-12 wt% of the hydroxylated flame retardant additive; or c) 80 wt% polyethylene, 10 wt% of the phosphonated polyethylene, and 10 wt% of the hydroxylated flame retardant additive. [00119] In embodiments, the polymer blend comprises: a) 70-90 wt% HDPE, LDPE or LLDPE, 5-15 wt% of the phosphonated polyethylene, and 5-15 wt% of the hydroxylated flame retardant additive;
b) 76-84 wt% HDPE, LDPE or LLDPE, 8-12 wt% of the phosphonated polyethylene and 8-12 wt% of the hydroxylated flame retardant additive; or c) 80 wt% LDPE, 10 wt% of the phosphonated polyethylene, and 10 wt% of the hydroxylated flame retardant additive. [00120] The melting temperature (Tm), temperature of 10% weight loss (T10%), temperature of 50% weight loss (T50%) and temperature at maximum weight loss rate (Tmax) of the polymer blend can be determined according to the protocols defined hereinbefore. [00121] The polymer blend may have a melting temperature (Tm) of 110-115 ⁰C. Suitably, the polymer blend has a melting temperature (Tm) of 111-113 ⁰C. [00122] The polymer blend may have a temperature of 10% weight loss (T10%) in air of 360-380 ⁰C. Suitably, the polymer blend has a temperature of 10% weight loss (T10%) in air of 362-372 ⁰C. [00123] In embodiments, the polymer blend has a melting temperature (Tm) of 110-115 ⁰C and a temperature of 10% weight loss (T10%) in air of 360-380 ⁰C. [00124] The polymer blend may have a temperature of 50% weight loss (T50%) in air of 470-480 ⁰C. Suitably, the polymer blend has a temperature of 50% weight loss (T50%) in air of 472-475 ⁰C. [00125] In embodiments, the polymer blend has a melting temperature (Tm) of 110-115 ⁰C and a temperature of 50% weight loss (T50%) in air of 470-480 ⁰C. [00126] The polymer blend may have a temperature at maximum weight loss rate (Tmax) in air of 460-470 ⁰C. Suitably, the polymer blend has a temperature at maximum weight loss rate (Tmax) in air of 475-478 ⁰C. [00127] In embodiments, the polymer blend has a melting temperature (Tm) of 110-115 ⁰C and a temperature at maximum weight loss rate (Tmax) in air of 460-470 ⁰C. [00128] In embodiments, the polymer blend has a temperature of 10% weight loss (T10%) in air of 360-380 ⁰C, a temperature of 50% weight loss (T50%) in air of 470-480 ⁰C and a temperature at maximum weight loss rate (Tmax) in air of 460-470 ⁰C. In embodiments, the polymer blend has a temperature of 10% weight loss (T10%) in air of 362-372 ⁰C, a temperature of 50% weight loss (T50%) in air of 472-475 ⁰C and a temperature at maximum weight loss rate (Tmax) in air of 475- 478 ⁰C. Polymer and polymer blend applications [00129] In an aspect, the invention provides a use of a polymer as defined herein or a polymer blend as defined herein as a flame retardant.
Process for the preparation of a polymer and a polymer blend [00130] In an aspect of the invention there is a provided a process for the preparation of a polymer, the process comprising the steps of: a) providing a precursor polymer comprising: (i) ethylene repeating units, A; and (ii) LG-functionalised ethylene repeating units, C, wherein LG is a leaving group; and b) phosphonating the precursor polymer provided in step a), such that the LG-functionalised repeating units, C, are converted into phosphonated ethylene repeating units, B. [00131] In another aspect of the invention there is a provided a process for the preparation of a polymer blend, the process comprising the steps of: a) providing a precursor polymer comprising: (i) ethylene repeating units, A; and (ii) LG-functionalised ethylene repeating units, C, wherein LG is a leaving group; b) phosphonating the precursor polymer provided in step a), such that the LG-functionalised repeating units, C, are converted into phosphonated ethylene repeating units, B; and c) mixing the polymer resulting from step b) with one or more polyolefins. [00132] In the precursor polymer provided in step a), ethylene repeating units, A, may have any of the definitions discussed herein in relation to the first aspect. Furthermore, the phosphonated ethylene repeating units, B, formed in step b), may have any of the definitions discussed herein in relation to the first aspect. [00133] Each LG-functionalised ethylene repeating unit, C, may independently have the structural formula C1:
wherein Y is linking group connecting C1 to LG; and
LG is a leaving group. [00134] Suitably, Y links C1 to LG by 5-18 bridging atoms. The term “bridging atoms” as defined herein will be understood to mean the fewest number of atoms directly connecting C1 to LG. More suitably, Y links C1 to LG by 5-12 bridging atoms. Yet more suitably, Y links C1 to LG by 5-9 bridging atoms. In embodiments, Y links C1 to LG by 5 bridging atoms. In embodiments, Y links C1 to LG by 9 bridging atoms. [00135] Y may be an alkylene, an alkenylene or an alkynylene group linking C1 to LG. Suitably, Y is a (5-18C)alkylene group, a (5-18C)alkenylene group, or a (5-18C)alkynylene group linking C1 to LG. More suitably Y is a (5-12C)alkylene group, a (5-12C)alkenylene group, or a (5- 12C)alkynylene group linking C1 to LG. Yet more suitably, Y is a (5-9C)alkylene group linking C1 to LG. [00136] In embodiments, Y is selected from:
wherein denotes the point of attachment to C1; and denotes the point of attachment to LG. [00137] Accordingly, each LG-functionalised ethylene repeating unit, C, may independently have the structural formula:
wherein LG is as defined herein.
[00138] LG may be a leaving group which can be replaced with a phosphonate group (i.e., converted to a phosphonate group following reaction with a phosphorus-containing reagent). Suitably LG is a halo group. More suitably, LG is bromo or iodo. In embodiments, LG is bromo. Accordingly, each LG-functionalised ethylene repeating unit, C, may independently be a halogenated ethylene repeating unit. Suitably, each LG-functionalised ethylene repeating unit, C, is a brominated ethylene repeating unit. [00139] The precursor polymer provided in step a) may comprise 86-99 mol% of ethylene repeating units, A. Suitably, the precursor polymer comprises 90-98.25 mol% of ethylene repeating units, A. More suitably, the precursor polymer comprises 92-98 mol% of ethylene repeating units, A. Even more suitably, the precursor polymer comprises 93-97.75 mol% of ethylene repeating units, A. In embodiments, the precursor polymer comprises 93.5-96 mol% of ethylene repeating units, A. [00140] The precursor polymer provided in step a) may comprise 1-14 mol% of LG- functionalised ethylene repeating units, C. Suitably, the precursor polymer comprises 1.75-10 mol% of LG-functionalised ethylene repeating units, C. More suitably, the precursor polymer comprises 2-8 mol% of LG-functionalised ethylene repeating units, C. Even more suitably, the precursor polymer comprises 2.25-7 mol% of LG-functionalised ethylene repeating units, C. In embodiments, the precursor polymer comprises 4-6.5 mol% of LG-functionalised ethylene repeating units, C. In such embodiments, LG is suitably bromo or iodo, more suitably bromo. [00141] The distribution of repeating units A and C within the precursor polymer may be random (e.g., ethylene repeating units, A, and LG-functionalised ethylene repeating units, C, are present
in any order in the precursor polymer). The LG-functionalised ethylene repeating units, C, may be randomly distributed along the length of the polymer. It may be that the polymer end groups are ethylene repeating units, A. Suitably, the LG-functionalised ethylene repeating units, C, are randomly distributed along the length of the polymer and the polymer end groups are ethylene repeating units, A. [00142] In embodiments, the precursor polymer may consist of / consist essentially of ethylene repeating units, A, and LG-functionalised ethylene repeating units, C. [00143] The precursor polymer may be linear or branched. [00144] The precursor polymer may have a molecular weight (Mw) of 20-70 kg mol-1. Suitably, the polymer has a molecular weight (Mw) of 25-65 kg mol-1. [00145] The precursor polymer may have a melting temperature (Tm) of 115-130 ⁰C. The melting temperature (Tm) of the precursor polymer can be determined according to the protocol defined hereinbefore. Suitably, the precursor polymer has a melting temperature (Tm) of 116-127 ⁰C. [00146] The precursor polymer may be prepared by polymerising ethylene monomers, A’, and LG-functionalised ethylene monomers, C’. [00147] Suitably, each ethylene monomer, A’, has the structural formula:
[00148] Each LG-functionalised ethylene monomer, C’, may independently have the structural formula C’1:
wherein Y and LG are as defined herein. [00149] Suitably, each LG-functionalised ethylene monomer, C’ independently has the structural formula:
wherein LG is as defined herein. [00150] Suitably, each LG-functionalised ethylene monomer, C’, is a bromoalkene. More suitably, each LG-functionalised ethylene monomer, C’, is an ω-bromo-α-alkene. In embodiments, each LG-functionalised ethylene monomer, C’ is 11-bromo-1-undecene or 7- bromo-1-heptene. Accordingly, the precursor polymer provided in step a) may be polyethylene- co-11-bromo-1-undecene or polyethylene-co-7-bromo-1-heptene. [00151] In embodiments wherein the precursor polymer provided in step a) is prepared by polymerising ethylene monomers, A’, and LG-functionalised ethylene monomers, C’, said polymerisation may be conducted in the presence of an olefin polymerisation catalyst. Suitably, the olefin polymerisation catalyst is a metallocene, ansa-metallocene, half-metallocene or ansa- half-metallocene, examples of which will be readily familiar to one of skill in the art. [00152] The olefin polymerisation catalyst may have a structure according to formula (D1): (L1)(L2)M1(Y1)(Y2) (D1) wherein M1 is zirconium, hafnium or titanium; L1 and L2 are each independently a ligand comprising a cyclopentadienyl moiety, said cyclopentadienyl moiety being η5 bound to M1, wherein L1 and L2 are optionally linked to one another; and Y1 and Y2 are each independently a ligand selected from hydride, halo and (1-3C)alkyl. [00153] In embodiments, L1 and L2 are each independently an optionally-substituted cyclopentadienyl group that is η5 bound to M1, an optionally-substituted indenyl group that is η5 bound to M1, or an optionally-substituted fluorenyl group that is η5 bound to M1, wherein L1 and L2 are optionally linked to one another. More suitably, L1 and L2 are each independently an optionally-substituted cyclopentadienyl group that is η5 bound to M1 or an optionally-substituted indenyl group that is η5 bound to M1, wherein L1 and L2 are optionally linked to one another. In embodiments, L1 and L2 are each independently an optionally-substituted indenyl group that is η5 bound to M1, wherein L1 and L2 are optionally linked to one another.
[00154] In embodiments, L1 and L2 are optionally linked to one another by an alkylene or a silylene linking group. In embodiments, L1 and L2 are optionally linked to one another by an ethylene group. [00155] In embodiments, M1 is zirconium. [00156] In embodiments, Y1 and Y2 are each independently selected from hydride, chloro and methyl. In embodiments, Y1 and Y2 are each chloro. [00157] It will be understood that the optional substituents present in L1 and L2 may be selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl (e.g., phenyl), aryl(1-2C)alkyl (e.g., benzyl), aryloxy (e.g., phenoxy) and heteroaryl. Particularly suitable optional substituents are selected from (1-4C)alkyl, (1-4C)alkoxy and phenyl. [00158] In particular embodiments, the olefin polymerisation catalyst is a bis-indenyl zirconocene compound. [00159] Most suitably, the olefin polymerisation catalyst is:
[00160] The olefin polymerisation catalyst may be used together with one or more suitable activators. Suitable activators are well known in the art and include organo aluminium compounds (e.g., alkyl aluminium compounds). Particularly suitable activators include aluminoxanes (e.g., methylaluminoxane (MAO)), triisobutylaluminium (TIBA), diethylaluminium (DEAC) and triethylaluminium (TEA). In embodiments, the olefin polymerisation catalyst is used together with MAO, TIBA, DEAC and/or TEA. [00161] In step b), the precursor polymer may be phosphonated by contacting the precursor polymer with a phosphonating reagent, B’. Suitably, phosphonating reagent, B’, has the structural formula B’1.
wherein R and any sub-groups associated therewith may have any of those definitions discussed herein in relation to repeating units, B of the first aspect. [00162] In step b), the precursor polymer provided in step a) may be phosphonated such that 50% of the LG-functionalised repeating units, C, are converted into phosphonated ethylene repeating units, B. Suitably, the precursor polymer provided in step a) is phosphonated such that 60% of the LG-functionalised repeating units, C, are converted into phosphonated ethylene repeating units, B. More suitably, the precursor polymer provided in step a) is phosphonated such that 70% of the LG-functionalised repeating units, C, are converted into phosphonated ethylene repeating units, B. Yet more suitably, the precursor polymer provided in step a) is phosphonated such that 80% of the LG-functionalised repeating units, C, are converted into phosphonated ethylene repeating units, B. Even more suitably, the precursor polymer provided in step a) is phosphonated such that 90% of the LG-functionalised repeating units, C, are converted into phosphonated ethylene repeating units, B. In embodiments, the precursor polymer provided in step a) is phosphonated such that greater than 95% of the LG-functionalised repeating units, C, are converted into phosphonated ethylene repeating units, B. In embodiments, the precursor polymer provided in step a) is phosphonated such that all (or substantially all) of the LG- functionalised repeating units, C, are converted into phosphonated ethylene repeating units, B. [00163] As discussed herein, an aspect of the invention provides a process for the preparation of a polymer blend, the process comprising the steps of: a) providing a precursor polymer comprising: (i) ethylene repeating units, A; and (ii) LG-functionalised ethylene repeating units, C, wherein LG is a leaving group; b) phosphonating the precursor polymer provided in step a), such that the LG-functionalised repeating units, C, are converted into phosphonated ethylene repeating units, B; and c) mixing the polymer resulting from step b) with one or more polyolefins. [00164] Suitably, steps a) and b) are as defined herein. [00165] Polymer blends are known in the art and refer to a mixture in which two or more polymers are combined to create a new material. In embodiments, step c) may comprise mixing the polymer resulting from step b) with polyethylene. Suitably, the polyethylene is selected from HDPE, LDPE and LLDPE. More suitably, the polyethylene is LDPE. [00166] Step c) may additionally comprise mixing the polymer resulting from step b) with a flame retardant additive. Suitably, the flame retardant additive is selected from a LDH, ATH, MDH,
Sb2O3, RDP, a triaryl phosphate, a metal phosphinate, DOPO, TCCP, APP and red phosphorus. More suitably, the flame retardant additive is ATH. [00167] In an aspect, the present invention provides a polymer obtained, directly obtained or obtainable by a process of the second aspect of the invention. [00168] In an eighth aspect, the present invention provides a polymer blend obtained, directly obtained or obtainable by a process of the sixth aspect of the invention. [00169] The following numbered statements 1 to 144 are not claims, but instead describe particular aspects and embodiments of the invention: . A polymer comprising: ethylene repeating units, A; and phosphonated ethylene repeating units, B. . The polymer of statement 1, wherein the polymer comprises 86-99 mol% of ethylene repeating units, A. . The polymer of statement 1 or 2, wherein the polymer comprises 90-98.25 mol% of ethylene repeating units, A. . The polymer of statement 1, 2 or 3, wherein the polymer comprises 92-98 mol% of ethylene repeating units, A. . The polymer of any one of the preceding statements, wherein the polymer comprises 93-97.75 mol% of ethylene repeating units, A. . The polymer of any one of the preceding statements, wherein the polymer comprises 93.5-96 mol% of ethylene repeating units, A. . The polymer of any one of the preceding statements, wherein the polymer comprises 1-14 mol% of phosphonated ethylene repeating units, B. . The polymer of any one of the preceding statements, wherein the polymer comprises 1.75-10 mol% of phosphonated ethylene repeating units, B. . The polymer of any one of the preceding statements, wherein the polymer comprises 2-8 mol% of phosphonated ethylene repeating units, B. 0. The polymer of any one of the preceding statements, wherein the polymer comprises 2.25-7 mol% of phosphonated ethylene repeating units, B. 1. The polymer of any one of the preceding statements, wherein the polymer comprises 4-6.5 mol% of phosphonated ethylene repeating units, B.
The polymer of any one of the preceding statements, wherein each phosphonated ethylene repeating unit, B, independently has the structural formula B1:
wherein Y is linking group connecting C1 to X; and X is a phosphonate containing group. The polymer of statement 13, wherein Y links C1 to X by 5-18 bridging atoms. The polymer of statement 12 or 13, wherein Y links C1 to X by 5-9 bridging atoms. The polymer of any one of statements 12-14, wherein Y links C1 to X by 5 or 9 bridging atoms. The polymer of any one of statements 12-15, wherein Y is a (5-18C)alkylene group, a (5- 18C)alkenylene group, or a (5-18C)alkynylene group linking C1 to X. The polymer of any one of statements 12-16, wherein Y is a (5-9C)alkylene group linking C1 to X. The polymer of any one of statements 12-17, wherein Y is selected from:
Table 1 Data from copolymerisation of ethylene and a series of bromoalkenes and 1-dodecene.a
aConditions: rac-ethylenebis(indenyl)zirconium dichloride (Zr) used as a catalyst, MAO used as a cocatalyst and scavenger with [Al]0:[Zr]0 = 1000:1, [comonomer]0 = 91 mM, [TIBA]0:[comonomer]0 = 1:10, 0.5 mL toluene, 49.5 mL hexanes, ethylene 2 bar, 0.5 h. bkgPE molM-1 h-1 bar-1. ckgPE gcat-1 h. dDetermined by 1H NMR spectroscopy in C2D2Cl4 at 130 °C (see SI). eg mol-1. fDetermined by GPC- IR. gDetermined by DSC.h[comonomer]0 = 182 mM. [00197] Due to highest comonomer incorporation and activity, ethylene/11-Br copolymerisation was further studied to assess the effect of varying concentrations of catalyst, comonomer and TIBA on the activity and comonomer incorporation level. The copolymerisation data are summarised in Table 2. Under analogous conditions, a reduction in activity was observed from copolymerisation of ethylene and 11-Br (entries 2–9) compared to ethylene homopolymerisation (entry 1). The decreased activity could be explained by the so-called “Polar Monomer Problem”.12 The copolymerisation without TIBA as a protecting agent of 11-Br showed that 34% of 11-Br was copolymerised resulting in copolymer containing 0.50 mol% incorporation level (entry 2). The molar ratio of 2:1 of TIBA:comonomer was used for the copolymerisation of ethylene and 11-Br (entry 3). The excess TIBA was employed to mitigate the Lewis basic functional group effects.19 A copolymer with 1.12 mol% incorporation level was obtained which 93% of 11-Br was copolymerised. However, its comonomer incorporation cannot be accurately determined from its 1H NMR spectrum due to the presence of signals tentatively corresponding to the residual oxides. A similar issue with the 1H NMR spectrum was also encountered from the copolymerisation with an absence of TIBA. To reduce this effect from the excess TIBA, a molar ratio of 1:10 TIBA:11- Br was employed leading to higher activity, productivity and incorporation (Table 2, entries 3–9).
Table 2 Data from copolymerisation of ethylene and 11-bromo-1-undecene (11-Br).a
aConditions: rac-ethylenebis(indenyl)zirconium dichloride (Zr), MAO used as a cocatalyst and scavenger with [Al]0:[Zr]0 = 1000:1, 0.5 mL toluene, 49.5 mL hexanes, ethylene 2 bar, 0.5 h. b[TIBA]0:[11-Br]0. ckgPE molM -1 h-1 bar-1. dkgPE gcat -1 h. eDetermined by 1H NMR in C2D2Cl4 at 130 °C. fDetermined by DSC. gg mol-1. hTime = 1, 45 and 60 minutes for entries 1, 8 and 9. [00198] Higher yield, productivity, activity and comonomer incorporation level was observed with decreasing catalyst concentration (entries 4–6). 92% of 11-Br was copolymerised when using 0.025 mM of Zr, followed by 88 and 61% when using 0.05 and 0.1 mM of Zr, respectively. The comonomer incorporation level determined from 1H NMR spectroscopy is in the range of 2.44– 6.10 mol% which is higher than those reported.17a, 18, 20 The signal at 3.49 ppm corresponds to the methylene protons adjacent to the bromide group indicating the successful incorporation of 11-Br. A reduction in melting temperature (Tm) and crystallinity from the copolymer containing bromide group compared to those of homopolyethylene was observed from DSC (Table 2). [00199] The molecular weights of the copolymers are lower than those of polyethylene and decline at higher concentrations of 11-Br (Table 2). The reduction in molecular weight of copolymer can be attributed to the chain transfer reactions induced by the spatial active site of Zr. In addition to the chain transfer to aluminium alkyl, β-H transfers to metal and monomer also play a part in the polymerisation using Zr.18, 21 The competing coordination to the metal centre between the 11-Br and ethylene can hinder the incorporation of ethylene and accelerate the chain transfer reactions resulting in a reduction in molecular weights of the resultant copolymers. Broad molecular weight distribution = 7.6–8.2) was observed at copolymerisation using
0.1 and 0.05 mM of Zr. Better weight distribution was observed when the Zr concentration was reduced to 0.025 mM, displaying narrower Mw/Mn values between 3.4–4.5. The FT-IR spectrum of copolymer (Figure 2) shows the adsorption band assigned to C-Br stretching at 656 cm-1. The bands at 719 and 1463 cm-1 correspond to the bending and rocking vibrations of methylene protons of polyethylene. Additionally, the bands at 2916 and 2848 cm-1 are attributed to the asymmetric and symmetrical stretching vibrations of CH2 of polyethylene.
Post-polymerisation modification of brominated functionalised polyethylene [00200] Attempted copolymerisation of ethylene and phosphonate comonomer, CH2=CH(CH2)nP=O(OiPr)2 (n = 2–6), using Zr/MAO was carried out. However, NMR and IR spectroscopy and DSC analyses indicate an absence of phosphonate group on polyethylene. An alternative route for the synthesis of phosphonate-functionalised polyethylene was therefore investigated. Reactions of poly(ethylene)-co-(11-bromo-1-undecene) and phosphite esters (P(OR)3, R = iPr and Ph) were used to synthesise phosphonate-functionalised polyethylene using the Michaelis-Arbuzov reaction.22,23 Scheme 1 Post-polymerisation modification of poly(ethylene)-co-(11-bromo-1-undecene) and phosphite esters.
Post-polymerisation modification of bromo-functionalised polyethylene using triisopropyl phosphite [00201] Poly(ethylene)-co-(11-bromo-1-undecene) was reacted with an excess of triisopropyl phosphite (P(OiPr)3, 50 eq.) in a neat condition at 130 °C for 48 h. Aliquots were collected at 3, 6, 24 and 48 h and analysed by 1H NMR spectroscopy (Figure 3). The 1H NMR spectrum of the aliquot taken at 48 h shows that 96% of the bromide group was converted to the diisopropyl phosphonate group. The reaction temperature was increased from 130 °C to 180 °C to reduce the reaction time. Under analogous conditions. aliquots were taken at 3, 6, 24 and 48 h. The 1H NMR spectra of the aliquot collected after 3 and 6 h (Figure 4) shows 97 and 100% of the bromide group converted to the phosphonate group, respectively. [00202] The signal of the methylene protons adjacent to the bromide group (CH2Br, δ = ca.3.50 ppm) were absent while those from the phosphonate moiety, PO(OCHMe2)2, was observed at 4.74 ppm. The COSY NMR spectrum (Figure 5) shows a through-bond correlation between the signals corresponding to the methine protons and the methyl protons from the phosphonate group (4.74 ppm vs.1.40 ppm). The 31P{1H} NMR spectrum (Figure 6) shows a sharp signal at 29.5 ppm indicating the presence of the phosphonate group into polyethylene. It is noted that the signal of triisopropyl phosphite at ca.140 ppm was not observed. The 1H-31P HMBC spectrum (Figure 7) shows cross-peaks at 4.7 ppm (1H)-29.5 ppm (31P{1H}) and 1.7 ppm (1H)-29.5 ppm (31P{1H}). This supports the assignment of the resonances corresponding to the iPr group of the phosphonate moiety and its neighbouring methylene protons. The DSC analysis of the phosphonate copolymer shows the melting temperature at 123 °C and the degree of crystallinity
of 40% (Figure 8). The presence of the phosphonate moiety on the polyethylene backbone is also confirmed by FT-IR spectroscopy (Figure 9). The peaks corresponding to P=O at 1243 cm- 1 and P-O-C at 1007–982 cm-1 were observed together with the transmission bands at 2916, 2848, 1463 and 719 cm-1 assigned to the (CH2)n of the copolymer. [00203] The bromine concentration in the copolymer samples was analysed using the oxygen combustion flask technique with the analytical uncertainty of 0.3% absolute.9.65 %wt of bromine was detected from poly(ethylene)-co-(11-bromo-1-undecene) with a 5.8 mol% incorporation level. After the post-polymerisation modification with P(OiPr)3, 0.23%wt of bromine was reported despite the absence of resonances assigned to bromide moiety from the 1H and 13C{1H} NMR spectra (Figures 10 and 11) of PE-PO(OiPr)2. Post-polymerisation modification of bromo functionalised polyethylene using triphenyl phosphite [00204] Poly(ethylene)-co-(11-bromo-1-undecene) was reacted with an excess of triphenyl phosphite (P(OPh)3, 50 eq.) in neat conditions at 180 °C for 24, 48 and 72 h. The 1H NMR spectra of the resulting polymer after purification suggest the incomplete conversion of the bromide group to the phosphonate group indicated by a signal at 3.49 ppm corresponding to the methylene protons of the bromide group (CH2Br). Signals in the region of 7.15-7.50 ppm are attributed to the aromatic protons on the phenyl ring of the phosphonate moiety. Based on the integral numbers, the mole ratios of the bromide group to the phosphonate group are 50:50, 30:70 and 20:80 determined from the terpolymers obtained from the reactions carried out for 24, 48 and 72 h (PE-Br-PO(OiPh)2_50%, PE-Br-PO(OiPh)2_70% and PE-Br-PO(OiPh)2_80%), respectively. [00205] Similar to the post-polymerisation modification using triisopropyl phosphite, higher conversion was achieved by increasing the reaction temperature from 180 °C to 200 °C. After 72 h at 200 °C, the bromide group was fully converted to the phosphonate group evidenced by its 1H NMR spectrum (Figure 12). The 31P{1H} NMR spectrum (Figure 13) shows a singlet at 25.14 ppm confirming the presence of the phosphonate group on the polyethylene backbone. The 1H- 31P HMBC spectrum (Figure 14) shows cross-peaks at 7.39–7.28, 2.16, 1.88 ppm (1H) with 25.2 ppm (31P{1H}) supporting the NMR spectroscopic assignment of the signals corresponding to the phenyl rings and the methylene groups adjacent to the phosphonate group. The melting temperatures (Tm) in the range of 122–124 °C and the degree of crystallinity of 20–32% were determined from DSC analysis. The FTIR spectrum of PE-Br-PO(OiPh)2 shows the absorption bands at 1270 cm–1 (P=O) and 1190 and 930 cm–1 (P-O-Ph) indicating the presence of the phosphonate moiety. The bands between 1594–1463 cm-1 were assigned to C-C stretching vibration of the aromatic ring.
Thermal stability and flammability studies [00206] Thermogravimetric analysis (TGA) is one of the widely used techniques for the study of the thermal stability of materials and also indicates the decomposition of the polymers at various temperatures.24 The thermal stability of the investigated polymers was evaluated by the temperatures at 10% and 50% weight loss (T10% and T50%) and the temperature of maximum rates of weight loss (Tmax) as well as the solid residual char yields at 700 °C. TGA was conducted under nitrogen and air atmosphere with a heating rate of 20 °C min-1. The TGA and derivative thermogravimetry (DTG) plots of the pyrolysis and thermal-oxidative of the commercial LDPE and phosphonate-functionalised polyethylene are displayed in Figure 15. The summarised results are shown in Table 3. Table 3 Data from DSC and TGA of LDPE and phosphonate functionalised polyethylenea Nitrogen atmosphere Air atmosphere Entry Sample TmCrystallinity 1 LDPE
2 PE-PO(OiPr) 123 19 307 5 293, 284, 2 09 1.1 270 492 4.01 509 487 3 PE-Br- 124 23 462 505 508 0.95 377 481 393, 2.83 PO(OPh)2_50% 483 PE-Br- 342, 4 PO(OPh) 122 32 423 503 506 1.16 360 496 3.24 2_70% 496 PE-Br- 344, 5 PO(OPh) _80 124 20 457 503 505 1.66 362 505 3.35 2 % 503 6 PE-PO(OPh) 333, 2 117 18 475 510 510 1.22 455 506 3.51
aTGA tests were performed between 50–800 °C under nitrogen and air atmospheres with a heating rate of 20 °C
bResidue at 700 °C. [00207] Under nitrogen atmosphere, TGA and DTG curves of PE-PO(OiPr)2, PE-PO(OPh)2, and LDPE (Table 3, Figures 15a, 15b) demonstrate comparable T50% and Tmax (500–510 °C). However, T10%, T50% and Tmax obtained from LDPE were lower when performed under air atmosphere than nitrogen atmosphere. A single-decomposition step was observed from testing LDPE under both atmospheres evidenced by a single DTG peak (Figures 15b and 15d). The residue of the LDPE at 700 °C is at 0.16–0.22%. The presence of the phosphonate group on polyethylene leads to higher thermal stability; thermal degradation of PE-PO(OiPr)2 and PE- PO(OPh)2 gives higher T50% and Tmax and residual percentage at 700 °C than those of LDPE. The T10% of PE-PO(OiPr)2 conducted under an air atmosphere (295 °C) is lower than LDPE (300 °C) which is attributed to the lower bond dissociation energy of O=P-O and P-O-C bonds than C- C bonds.25 The phosphonate group decomposes during the first stage of heating between ca. 200–350 °C resulting in the formation of a carbonaceous char layer, shielding the material from
oxygen and preventing the formation of flammable gases.4b Therefore. the degradation of polyethylene occurred at higher temperatures indicated by higher T50% and Tmax and an increased residual char yield (3.51–4.01%) compared to LDPE.26 Higher T10% from PE-PO(OPh)2 than PE- PO(OiPr)2 (455 vs. 270 °C) is attributed to the aromatic rings incorporated into PE backbone resulting in the delayed first stage of decomposition (Figures 15c and 15d).27 The highest char yield (4.01%) was gained from thermal-oxidative degradation of PE-PO(OiPr)2 (Table 3, entry 2), whilst the highest Tmax and T50% were observed from the TGA test of PE-PO(OPh)2 under an air atmosphere (Table 3, entry 6). [00208] The effect of the incorporation level of the phosphonate group on thermal stability was observed from the TGA curves of PE-Br-PO(OPh)2_x% (x = 50, 70 and 80) and PE-PO(OPh)2 conducted under nitrogen and air atmospheres. During the first thermal-oxidative degradation stage, a higher phosphonate incorporation level results in lower T10%. During the second decomposition stage, higher T50% and Tmax were observed as well as higher char residual percentage correlated with a higher phosphonate incorporation level. [00209] MCC is a thermal analysis method evaluating for flammability screening of polymers. The MCC method directly measures the heat of combustion of the gases evolved during controlled heating of milligram-sized samples.28 The MCC test was conducted three times for each sample and the average values of the flammability parameters of PE-Br-PO(OPh)2_50% and PE-Br-PO(OPh)2_80% including the heat release capacity (HRC), the peak heat release rate (pHRR), the total heat release (THR) and the temperature at pHRR (TpHRR) are listed in Table 4. Table 4 MCC Data of HDPE and phosphonate functionalised polyethylene. Sample HRC (J g-1 K) pHRR (W g-1) THR (kJ g-1) TpHRR (°C) HDPE28, 30 1486 1351 43.5 504 LDPE foam 984.0 971.5 37.0 493.0 PE-Br-PO(OPh)2_50% 271.39 228.70 8.52 488.2 PE-Br-PO(OPh)2_80% 223.16 188.49 7.36 488.7 PE-PO(OPh)2_100% 218.37 185.79 11.10 496.2 [00210] The HDPE sample gives high values of HRC, pHRR and THR indicating a high release amount of the flammable products. More than 80% reduction in the values of HRC, pHRR and THR was observed from PE-Br-PO(OPh)2_50% and PE-Br-PO(OPh)2_80% compared to those of HDPE. These indicate that the incorporation of the phosphonate group increases the flame
retardancy performance of polyethylene. Lower values of MCC parameters from PE-Br- PO(OPh)2_80% compared to those of PE-Br-PO(OPh)2_50% were observed highlighting the enhanced flame resistance correlating with higher phosphonate group incorporation level. The HRC value from the MCC test was utilised to predict the fire behaviour and flame resistance of flame-retardant polymers.28 The HRC of PE-Br-PO(OPh)2_50% and PE-Br-PO(OPh)2_80% are lower than 300 J g-1 K (HRC = 223–271 J g-1 K) suggesting the limiting oxygen index (LOI) above 21% and the UL 94 V-0 rating. These show the self-extinguishing property of the phosphonate functionalised polyethylene due to the predicted LOI greater than 21%.29 Polymer compounding with LDPE and inorganic flame retardant additive [00211] The mixtures of LDPE and PE-PO(OiPr)2 or PE-PO(OPh)2 in a ratio of 90:10, 95:5 and 99:1 wt% were prepared via melting in xylene at 120 °C for 5 minutes to obtain a clear solution. The polymer was precipitated with addition of pentane, filtered and dried under vacuum at 90 °C for 18 h. Their thermal properties were studied using TGA performed under an air atmosphere. The TGA parameters and curves are listed in Table 5 and Figure 17. LDPE was employed due to its application as a protective jacket for wires and cables.31 However, LDPE is a highly flammable thermoplastic with melt dripping behaviour when burning. Table 5 TGA and DSC data of reference polymersa Sample wt% T10% T50% Tmax Residue at 700 °C Tm Crystallinity (°C) (°C) (°C) (%) (°C) (%)
[00212] Compared with the pure phosphonate-functionalised polyethylene; as expected, reduced thermal stability was observed when blending PE-PO(OiPr)2 or PE-PO(OPh)2 with LDPE according to their decreased T10%, T50%, Tmax and% residual at 700 °C. The blended polymers, however, have higher T10%, T50% and Tmax compared to those of pure LDPE regardless of 10, 5 and 1 wt% substitution of LDPE with PE-PO(OiPr)2 or PE-PO(OPh)2. These signify that a low concentration of the phosphonate group on polyethylene can lead to enhanced thermal stability.
[00213] The flame retardant additive, ATH, was blended with LDPE and PE-PO(OiPr)2 or PE- PO(OPh)2. ATH has been commercially used in polyethylene wire and cable formulations due to its low toxicity, cost efficiency, white colour and excellent flame retardancy and smoke suppression property.32 ATH functions by liberating water vapour endothermically from the decomposition reaction at 220–400 °C. Water vapour can hinder the combustion process by diluting the flammable gases and shielding the polymer surface from oxygen. However, high loading of ATH at least 35 wt% led to degraded physical properties (increasing part density and brittleness). [00214] The ratio of LDPE:ATH:phosphonate-functionalised polyethylene is 80:10:10 wt%. TGA and DTG curves of LDPE:ATH (90:10 wt%) show comparable thermal stability to those of pure LDPE (Figures 18a and 18b). Higher T10%, T50%, Tmax and % char residue at 700 °C (7.1–8.2%) was obtained from LDPE:ATH:PE-PO(OR)2 (80:10:10 wt%), compared to those with LDPE:ATH (90:10 wt%) and LDPE:PE-PO(OR)2 (90:10 wt%). The enhanced thermal stability can be attributed to the synergistic effect in the condensed phase.33b-d During the combustion process, phosphonate group on polyethylene degrades generating polyphosphoric acid. In the meantime, ATH releases water and forms aluminium oxide. Polyphosphoric acid then reacts with aluminium oxide to form aluminium metaphosphate (Al(PO3)3), increasing the density and isolation effect of the char residual layer and inhibiting the transmission of oxygen and heat. [00215] While specific embodiments of the invention have been described herein for the purpose of reference and illustration, various modifications will be apparent to a person skilled in the art without departing from the scope of the invention as defined by the appended claims. REFERENCES 1. a) Y. Liu, D.-Y. Wang, J.-S. Wang, Y.-P. Song and Y.-Z. Wang, Polym. Adv. Technol., 2008, 19, 1566-1575; b) E. Rezvani Ghomi, F. Khosravi, Z. Mossayebi, A. Saedi Ardahaei, F. Morshedi Dehaghi, M. Khorasani, R. E. Neisiany, O. Das, A. Marani, R. A. Mensah, L. Jiang, Q. Xu, M. Försth, F. Berto and S. Ramakrishna, Molecules, 2020, 25, 5157. 2. V. I. Babushok, P. Deglmann, R. Krämer and G. T. Linteris, Combust. Sci. Technol., 2017, 189, 290-311. 3. a) R. J. Law, A. Covaci, S. Harrad, D. Herzke, M. A. E. Abdallah, K. Fernie, L.-M. L. Toms and H. Takigami, Environ. Int., 2014, 65, 147-158; b) M. Venier, A. Salamova and R. A. Hites, Acc. Chem. Res., 2015, 48, 1853-1861; c) I. T. Cousins, C. A. Ng, Z. Wang and M. Scheringer, Environ. Sci.: Processes Impacts, 2019, 21, 781-792; d) P. Schmid, M. Kohler, A. C. Gerecke, E. Gujer, M. Zennegg and M. Wolfensberger, CHIMIA, 2003, 57, 509-513. 4. a) L. Chen and Y.-Z. Wang, Polym. Adv. Technol., 2010, 21, 1-26; b) I. van der Veen and J. de Boer, Chemosphere, 2012, 88, 1119-1153; c) S. Hörold, in Polymer Green Flame Retardants, eds. C. D. Papaspyrides and P. Kiliaris, Elsevier, Amsterdam, 2014, pp.221-254.
5. a) M. M. Velencoso, A. Battig, J. C. Markwart, B. Schartel and F. R. Wurm, Angew. Chem. Int. Ed., 2018, 57, 10450-10467; b) B. Schartel, Materials, 2010, 3, 4710-4745. 6. S. Rabe, Y. Chuenban and B. Schartel, Materials, 2017, 10, 455. 7. a) J. Green, J. Fire Sci., 1992, 10, 470-487; b) J. Green, J. Fire Sci., 1996, 14, 426-442. 8. a) O. P. Korobeinichev, A. A. Paletsky, L. V. Kuibida, M. B. Gonchikzhapov and I. K. Shundrina, Proc. Combust. Inst., 2013, 34, 2699-2706; b) K. Salasinska, K. Mizera, M. Celiński, P. Kozikowski, M. Borucka and A. Gajek, Fire Saf. J., 2020, 115, 103137; c) F. Xie, Y.-Z. Wang, B. Yang and Y. Liu, Macromol. Mater. Eng., 2006, 291, 247-253; d) Y. Z. Wang, in Advances in Fire Retardant Materials, eds. A. R. Horrocks and D. Price, Woodhead Publishing, 2008, pp.67- 94; e) Q. Wang, J. P. Undrell, Y. Gao, G. Cai, J.-C. Buffet, C. A. Wilkie and D. O’Hare, Macromolecules, 2013, 46, 6145-6150; f) Y. Luo, Y. Xie, R. Chen, R. Zheng, H. Wu, X. Sheng, D. Xie and Y. Mei, Front. Chem. Sci. Eng., 2021, 15, 1332-1345. 9. a) H. Wang, H. Niu and J.-Y. Dong, Polymer, 2017, 126, 109-115; b) J. R. Ebdon, D. Price, B. J. Hunt, P. Joseph, F. Gao, G. J. Milnes and L. K. Cunliffe, Polym. Degrad. Stab., 2000, 69, 267-277; c) T. Xu, L. Zhang, Z. Cheng and X. Zhu, Sci. China Chem., 2015, 58, 1633-1640; d) M. Yılmaz, A. Akar, N. Köken and N. Kızılcan, J. Appl. Polym. Sci., 2020, 137, 49023; e) D. Price, L. K. Cunliffe, K. J. Bullet, T. R. Hull, G. J. Milnes, J. R. Ebdon, B. J. Hunt and P. Joseph, Polym. Adv. Technol., 2008, 19, 710-723; f) W. Hu, J. Zhan, N. Hong, T. R. Hull, A. A. Stec, L. Song, J. Wang and Y. Hu, Polym. Adv. Technol., 2014, 25, 631-637. 10. J. Gao, W. Cai, Y. Hu and C. Chen, Polym. Chem., 2019, 10, 1416-1422. 11. D. Price, K. Pyrah, T. R. Hull, G. J. Milnes, J. R. Ebdon, B. J. Hunt, P. Joseph and C. S. Konkel, Polym. Degrad. Stab., 2001, 74, 441-447. 12. A. Keyes, H. E. Basbug Alhan, E. Ordonez, U. Ha, D. B. Beezer, H. Dau, Y.-S. Liu, E. Tsogtgerel, G. R. Jones and E. Harth, Angew. Chem. Int. Ed., 2019, 58, 12370-12391. 13. a) H. Hagihara, K. Tsuchihara, J. Sugiyama, K. Takeuchi and T. Shiono, Macromolecules, 2004, 37, 5145-5148; b) J.-i. Imuta, N. Kashiwa and Y. Toda, J. Am. Chem. Soc., 2002, 124, 1176-1177; c) H. Terao, S. Ishii, M. Mitani, H. Tanaka and T. Fujita, J. Am. Chem. Soc., 2008, 130, 17636-17637. 14. a) J. Chen, A. Motta, B. Wang, Y. Gao and T. J. Marks, Angew. Chem. Int. Ed., 2019, 58, 7030-7034; b) L. S. Boffa and B. M. Novak, Chem. Rev., 2000, 100, 1479-1494. 15. a) B. P. Carrow and K. Nozaki, Macromolecules, 2014, 47, 2541-2555; b) R. Nakano and K. Nozaki, J. Am. Chem. Soc., 2015, 137, 10934-10937; c) Y. Ota, S. Ito, M. Kobayashi, S. Kitade, K. Sakata, T. Tayano and K. Nozaki, Angew. Chem. Int. Ed., 2016, 55, 7505-7509; d) L. Guo, W. Liu and C. Chen, Mater. Chem. Front., 2017, 1, 2487-2494; e) L. Guo, S. Dai, X. Sui and C. Chen, ACS Catal., 2016, 6, 428-441; f) Z. Chen and M. Brookhart, Acc. Chem. Res., 2018, 51, 1831-1839. 16. a) T. P. Coogan, D. M. Latta, E. T. Snow, M. Costa and A. Lawrence, CRC Crit. Rev. Toxicol., 1989, 19, 341-384; b) K. K. Das, R. C. Reddy, I. B. Bagoji, S. Das, S. Bagali, L. Mullur, J. P. Khodnapur and M. S. Biradar, J. Basic Clin. Physiol. Pharmacol., 2019, 30, 141-152; c) E. Denkhaus and K. Salnikow, Crit. Rev. Oncol. Hematolo., 2002, 42, 35-56; d) Nat. Catal., 2019, 2, 735-735. 17. a) W. Zhao, B. Wang, B. Dong, H. Liu, Y. Hu, M. S. Eisen and X. Zhang, Organometallics, 2020, 39, 3983-3991; b) X. Wang, Y. Wang, X. Shi, J. Liu, C. Chen and Y. Li,
Macromolecules, 2014, 47, 552-559; c) S. Dai and C. Chen, Angew. Chem. Int. Ed., 2016, 55, 13281-13285. 18. X.-Y. Wang, Y.-Y. Long, Y.-X. Wang and Y.-S. Li, J. Polym. Sci. Part A: Polym. Chem., 2014, 52, 3421-3428. 19. J. Chen, Y. Gao and T. J. Marks, Angew. Chem. Int. Ed., 2020, 59, 14726-14735. 20. a) S. Bruzaud, H. Cramail, L. Duvignac and A. Deffieux, Macromol. Chem. Phys., 1997, 198, 291-303; b) T. Toda, I. Miura, M. Miya and K. Takenaka, Catalysts, 2019, 9, 660. 21. L. Resconi, L. Cavallo, A. Fait and F. Piemontesi, Chem. Rev., 2000, 100, 1253-1346. 22. A. K. Bhattacharya and G. Thyagarajan, Chem. Rev., 1981, 81, 415-430. 23. a) W. Nzahou Ottou, S. Norsic, F. D'Agosto and C. Boisson, Macromol. Rapid Commun., 2018, 39, 1800154; b) C. Negrell-Guirao, G. David, B. Boutevin and K. Chougrani, J. Polym. Sci. A Polym. Chem., 2011, 49, 3905-3910; c) R. Tayouo, G. David, B. Améduri, J. Rozière and S. Roualdès, Macromolecules, 2010, 43, 5269-5276; d) Z. Yu, W.-X. Zhu and I. Cabasso, J. Polym. Sci. A Polym. Chem., 1990, 28, 227-230. 24. X. Chen, Y. Hu and L. Song, Polym. Eng. Sci., 2008, 48, 116-123. 25. a) K. Wazarkar, M. Kathalewar and A. Sabnis, Polym. Compos., 2017, 38, 1483-1491; b) M. Hussain, R. J. Varley, Z. Mathys, Y. B. Cheng and G. P. Simon, J. Appl. Polym. Sci., 2004, 91, 1233-1253; c) L.-P. Gao, D.-Y. Wang, Y.-Z. Wang, J.-S. Wang and B. Yang, Polym. Degrad. Stab., 2008, 93, 1308-1315. 26. K. Sałasińska, M. Borucka, M. Celiński, A. Gajek, W. Zatorski, K. Mizera, M. Leszczyńska and J. Ryszkowska, Adv. Polym. Technol., 2018, 37, 2394-2410. 27. a) B. Yang, L. Wang, Y. Guo, Y. Zhang, N. Wang, J. Cui, J. Guo and L. Tian, Polym. Adv. Technol., 2020, 31, 472-481; b) Z. Bai, L. Song, Y. Hu and R. K. K. Yuen, Ind. Eng. Chem., 2013, 52, 12855-12864. 28. R. E. Lyon, R. N. Walters and S. I. Stoliarov, Polym. Eng. Sci., 2007, 47, 1501-1510. 29. M. J. John, in Green Composites for Automotive Applications, eds. G. Koronis and A. Silva, Woodhead Publishing, 2019, DOI: https://doi.org/10.1016/B978-0-08-102177-4.18001-2, pp.301-308. 30. Q. Tai, Y. Hu, R. K. K. Yuen, L. Song and H. Lu, J. Mater. Chem., 2011, 21, 6621-6627. 31. N. H. Thi, T. N. Nguyen, H. T. Oanh, N. T. T. Trang, D. Q. Tham, H. T. Nguyen, T. Van Nguyen and M. H. Hoang, J. Appl. Polym. Sci., 2021, 138, 50317. 32. E. A. Coleman, in Applied Plastics Engineering Handbook (Second Edition), ed. M. Kutz, William Andrew Publishing, 2017, DOI: https://doi.org/10.1016/B978-0-323-39040-8.00021-3, pp.489-500. 33. a) Z.-s. Xu, L. Yan and L. Chen, Procedia Eng., 2016, 135, 631-636; b) L. Yan, Z. Xu, X. Wang, N. Deng and Z. Chu, J. Coat. Technol. Res., 2018, 15, 1357-1369; c) P. Khalili, K. Y. Tshai, D. Hui and I. Kong, Compos. B Eng., 2017, 114, 101-110; d) Z. Qin, D. Li, Q. Li and R. Yang, Materials & Design, 2016, 89, 988-995; e) Q. Li, P. Jiang, Z. Su, P. Wei, G. Wang and X. Tang, J. Appl. Polym. Sci., 2005, 96, 854-860; f) Y. Wang, L. Zhang, Y. Yang and X. Cai, J. Therm. Anal. Calorim., 2016, 125, 839-848; g) D. Yang, Y. Hu, H. Li, L. Song, H. Xu and B. Li, J. Therm. Anal. Calorim., 2015, 119, 619-624.
34. P. Wei, Z. Han, X. Xu and Z. Li, J. Fire Sci., 2006, 24, 487-498. 35. Z.-Y. Wang, Y. Liu and Q. Wang, Polym. Degrad. Stab., 2010, 95, 945-954. 36. a) L. Ai, S. Chen, L. Yang and P. Liu, Fibers Polym., 2021, 22, 354-365; b) C. Hoffendahl, G. Fontaine, S. Duquesne, F. Taschner, M. Mezger and S. Bourbigot, Polym. Degrad. Stab., 2015, 115, 77-88; c) S. Bourbigot, M. L. Bras, R. Leeuwendal, K. K. Shen and D. Schubert, Polym. Degrad. Stab., 1999, 64, 419-425; d) N. A. Isitman and C. Kaynak, J. Fire Sci., 2013, 31, 73-84.
Claims
CLAIMS 1. A polymer comprising: ethylene repeating units, A; and phosphonated ethylene repeating units, B.
2. The polymer of claim 1, wherein the polymer comprises 92-98 mol% of ethylene repeating units, A.
3. The polymer of claim 1 or 2, wherein each ethylene repeating unit, A, has the structural formula: .
4. The polymer of claim 1, 2 or 3, wherein the polymer comprises 2-8 mol% of phosphonated ethylene repeating units, B.
5. The polymer of any one of the preceding claims, wherein each phosphonated ethylene repeating unit, B, independently has the structural formula B1:
wherein Y is linking group connecting C1 to X; and X is a phosphonate containing group.
6. The polymer of claim 5, wherein Y links C1 to X by 5-18 bridging atoms.
7. The polymer of claim 5 or 6, wherein Y is a (5-9C)alkylene group linking C1 to X.
8. The polymer of claim 5, 6 or 7, wherein Y is selected from:
wherein denotes the point of attachment to C1; and denotes the point of attachment to X.
9. The polymer of any one of claims 5-8, wherein X has the structural formula B1a:
wherein: denotes the point of attachment to Y; and each R is independently selected from (1-6C)alkyl and aryl, wherein each R is optionally substituted.
10. The polymer of claim 9, wherein each R is independently selected from methyl, propyl, butyl, pentyl, hexyl and phenyl, wherein each R is optionally substituted.
11. The polymer of any one of the preceding claims, wherein each phosphonated ethylene repeating unit, B, is independently selected from:
12. The polymer of any one the preceding claims, wherein the phosphonated ethylene repeating units, B, are randomly distributed along the length of the polymer. 13. The polymer of any one the preceding claims, wherein the polymer consists of / consists essentially of ethylene repeating units, A, and phosphonated ethylene repeating units, B. 14. A polymer blend comprising: a polymer of any one of the preceding claims; and polyethylene. 15. The polymer blend of claim 14, wherein the polymer blend comprises 1-20 wt% of the polymer. 16. The polymer blend of claim 14 or 15, wherein the polymer blend comprises 80-99 wt% polyethylene. 17. The polymer blend of claim 14, 15 or 16, wherein the polymer blend further comprises one or more flame retardant additives.
18. The polymer blend of claim 17, wherein the flame retardant is selected from a LDH, ATH, MDH, Sb2O3, RDP, a triaryl phosphate, a metal phosphinate, DOPO, TCCP, APP and red phosphorus. 19. A polymer blend comprising: phosphonated polyethylene; a polyolefin; and a hydroxylated flame retardant additive. 20. The polymer blend of claim 19, wherein the phosphonated polyethylene comprises an ethylene repeating unit substituted with a phosphonate containing group. 21. The polymer blend of claim 19 or 20, wherein the phosphonated polyethylene is a polymer of any one of claims 1-13. 22. The polymer blend of claim 19, 20 or 21, wherein the polyolefin is selected from HDPE, LDPE and LLDPE. 23. The polymer blend of any one of claims 19-22, wherein the hydroxylated flame retardant additive is selected from a LDH, ATH and MDH. 24. The polymer blend of any one of claims 19-23, wherein the polymer blend comprises: 5-15 wt% of the phosphonated polyethylene 70-90 wt% of the polyolefin 5-15 wt% of the hydroxylated flame retardant additive. 25. Use of the polymer of any one of claims 1-13, the polymer blend of any one of claims 14-18, or the polymer blend of any one of claims 19-24 as a flame retardant.
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| GBGB2218266.1A GB202218266D0 (en) | 2022-12-05 | 2022-12-05 | Flame retardant polymers and blends |
| GB2218266.1 | 2022-12-05 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB838745A (en) * | 1957-01-30 | 1960-06-22 | Spencer Chem Co | Polyethylene derivatives |
| CA679847A (en) * | 1964-02-11 | Shell Oil Company | LUBRICATING COMPOSITIONS CONTAINING POLYPHOSPHONATED ETHYLENE/.alpha.-OLEFIN COPOLYMERS | |
| US3290276A (en) * | 1959-12-21 | 1966-12-06 | Shell Oil Co | Oil-soluble phospho-halo-containing ethylene/propylene copolymers |
| US4255540A (en) * | 1979-04-19 | 1981-03-10 | Exxon Research & Engineering Co. | Neutralized phosphonated elastomeric polymers |
| US11046798B2 (en) * | 2017-12-11 | 2021-06-29 | The Procter & Gamble Company | Phosphono-phosphate containing compounds and polymers |
| WO2022106688A1 (en) * | 2020-11-23 | 2022-05-27 | Sabic Global Technologies B.V. | Solution process for production of halide- or tertiary amine- functionalized polyolefins |
-
2022
- 2022-12-05 GB GBGB2218266.1A patent/GB202218266D0/en not_active Ceased
-
2023
- 2023-12-04 WO PCT/GB2023/053126 patent/WO2024121540A1/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA679847A (en) * | 1964-02-11 | Shell Oil Company | LUBRICATING COMPOSITIONS CONTAINING POLYPHOSPHONATED ETHYLENE/.alpha.-OLEFIN COPOLYMERS | |
| GB838745A (en) * | 1957-01-30 | 1960-06-22 | Spencer Chem Co | Polyethylene derivatives |
| US3290276A (en) * | 1959-12-21 | 1966-12-06 | Shell Oil Co | Oil-soluble phospho-halo-containing ethylene/propylene copolymers |
| US4255540A (en) * | 1979-04-19 | 1981-03-10 | Exxon Research & Engineering Co. | Neutralized phosphonated elastomeric polymers |
| US11046798B2 (en) * | 2017-12-11 | 2021-06-29 | The Procter & Gamble Company | Phosphono-phosphate containing compounds and polymers |
| WO2022106688A1 (en) * | 2020-11-23 | 2022-05-27 | Sabic Global Technologies B.V. | Solution process for production of halide- or tertiary amine- functionalized polyolefins |
Non-Patent Citations (75)
| Title |
|---|
| A. K. BHATTACHARYAG. THYAGARAJAN, CHEM. REV., vol. 81, 1981, pages 415 - 430 |
| A. KEYESH. E. BASBUG ALHANE. ORDONEZU. HAD. B. BEEZERH. DAUY.-S. LIUE. TSOGTGERELG. R. JONESE. HARTH, ANGEW. CHEM. INT. ED., vol. 58, 2019, pages 12370 - 12391 |
| B. SCHARTEL, MATERIALS, vol. 3, 2010, pages 4710 - 4745 |
| B. YANGL. WANGY. GUOY. ZHANGN. WANGJ. CUIJ. GUOL. TIAN, POLYM. ADV. TECHNOL., vol. 31, 2020, pages 472 - 481 |
| B. YANGY. LIU, MACROMOL. MATER. ENG., vol. 291, 2006, pages 247 - 253 |
| C. HOFFENDAHLG. FONTAINES. DUQUESNEF. TASCHNERM. MEZGERS. BOURBIGOT, POLYM. DEGRAD. STAB., vol. 115, 2015, pages 77 - 88 |
| C. NEGRELL-GUIRAOG. DAVIDB. BOUTEVINK. CHOUGRANI, J. POLYM. SCI. A POLYM. CHEM., vol. 49, 2011, pages 3905 - 3910 |
| D. PRICE, L. K. CUNLIFFE, K. J. BULLET, T. R. HULL, G. J. MILNES, J. R. EBDON, B. J. HUNT AND P. JOSEPH, POLYM. ADV. TECHNOL., vol. 19, 2008, pages 1566 - 1575 |
| D. PRICEK. PYRAHT. R. HULLG. J. MILNESJ. R. EBDONB. J. HUNTP. JOSEPHC. S. KONKEL, POLYM. DEGRAD. STAB., vol. 74, 2001, pages 441 - 447 |
| D. YANGY. HUH. LIL. SONGH. XUB. LI, J. THERM. ANAL. CALORIM., vol. 119, 2015, pages 619 - 624 |
| DENKHAUSK. SALNIKOW, CRIT. REV. ONCOL. HEMATOLO., vol. 42, 2002, pages 35 - 56 |
| E. REZVANI GHOMIF. KHOSRAVIZ. MOSSAYEBIA. SAEDI ARDAHAEIF. MORSHEDI DEHAGHIM. KHORASANIR. E. NEISIANYO. DASA. MARANIR. A. MENSAH, MOLECULES, vol. 25, 2020, pages 5157 |
| H. HAGIHARAK. TSUCHIHARAJ. SUGIYAMAK. TAKEUCHIT. SHIONO, MACROMOLECULES, vol. 37, 2004, pages 5145 - 5148 |
| H. TERAOS. ISHIIM. MITANIH. TANAKAT. FUJITA, J. AM. CHEM. SOC., vol. 130, 2008, pages 17636 - 17637 |
| H. WANGH. NIUJ.-Y. DONG, POLYMER, vol. 126, 2017, pages 109 - 115 |
| I. T. COUSINSC. A. NGZ. WANGM. SCHERINGER, ENVIRON. SCI.: PROCESSES IMPACTS, vol. 21, 2019, pages 781 - 792 |
| I. VAN DER VEENJ. DE BOER, CHEMOSPHERE, vol. 88, 2012, pages 1119 - 1153 |
| J. CHENY. GAOT. J. MARKS, ANGEW. CHEM. INT. ED., vol. 59, 2020, pages 14726 - 14735 |
| J. GAOW. CAIY. HUC. CHEN, POLYM. CHEM., vol. 10, 2019, pages 1416 - 1422 |
| J. GREEN, J. FIRE SCI., vol. 10, 1992, pages 470 - 487 |
| J. GREEN, J. FIRE SCI., vol. 14, 1996, pages 426 - 442 |
| J. P. KHODNAPURM. S. BIRADAR, J. BASIC CLIN. PHYSIOL. PHARMACOL., vol. 30, 2019, pages 141 - 152 |
| J. R. EBDOND. PRICEB. J. HUNTP. JOSEPHF. GAOG. J. MILNESL. K. CUNLIFFE, POLYM. DEGRAD. STAB., vol. 69, 2000, pages 267 - 277 |
| J.-I. IMUTAN. KASHIWAY. TODA, J. AM. CHEM. SOC., vol. 124, 2002, pages 1176 - 1177 |
| K. SATASINSKAM. BORUCKAM. CELIRISKIA. GAJEKW. ZATORSKIK. MIZERAM. LESZCZYNSKAJ. RYSZKOWSKA, ADV. POLYM. TECHNOL., vol. 37, 2018, pages 2394 - 2410 |
| K. WAZARKARM. KATHALEWARA. SABNIS, POLYM. COMPOS., vol. 38, 2017, pages 1483 - 1491 |
| L. AIS. CHENL. YANGP. LIU, FIBERS POLYM., vol. 22, 2021, pages 354 - 365 |
| L. CHENY.-Z. WANG, POLYM. ADV. TECHNOL., vol. 21, 2010, pages 1 - 26 |
| L. GUOS. DAIX. SUIC. CHEN, ACS CATAL., vol. 6, 2016, pages 428 - 441 |
| L. GUOW. LIUC. CHEN, MATER. CHEM. FRONT., vol. 1, 2017, pages 2487 - 2494 |
| L. RESCONIL. CAVALLOA. FAITF. PIEMONTESI, CHEM. REV., vol. 100, 2000, pages 1253 - 1346 |
| L. YANZ. XUX. WANGN. DENGZ. CHU, J. COAT. TECHNOL. RES., vol. 15, 2018, pages 1357 - 1369 |
| L.-P. GAO, D.-Y. WANG, Y.-Z. WANG, J.-S. WANG AND B. YANG, STAB., vol. 93, 2008, pages 1308 - 1315 |
| M. HUSSAINR. J. VARLEYZ. MATHYSY. B. CHENGG. P. SIMON, J. APPL. POLYM. SCI., vol. 91, 2004, pages 1233 - 1253 |
| M. J. JOHN: "Green Composites for Automotive Applications", 2019, WOODHEAD PUBLISHING, pages: 301 - 308 |
| M. M. VELENCOSOA. BATTIGJ. C. MARKWARTB. SCHARTELF. R. WURM, ANGEW. CHEM. INT. ED., vol. 57, 2018, pages 10450 - 10467 |
| M. VENIERA. SALAMOVAR. A. HITES, ACC. CHEM. RES., vol. 48, 2015, pages 1853 - 1861 |
| M. YILMAZA. AKARN. KOKENN. KIZILCAN, J. APPL. POLYM. SCI., vol. 137, 2020, pages 49023 |
| N. A. ISITMANC. KAYNAK, J. FIRE SCI., vol. 31, 2013, pages 73 - 84 |
| N. H. THIT. N. NGUYENH. T. OANHN. T. T. TRANGD. Q. THAMH. T. NGUYENT. VAN NGUYENM. H. HOANG, J. APPL. POLYM. SCI., vol. 138, 2021, pages 50317 |
| NAT. CATAL., vol. 2, 2019, pages 735 - 735 |
| O. P. KOROBEINICHEVA. A. PALETSKYL. V. KUIBIDAM. B. GONCHIKZHAPOVI. K. SHUNDRINA, PROC. COMBUST. INST., vol. 34, 2013, pages 2699 - 2706 |
| P. KHALILIK. Y. TSHAID. HUII. KONG, COMPOS. 6 ENG., vol. 114, 2017, pages 101 - 110 |
| P. KOZIKOWSKIM. BORUCKAA. GAJEK, FIRE SAF. J., vol. 115, 2020, pages 103137 |
| P. SCHMIDM. KOHLERA. C. GERECKEE. GUJERM. ZENNEGGM. WOLFENSBERGER, CHIMIA, vol. 57, 2003, pages 509 - 513 |
| P. WEIZ. HANX. XUZ. LI, J. FIRE SCI., vol. 24, 2006, pages 487 - 498 |
| Q. LIP. JIANGZ. SUP. WEIG. WANGX. TANG, J. APPL. POLYM. SCI., vol. 96, 2005, pages 854 - 860 |
| Q. TAIY. HUR. K. K. YUENL. SONGH. LU, J. MATER. CHEM., vol. 21, 2011, pages 6621 - 6627 |
| Q. WANGJ. P. UNDRELLY. GAOG. CAIJ.-C. BUFFETC. A. WILKIED. O'HARE, MACROMOLECULES, vol. 46, 2013, pages 6145 - 6150 |
| R. E. LYONR. N. WALTERSS. I. STOLIAROV, POLYM. ENG. SCI., vol. 47, 2007, pages 1501 - 1510 |
| R. J. LAWA. COVACIS. HARRADD. HERZKEM. A. E. ABDALLAHK. FERNIEL.-M. L. TOMSH. TAKIGAMI, ENVIRON. INT., vol. 65, 2014, pages 147 - 158 |
| R. NAKANOK. NOZAKI, J. AM. CHEM. SOC., vol. 137, 2015, pages 10934 - 10937 |
| R. TAYOUOG. DAVIDB. AMEDURIJ. ROZIERES. ROUALDES, MACROMOLECULES, vol. 43, 2010, pages 5269 - 5276 |
| S. BOURBIGOTM. L. BRASR. LEEUWENDALK. K. SHEND. SCHUBERT, POLYM. DEGRAD. STAB., vol. 64, 1999, pages 419 - 425 |
| S. BRUZAUDH. CRAMAILL. DUVIGNACA. DEFFIEUX, MACROMOL. CHEM. PHYS., vol. 198, 1997, pages 291 - 303 |
| S. RABEY. CHUENBANB. SCHARTEL, MATERIALS, vol. 10, 2017, pages 455 |
| T. P. COOGAND. M. LATTAE. T. SNOWM. COSTAA. LAWRENCE, CRC CRIT. REV. TOXICOL., vol. 19, 1989, pages 341 - 384 |
| T. TODAI. MIURAM. MIYAK. TAKENAKA, CATALYSTS, vol. 9, 2019, pages 660 |
| T. XUL. ZHANGZ. CHENGX. ZHU, SCI. CHINA CHEM., vol. 58, 2015, pages 1633 - 1640 |
| V. I. BABUSHOKP. DEGLMANNR. KRAMERG. T. LINTERIS, COMBUST. SCI. TECHNOL., vol. 189, 2017, pages 290 - 311 |
| W. HUJ. ZHANN. HONGT. R. HULLA. A. STECL. SONGJ. WANGY. HU, POLYM. ADV. TECHNOL., vol. 25, 2014, pages 631 - 637 |
| W. NZAHOU OTTOUS. NORSICF. D'AGOSTOC. BOISSON, MACROMOL. RAPID COMMUN., vol. 39, 2018, pages 1800154 |
| W. ZHAOB. WANGB. DONGH. LIUY. HUM. S. EISENX. ZHANG, ORGANOMETALLICS, vol. 39, 2020, pages 3983 - 3991 |
| X. CHENY. HUL. SONG, POLYM. ENG. SCI., vol. 48, 2008, pages 116 - 123 |
| X. WANG, Y. WANG, X. SHI, J. LIU, C. CHEN AND Y. LI, MACROMOLECULES, vol. 47, 2014, pages 2541 - 2555 |
| X.-Y. WANGY.-Y. LONGY.-X. WANGY.-S. LI, J. POLYM. SCI. PART A: POLYM. CHEM., vol. 52, 2014, pages 3421 - 3428 |
| Y. LUOY. XIER. CHENR. ZHENGH. WUX. SHENGD. XIEY. MEI, FRONT. CHEM. SCI. ENG., vol. 15, 2021, pages 1332 - 1345 |
| Y. OTAS. ITOM. KOBAYASHIS. KITADEK. SAKATAT. TAYANOK. NOZAKI, ANGEW. CHEM. INT. ED., vol. 55, 2016, pages 13281 - 13285 |
| Y. WANGL. ZHANGY. YANGX. CAI, J. THERM. ANAL. CALORIM., vol. 125, 2016, pages 839 - 848 |
| Z. BAIL. SONGY. HUR. K. K. YUEN, IND. ENG. CHEM., vol. 52, 2013, pages 12855 - 12864 |
| Z. CHENM. BROOKHART, ACC. CHEM. RES., vol. 51, 2018, pages 1831 - 1839 |
| Z. QIND. LIQ. LIR. YANG, MATERIALS & DESIGN, vol. 89, 2016, pages 988 - 995 |
| Z. YUW.-X. ZHUI. CABASSO, J. POLYM. SCI. A POLYM. CHEM., vol. 28, 1990, pages 227 - 230 |
| Z.-S. XUL. YANL. CHEN, PROCEDIA ENG., vol. 135, 2016, pages 631 - 636 |
| Z.-Y. WANGY. LIUQ. WANG, POLYM. DEGRAD. STAB., vol. 95, 2010, pages 945 - 954 |
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