IE86186B1 - Polyurethane elastomers and methods of manufacture thereof - Google Patents
Polyurethane elastomers and methods of manufacture thereof Download PDFInfo
- Publication number
- IE86186B1 IE86186B1 IE20100115A IE20100115A IE86186B1 IE 86186 B1 IE86186 B1 IE 86186B1 IE 20100115 A IE20100115 A IE 20100115A IE 20100115 A IE20100115 A IE 20100115A IE 86186 B1 IE86186 B1 IE 86186B1
- Authority
- IE
- Ireland
- Prior art keywords
- polymer
- component
- polyurethane elastomer
- amount
- polyol
- Prior art date
Links
- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 239000004606 Fillers/Extenders Substances 0.000 claims abstract description 114
- 239000000203 mixture Substances 0.000 claims abstract description 62
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 55
- 229920005862 polyol Polymers 0.000 claims description 124
- 150000003077 polyols Chemical class 0.000 claims description 124
- 239000003921 oil Substances 0.000 claims description 111
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 110
- 239000012948 isocyanate Substances 0.000 claims description 105
- 150000002513 isocyanates Chemical class 0.000 claims description 102
- 229920001971 elastomer Polymers 0.000 claims description 59
- 150000001875 compounds Chemical class 0.000 claims description 42
- 239000000806 elastomer Substances 0.000 claims description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 30
- 239000004814 polyurethane Substances 0.000 claims description 28
- 229910021536 Zeolite Inorganic materials 0.000 claims description 26
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 26
- 239000010457 zeolite Substances 0.000 claims description 26
- 125000003118 aryl group Chemical group 0.000 claims description 25
- 229920002635 polyurethane Polymers 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- -1 Polysiloxane Polymers 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 235000006708 antioxidants Nutrition 0.000 claims description 16
- 230000003078 antioxidant effect Effects 0.000 claims description 15
- 239000001569 carbon dioxide Substances 0.000 claims description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 11
- 229920001903 high density polyethylene Polymers 0.000 claims description 11
- 239000004700 high-density polyethylene Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 229920000582 polyisocyanurate Polymers 0.000 claims description 11
- 239000011495 polyisocyanurate Substances 0.000 claims description 11
- 239000004305 biphenyl Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- UJURFSDRMQAYSU-UHFFFAOYSA-N N=C=O.N=C=O.C1=CC=CC2=C(C=CC=C3)C3=C21 Chemical compound N=C=O.N=C=O.C1=CC=CC2=C(C=CC=C3)C3=C21 UJURFSDRMQAYSU-UHFFFAOYSA-N 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 150000004985 diamines Chemical class 0.000 claims description 7
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000004359 castor oil Substances 0.000 claims description 5
- 235000019438 castor oil Nutrition 0.000 claims description 5
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 5
- 229920005906 polyester polyol Polymers 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 239000000429 sodium aluminium silicate Substances 0.000 claims description 5
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 4
- AXGZHADQIWOFBE-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1NC1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1NC1=CC=CC=C1 AXGZHADQIWOFBE-UHFFFAOYSA-N 0.000 claims description 4
- IXHOXXFTTQTNQS-UHFFFAOYSA-N [Ca].[Na].[K] Chemical compound [Ca].[Na].[K] IXHOXXFTTQTNQS-UHFFFAOYSA-N 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 201000007902 Primary cutaneous amyloidosis Diseases 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 208000014670 posterior cortical atrophy Diseases 0.000 claims description 2
- 238000000513 principal component analysis Methods 0.000 claims description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 30
- 239000011800 void material Substances 0.000 abstract description 4
- 239000003981 vehicle Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 11
- 239000010692 aromatic oil Substances 0.000 description 9
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 239000004970 Chain extender Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 231100001223 noncarcinogenic Toxicity 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229920005863 Lupranol® Polymers 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical class OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 229920002209 Crumb rubber Polymers 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000013466 adhesive and sealant Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 231100000003 human carcinogen Toxicity 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005547 polycyclic aromatic hydrocarbon Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C73/00—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
- B29C73/16—Auto-repairing or self-sealing arrangements or agents
- B29C73/163—Sealing compositions or agents, e.g. combined with propellant agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D30/00—Producing pneumatic or solid tyres or parts thereof
- B29D30/04—Resilient fillings for rubber tyres; Filling tyres therewith
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C19/00—Tyre parts or constructions not otherwise provided for
- B60C19/12—Puncture preventing arrangements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C5/00—Inflatable pneumatic tyres or inner tubes
- B60C5/002—Inflatable pneumatic tyres or inner tubes filled at least partially with foam material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/088—Removal of water or carbon dioxide from the reaction mixture or reaction components
- C08G18/0885—Removal of water or carbon dioxide from the reaction mixture or reaction components using additives, e.g. absorbing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
- C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2380/00—Tyres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a polyurethane elastomer comprising an environmentally friendly extender oil with relatively low levels of polycyclic aromatic hydrocarbons (PAH). The polyurethane elastomers of the present invention ideally provide a deflation proof tyre fill compositions. The invention also relates to a method to manufacture of polyurethane elastomers comprising the use of environmentally friendly extender oil with relatively low levels of polycyclic aromatic hydrocarbons (PAH); and further aspect there is provided a method for manufacturing deflation proof tyres comprising filing tyre casing with the polyurethane elastomers of the invention, comprising an extender oil with relatively low levels of polycyclic aromatic hydrocarbons (PAH), and curing the polyurethane elastomers to produce a substantially void free elastomeric filing material within the tyre casing.
Description
POLYURETHANE ELASTOMER USED AS A DEFLATION-PROOF TYRE FILL COMPOSITION The present invention relates to polyurethane elastomers and methods of manufacture thereof. The polyurethane elastomers of the invention comprise polyurethane (PU) elastomer compositions for filling deflation proof tyres. Thus, the present invention relates especially to deflation proof tyre filling polyurethane elastomer compositions and methods of manufacturing said polyurethane elastomers. The present invention also relates to tyres filled with said PU elastomers.
Background ofthe Invention It is known that mixing liquid polyols and isocyanates produces polyurethane polymers of varying elasticity, ranging from very flexible elastomers to semi-rigid and rigid foams. Polyurethane formulations cover an extremely wide range of stiffness, hardness, and densities. Immediately after mixing a polyol and isocyanate, a chemical reaction occurs this is accompanied by a rise in temperature. Blowing agents in the polyol-isocyanate mix start to evaporate due to the heat of the reaction, causing the mixture to expand. The resulting polyurethane polymers are used in a very diverse range of applications, including thermal insulation, upholstery, adhesives and sealants. One of the uses of polyurethane polymers is the manufacturing of wheels and tyres, including rubber tyre treads and deflation proof tyres.
Polyurethane elastomers conventionally used in tyre filling applications are typically ^composed of 30% to 50% (w/w) of an "extender materiar, such as an extender or process oil. Such an extender material has an influence on the final Durometer hardness of the resulting polyurethane elastomers. However, the prime function of the extender material is as an unreactive diluent, thereby making the cost per kilo of the polyurethane elastomers lower than that of unextended polyurethane. Extender materials, such as aromatic oils are conventionally obtained from the petroleum industry and generally consist of approximately 77% to 78% aromatic compounds and approximately 3% to 9% polar compounds. These extender oil materials, such as aromatic process oils, contain very high levels of aromatic compounds, the polycyclic aromatic hydrocarbons (PAH or PCA). Polycyclic aromatic hydrocarbons carry an R45 classification and are carcinogenic.
US Patent Nos. 4 416 844 and 5 070 138 are directed to highly aromatic (78%) oil extended polyurethane compositions suitable for use as deflation proof fillings for tyres. 861 8& US Patent No. 4 416 844, states that aromatic extender oils containing the highest possible amounts of aromatic and polar compounds has better compatibility in the resultant polyurethane elastomer. It has also been determined that extender oil compatibility increases when polyols of high molecular weight are used. However, high molecular weight polyols lead to hard elastomers and so a delicate balance of polyol molecular weight/ oil aromaticity is required. Often achieving this balance to result in an elastomer with desirable properties is difficult.
US Patent No. 4 230 168 is directed to deflation proof tyre filling products where a 10 chlorinated paraffin or dialkyl phthalate plasticiser is used as the extender oil. Such chlorinated paraffin’s have a high negative environmental impact. Furthermore, these dialkyl phthalate plasticisers are known to cause negative effects on human health and the environment United States Patent Specification No. 5 070 138 A "POLYURETHANE ELASTOMER TYRE FILL COMPOSITIONS AND METHOD OF MAKING SAME" discloses a method for making a polyurethane elastomer tyre fill composition wherein a mixture of a) a low functionality (2.0-2.3) 4,4'-diphenylmethane diisocyanate, such as a carboiimide-modified (2.0 functionality) 4,4'-diphenylmethane diisocyanate and b) a nonreactive diluent, such as an oil extender, is mixed with a polyol, such as polypropylene oxide triok The reaction mixture is inserted into a tyre casing under pressure and cured therein to form an essentially void-free tyre filler. The tyre fill composition maintains pressure within the tyre during use. No prepolymer step is necessary in the method of US 5 070 138 A.
United States Patent Specification No. 5 070 138 A discloses that a typical polyurethane elastomer is produced by the reaction of two components, an A component containing the isocyanate and a B component, usually a polyol containing the hydrogen donor. According to US 5 070 138 A, tyre fill polyurethane elastomers made in accordance with known prior art methods have used an isocyanate A component consisting of an isocyanate prepoiymer. In US 5 070 138 A, the A component consists essentially of a mixture of a low functionality (2.0-2.3) 4,4’-diphenylmethane diisocyante with a nonreactive diluent, such as an extender oil, adjusted to a specific % NCO such that a one-to-one volume mix with the B component can be obtained. According to US 5 070 138 A, the non-reactive diluents used in making the component A mixture with the Eow functionality 4,435 diphenylmethane diisocyanate include a number of extender oils. US 5 070 138 A discloses that these oils are complex distillates of crude oil and have a high percentage of aromatic content and that some oils may also contain polar compounds. US 5 070 138 A also discloses that a typical oil for use as a polyurethane extender is sold under the trademark Califlux LP by its manufacturer, Witco Corporation and that such extender oil has about 78 percent aromatics and 9 percent polar compounds with the remainder being saturates. The extender oil of US 5 070 138 A may be present in amounts from at least about 10% up to about 50% and even as high as 60% of the final reaction product. Thus, US 5 070 138 A discloses a polyurethane elastomer tyre filling composition which contains extender oil having a high aromatic content including a high level of polycyclic aromatic hydrocarbons (PAH’s).
International Patent Publication No. WO 2008/080557 A "SELF-SEALING COMPOSITION FOR A PNEUMATIC OBJECT" discloses the use of an elastomer composition as a seifsealing composition in a pneumatic object, such as a pneumatic tyre, the elastomer composition comprising at least, as the main elastomer, a styrene thermoplastic (TPS) elastomer and an extension oil at a concentration of between 200 and 700 pee (parts by weight per 100 parts of elastomer). The disclosure of WO 2008/080557 A also relates to an airtight anti-puncture laminate which can be used, in particular, in the above-mentioned pneumatic object, comprising at least a first anti-puncture layer consisting of the self20 sealing composition and a second airtight layer, for example based on butyl rubber. The patent specification of WO 2008/080557 A discloses that preferably, the extender oil is selected from the group consisting of oils from the polymerization of olefins, diolefins or monoolefin, Naphthenic oils (a high or low viscosity), aromatic oils, mineral oils, and mixtures of these oils.
United States Patent Specification No. 4 416 844 A DEFLATION-PROOF PNEUMATIC TYRE AND ELASTOMERIC FILLINGS THEREFOR" discloses a deflation-proof pneumatic tyre comprises a casing and a substantially void-free, preferably oil-containing elastomeric filling material. The tyre casing is injected with a combination comprising a polyol, an organic polyisocyanate and water, in amounts and under conditions sufficient to produce carbon dioxide and form a polyurea-containing polyurethane elastomer in which the carbon dioxide is dissolved in the elastomer, thereby providing a substantially voidfree filling material. The formulation permits the addition of a substantial amount of extender oil while retaining an acceptable level of hardness.
According to US 4 416 844 A, it is preferred to add at (east 10 volume percent, up to about 60 volume percent, of an extender oil while retaining a Durometer hardness of at least 20 on the A scale. US 4 416 844 A discloses that preferably, the extender oil is substantially aromatic and may contain polar compounds. According to US 4 416 844, a particularly effective oil is the aromatic extender oil sold under the trade mark Califlux LP or Bearflex LPO, both sold by the Whitco Chemical Company. Califlux LP comprises about 78 percent aromatics and 9 percent polar compounds, the remainder being saturates. Thus, US 4 416 844 A discloses a deflation-proof tyre comprising an elastomeric filling material; the filling material comprising a polyurea-containing polyurethane elastomer and extender oil and the extender oil used in the process of US 4 416 844 A comprises about 78 percent aromatics.
Problems associated with Prior Art The conventional extender oils disclosed in the prior art in the patent publications referred 15 to above pose problems in terms of personal and environmental toxicity. Such extender oils, i.e. the aromatic oils used in the prior art, are waste products from the petroleum industry, contain high levels of polycyclic hydrocarbons (PAH’s) and are known to act as human carcinogens. As such, the handling and disposal of such materials present both environmental and health hazards. In addition, it is likely that the use of high aromatic content extender materials will be strictly regulated and potentially banned in the future.
The present invention seeks to alleviate these disadvantages and in particular, aims to overcome the toxicity problems associated with conventional polyurethane elastomers, whilst at the same time maintaining the integrity of the resultant elastomers, in terms of hardness, rebound etc for tyre fill applications including in particular, deflation proof tyre fill compositions.
Often, balancing the need to use different non-environmentally toxic materials with the need to obtain elastomers with suitable properties presents technical problems and difficulties. The present invention also seeks to alleviate these problems.
Summary of the Invention According to a general aspect of the invention, there is provided a polyurethane elastomer comprising an environmentally friendly extender oil with relatively low amounts of polycyclic aromatic hydrocarbons (PAH) compared with known polyurethane elastomers.
Thus, the present invention provides a polyurethane (PU) elastomer for use as a deflation proof tyre fill composition, the polyurethane elastomer produced from a polyol pre-polymer (Component A) and an isocyanate pre-polymer (Component B), the polyol pre-polymer (Component A) comprising a polyol and the isocyanate pre-polymer (Component B) comprising an isocyanate; the polyol pre-polymer and/or the isocyanate pre-polymer comprising an extender oil having a relatively low polycyclic aromatic hydrocarbons content of less than 10% (w/w) of polycyclic aromatic hydrocarbons.
According to another general aspect of the invention, there is provided a method for manufacture of polyurethane elastomers comprising the use of environmentally friendly extender oil with relatively low levels of polycyclic aromatic hydrocarbons (PAH).
By "relatively low amounts of polycyclic aromatic hydrocarbons is meant less than 10% by weight; preferably less than 5% and more preferably 3% (w/w).
By relatively low aromatic(s) content is meant less than 60% aromatic(s) content; preferably 40-60% aromatic(s) content.
Thus, the present invention also provides a method for producing a polyurethane 20 elastomer for use as deflation proof tyre fill compositions, the method comprising the following steps: (a) preparing a polyol pre-polymer (Component A); (b) preparing an isocyanate pre-polymer (Component B); and (c) combining the polyol pre-polymer (Component A) with the isocyanate pre-polymer (Component B) and curing to form the polyurethane elastomer, and wherein the polyol pre-polymer and/or the isocyanate pre-polymer comprise an extender oil having a relatively low polycyclic aromatic hydrocarbons content of less than 10% (w/w) of polycyclic aromatic hydrocarbons.
Ideally, the polyurethane elastomers of the. present invention are used as deflation proof . tyre filling polyurethane elastomers compositions.
According to yet another general aspect of the invention, there is provided the use of a polyurethane elastomer of the invention comprising environmentally friendly extender oil with relatively low levels of polycyclic aromatic hydrocarbons (PAH) in the manufacture of a deflation proof filled tyre.
According to a still further aspect of the invention, there is provided a method for manufacturing deflation proof tyres comprising filing a tyre casing with the polyurethane elastomers of the invention, comprising an environmentally friendly extender oil with reduced levels of polycyclic aromatic hydrocarbons (PAH), and curing the polyurethane elastomers to produce a substantially void free elastomeric filing material within the tyre casing.
Advantageously, this invention involves the use of non-toxic environmentally friendly extender oil materials with relatively low levels of polycyclic aromatic hydrocarbons (PAH) in the manufacture of the polyurethane elastomers. The extender oil of the invention is used as a direct replacement for conventional aromatic oils, chlorinated paraffin's and dialkyl phthalate plasticisers which are currently used in the manufacture of polyurethane elastomers. Thus, this invention overcomes the toxicity problems associated with conventional extenders oils and provides a resultant polyurethane elastomer which is non. toxic. In addition, we have found that the resultant polyurethane elastomer has ideal properties for deflation proof tyre filling applications.
It will be understood that the general method of manufacture of the two component polyurethane elastomers involves the preparation of a polyol pre-polymer (Component A) and an isocyanate pre-polymer (Component B), which are combined and cured to form the resultant polyurethane elastomers. The extender oil of the present invention is used in the manufacture of both the polyol prepolymer (Component A) and isocyanate prepolymer (Component B). Alternatively, the extender oil may be used entirely in Component A only or Component B only.
Accordingly, the present invention provides a polyurethane (PU) elastomer for use as a deflation proof tyre fiii composition, the polyurethane elastomer produced from a polyol pre-pofymer (Component A) (comprising a polyol) and an isocyanate pre-polymer (Component B) (comprising an isocyanate); the polyol pre-polymer and/or the isocyanate pre-polymer comprising an extender oil having relatively low polycyclic aromatic hydrocarbons content.
Preferably, the poiyol comprises polyester polyol and/or polyether polyol, or combinations 10 thereof.
Ideally, the polyol has a molecular weight of at least 3000 and has a preferred molecular weight of 6000 to 7000.
The isocyanate may be selected from any one or more of the following group: polymeric diphenylmethane-4-4 Diisocyanate, hexamethylene Diisocyanate, polymethylene polypheny! isocyanate, m-phenylene Diisocyanate, p-phenylerte Diisocyanate, 3,3-dimethyl - 4-4 diphenyl Diisocyanate, 3,3-dimethoxy-4-4 biphenylene Diisocyanate, 2-2,4-4 tetramethyt-4-4 biphenylene Diisocyanate, 3,3-dimethyl-4-4 diphenylamine Diisocyanate, 4'4-diphenyl isopropylidene and/or polymethylene polypheny! isocyanate. _____________________ ______________________ ........ __________ Advantageously, the polyurethane elastomer includes an extender oil which is an environmentally friendly, substantially non-carcinogenic extender oil having relatively low levels of polycyclic aromatic hydrocarbons (PAH or PCA) of less than 10% (w/w) and preferably of less than 5% (w/w) and more preferably of about 3% (w/w).
Preferably, the extender oil included in the polyurethane elastomer compositions of the present invention is CATENEX SNR ™ (supplied by Shell Chemicals). This particular extender oil has an aromatic content of less than 60% (specifically about 44% (w/w)) while having a polycyclic aromatic hydrocarbon (PAH) content of 3%. Since the PAH content is low (at 3%), this extender oil is classified as non-carci nogen ic.
The extender oil used in the present invention is not derived as a waste product from the petroleum industry.
Preferably, the extender oil is included in an amount from 5% to 60% (w/w).
Advantageously, the extender oil may be included in the polyol pre-polymer (Component A) and/or the isocyanate pre-polymer (Component B). ideally, the extender oil has an aromatic content of approximately 44% and a polar content of approximately 1% (w/w).
Ideally, the extender oil of the present invention has the following properties: - a polycyclic aromaticcompound content of about 3% or less by weight; - ___a kinematics viscosity at 40 degrees C of approximately 175 mm2/s; a flash point of 240 degrees C or more; an aromatic hydrocarbon content of about 40-45% by weight; and - a polar compound content between 1.0% and 4.0% (preferably, between 0.1% and 2.5%).
Thus, the extender oil of the present invention has relatively low aromatic content and relatively low polycyclic aromatic hydrocarbons.
Ideally, the polyurethane elastomer includes a tin based amine catalyst, preferably included in an amount in the range from 0.01 % to 2.00% (w/w).
The polyurethane elastomer preferably includes high density polyethylene (HDPE) having 35 a crystalline melting point of 132 degrees Celsius and ideally, is included in an amount in the range from 0.5% to 5.0% (w/w) based on the weight of the polyol pre-polymer (Component A).
Conveniently, the polyurethane elastomer comprises Zeolite (ideally, in the form of Zeolite 5 paste), preferably in an amount in the range from 0.5% to 2.0% (w/w) based on the weight of the polyol pre-polymer (Component A).
The Zeolite may comprise a Potassium-calcium-sodium alumino-silicate type Zeolite in Castor Oil.
Advantageously, the polyurethane elastomer may comprise an anti-oxidant. The amount of antioxidant included can be up to 2.0% (w/w) based on the weight of the polyol prepolymer (Component A). The anti-oxidant may comprise a Zeolite.
Preferably, the polyurethane elastomer of the present invention comprises water in an amount up to 2.0% (w/w) based on the weight of the polyol pre-polymer (Component A). The water is added to the polyol pre-polymer (Component A), not to the isocyanate prepolymer (Component B) The polyurethane elastomer ideally includes recycled polyurethane or polyisocyanurate ______powder; preferably in an amount from 0.5% to 6.92 % (w/w) and most preferably, in an amount from 2.9% to 3.0% (w/w)·____ Advantageously, the polyurethane or polyisocyanurate powder included in the composition of the present invention, was heretofore a waste product which was left over after manufacturing processes including manufacturing of polyurethane or polyisocyanurate insulation. Heretofore, this waste material was dumped in land fills but now can be used as a useful ingredient in the polyurethane elastomer of the present invention.
Advantageously, the polyurethane elastomer of the present invention comprises recycled rubber crumb, preferably having a particle size in the range from 0.5 mm to 1.5 mm, and most preferably, the particle size is 1.0 mm.
The inclusion of rubber crumb from waste tyres which have heretofore been a waste product, is a further significant advantage of the polyurethane elastomer compositions of the present invention.
Previously, used vehicle tyres were entirely a waste product with all the environmental implications that entails but now such used vehicle tyres can find useful application as an ingredient in the compositions of the present invention.
Ideally, the polyurethane elastomers of the present invention comprise recycled rubber crumb included in an amount from 1% to 7% (w/w) and preferably, included in an amount of 5.77% (w/w).
The polyurethane elastomer of the present invention comprise a Polysiloxane based surfactant in hydrocarbon and preferably, in an amount up to 2.0% (w/w) based on the weight of the polyol pre-polymer (Component A).
The polyurethane elastomer of the present invention may comprise an amine extender such as metaphenylamine diamine. Preferably, the diamine extender is included in an amount from 0.1% and 2.0% (w/w) based on the weight of the polyol pre-polymer (Component A).
Advantageously, the polyurethane elastomer cf the present invention comprises a compound which absorbs Carbon Dioxide.
Ideally, the carbon dioxide absorbing compound comprises Zinc oxide. Preferably the carbon dioxide absorbing compound is included in an amount up to 5.0% (w/w) based on the weight of the polyol pre-polymer (Component A).
Ideally, the polyurethane elastomer includes Monofunctional isocyanate preferably included in an amount in the range from 0.1 to 5% (w/w) based on the total weight of the isocyanate pre-polymer (Component δ).
Potential end applications for a deflation proof tyre include use to deflation-proof and extend, the life of off-the-road, industrial and mining tyres.
Ideally, a deflation proof tyre manufactured in accordance with the invention has a Durometer hardness in the range, Shore A scale, of 5 to 60 depending on the requirements of the tyre. For instance, a tyre for a golf buggy can have a hardness of 7-8 shore, whereas a tyre for a dumper truck would be much higher. For example, a golf buggy tyre or a ride-on lawn mower vehicle would use a tyre having relatively low Durometer, whereas a high Durometer may be used on heavy mining equipment vehicles. The actual hardness of the tyre depends on the size/weight of the vehicle on which the tyre will be used and its application. For example, a 40 tonne vehicle may need tyres of hardness 35 shore whereas an 80 tonne vehicle may need a tyre having hardness of 55 shore.
Thus, the resulting hardness of a tyre Oiled with the polyurethane elastomer of the present invention can be controlled by the formulation of the polyurethane elastomer composition. Thus for instance, very hard tyres would be required for tyres on a dumper truck whereas for lighter vehicles such as cars and even gotf buggy wheels where very light, noncompressive tyre would be needed on a golf course, a much softer filling composition can be selected.
Thus, in a preferred application, the polyurethane elastomers of the present invention, are 20 deflation proof tyre fill compositions.
In a further aspect, the present invention atso provides a method for producing a polyurethane elastomer for use in the manufacture of deflation proof tyre fill, the method comprising the following steps: (a) preparing a polyol pre-polymer (Component A) comprising a poiyot; (b) preparing an isocyanate pre-polymer (Component B) comprising an isocyanate; and (c) combining the polyol pre-polymer (Component A) with the isocyanate pre-polymer (Component B) and curing to form the polyurethane elastomer; wherein the polyol pre-polymer an/or the isocyanate pre-polymer comprise an extender oil having a relatively low polycyclic aromatic hydrocarbons content of less than 10% wfw of polycyclic aromatic hydrocarbons.
Step (c) of the above method is carried out in situ i.e. the components are mixed with each other just before being pumped into a tyre, resulting in a reaction inside the tyre producing the polyurethane elastomer tyre filling composition of the present invention.
Ideally, the polyol pre-polymer comprises polyester polyol and/or polyether polyol, or combinations thereof.
Advantageously, the polyol has a molecular weight of at least 3000 and has a preferred molecular weight in the range from 6000 to 7000.
Ideally, the isocyanate is selected from any one or more of the following group: polymeric diphenylmethane-4-4 Diisocyanate, hexamethylene Diisocyanate, polymethylene polyphenyl isocyanate, m-phenylene Diisocyanate, p-phenylene Diisocyanate, 3,3-dimethyl - 4-4 diphenyl Diisocyanate, 3,3-dimethoxy-4-4 biphenylene Diisocyanate, 2-2,4-4 tetramethyl-4-4 biphenylene Diisocyanate, 3,3-dimethyl-4-4 diphenylamine Diisocyanate, 4’4-diphenyl isopropylidene and/or polymethylene polyphenyl isocyanate.
Advantageously, the method of the present invention further includes an extender oil which is an environmentally friendly, substantially non-carcinogenic extender oil having relatively low levels of polycyclic aromatic hydrocarbons (PAHs or PCAs). The extender oil may be included in the polyol pre-polymer (Component A) and/or the isocyanate prepolymer (Component B). The extender oil is preferably included in an amount from 5% to 60% (w/w).
The extender oil most preferably has an aromatic content of approximately 44% of which polycyclic aromatic hydrocarbon content is about 3%; and the extender oil preferably has a polar content of approximately 1% (w/w).
The method of the present invention ideally also includes the step of adding a tin based amine catalyst, ideally, in an amount in the range from 0.01 % to 2.00% (w/w).
In the method of the present invention, the polyurethane elastomer preferably includes high density polyethylene (HDPE) having a crystalline melting point of 132 degrees Celsius. Preferably, the HDPE is included in an amount of 0.5% to 5.0% (w/w) based on the weight of the polyol pre-polymer (Component A), The method ideally comprises the step of including Zeolite; preferably, the Zeolite is 5 included in an amount from 0.5% to 2.0% (w/w) based on the weight of the polyol prepolymer (Component A).
Preferably the Zeolite is included In the form of a paste.
Ideally, the Zeolite comprises a Potassium-calcium-sodium alumino-silicate type Zeolite in Castor Oil.
The method may include the step of including an anti-oxidant.
The amount of antioxidant included is preferably, up to 2.0% (w/w) based on the weight of the polyol pre-polymer (Component A).
Advantageously, the method comprises the step of including water in the polyol prepolymer (Component A); preferably, in an amount up to 2.0% (w/w) based on the weight of the polyol pre-polymer (Component A).
The method of the present invention ideally comprises the step of including recycled polyurethane or polyisocyanurate powder; preferably, in an amount in the range from 0.5% to 6.92 % (w/w) and most preferably, in an amount of 2.9% to 3.0% (w/w).
The method of the present invention may also advantageously, comprise the step of including recycled rubber crumb; ideally, having a preferred particle size of 0.5 mm to 1.5 mm. The most preferred particle size is 1.0 mm.
The recycled rubber crumb may be included in an amount in the range from 1 % to 7% (w/w). Most preferably, the recycled rubber crumb may be included in an amount of 5.77% (w/w).
The method may comprise the step of including a Polysiloxane based surfactant in hydrocarbon in an amount from 0% to 2.0% (w/w) based on the weight of the polyol prepolymer (Component A).
The method may comprise the step of including an amine extender such as metaphenylamine diamine. Preferably, the amine extender is included in an amount from 0.1% and 2.0% (w/w) based on the weight of the polyol pre-polymer (Component A).
The method may advantageously, comprise the step of including a compound which absorbs Carbon Dioxide, ideally, the carbon dioxide absorbing compound comprises Zinc oxide. Preferably, the carbon dioxide absorbing compound may be included in an amount in the range of 0% to 5.0% (w/w) based on the weight of the polyol pre-polymer (Component A).
The method may comprise the step of further including an additive comprising a Monofunctional isocyanate preferably in an amount in the range from 0.1 to 5% (w/w) based on the total weight of the isocyanate pre-polymer (Component B).
In another aspect, the present invention also provides a deflation proof tyre filled with the above referred to polyurethane elastomers and also provides a deflation proof tyre produced using the above method of the present invention.
Detailed Description of the Invention Each component of the invention, comprising the extender oil, polyol pre-polymer (Component A) and isocyanate pre-polymer (Component B) is described in more detail.
EXTENDER OIL The extender oil of the invention serves as a filler or extender for the polyurethane elastomer. The extender oil of the invention is environmentally friendly extender oil which is not toxic to humans or environmentally hazardous and has relatively low levels (much reduced below the levels of the prior art) of polycyclic aromatic hydrocarbons (PAH), otherwise known as polycyclic aromatic compounds (PCA).
Advantageously, the extender oil of the invention does not comprise polycyclic aromatic hydrocarbons (PAH). This ensures that the resultant polyurethane elastomer is environmentally friendly and non-toxic.
Ideally, the extender oil of the invention has an aromatic content of approximately 40% to 60% and a polar content of approximately 1 % to 2.5%.
We have found that this extender oil shows high compatibility with polyurethane systems while maintaining optimum performance properties in the resultant polyurethane.
Ideally, the extender oil of the present invention has the following properties: a polycyclic aromatic hydrocarbons content less than 10%, more preferably, less than 5% and most preferably about 3% by weight; - a kinematics viscosity at 40 degrees C of approximately 175 mmz/s; a flash point of 240 degrees C or more; an aromatic hydrocarbon content is 40-45% by weight; and a polar compound content between 0.1 % and 4.0% (preferably between 1 % and 2.5% (w/w).
Ideally, the extender oil is used in amounts of from approximately 5% to 60% (w/w) based on weight of total polyurethane elastomer. It is important to ensure that the correct level of extender oil is used; addition levels up to a maximum of approximately 60% (w/w) based on the weight of total polyurethane elastomer are possible. However, the hardness of the tyre fill decreases greatly at levels higher than this.
In addition, it will be understood that the quantity of the extender oil may be reduced and replaced with the equivalent weight of recycled powdered rubber or other filling materials such as recycled plastic. In this situation, it may be desirable to increase the quantity of catalyst, so as to accelerate the crosslinking time and crosslinking density.
This extender oil of the invention is used in the manufacture of the two component polyurethane elastomers of the present invention. As such, the extender oil of the invention may be used in the manufacture of both the polyol pre-polymer (Component A) and the isocyanate pre-polymer (Component B). This is dependant on the type of metering equipment used to fill the tyre with the elastomers.
The preferred extender oil which may be used is Catenex SNR® (supplied by Shell 5 Chemicals). Ideally, the Catenex SNR® is used in amounts of from 5% to 60% (w/w) on total formulation. Catenex SNR® has an aromatic content of approximately 44% and a polar content of approximately 1% and is non-carcinogenic. Typical physical characteristics of the Catenex SNR® extender oil are shown in the table below: CATENEX SNR PHYSICAL & CHEMICAL PROPERTIES Catenex SNR SNR Colour (ASTM) ISO 2049 2.0 Density at 15 °C kg/m3 ISO 12185 909 Refractive Index at 20°C ASTM D 12118 1.501 Flashpoint PMCC °C ISO 2719 240 Pour Point °C ISO 3016 -6 Kinetic Viscosity at 20 °C mm2/s at 40 °C mm2/s at 100 °C mm2/s ISO 3014 175 14 Carbon Type Distribution CA/CN/CP (non S-corrected) % CA/CN/CP (S-corrected) % DIN 51378 / ASTM D 2140 mod. 12/30/58 12/29/59 Refractive Intercept (Rl) 1.0480 Viscosity Gravity Constant (VGC) 0.840 Sulphur (X-ray) %m/m ISO 14596 0.2 Aniline Point °C ISO 2977 99 Clay Gel Analysis polar components %m/m aromatic components %m/m saturated components %m/m ASTM D 2007 1 44 55 Evaporation Loss (22h/107°C) %m/m ASTM D 972 <0.5 Neutralisation Value KOH/g mg ASTMD664 0.03 PCA-Constant (DMSO method) %m/m IP 346 2.0 Sum of 6 Individual PAHs (BLIC) mg/kg Grimmer <2 Other oils which may be used are outlined as follows: Catenex™ Oil S321 Catenex ™ PH 908 Catenex ™ Oil S232 Catenex™ PH 908 Catenex ™ Oil S326 Catenex ™ PH941 FU Catenex™ Oil S373 Catenex ™ S946 Catenex ™ Oil S379 Catenex ™S 321 Prorex™ 15 Flexon™683 Vivatec ™ 200 Plaxolene ™ MS Further details on polyol pre-polymer (Component A) and isocyanate pre-polymer (Component B) are given below, together with the various additives ideally used in the preparation ofthe polyurethane elastomers ofthe present invention.
POLYOL - COMPONENTA Any polyol may be used in the manufacture of the polyol pre-polymer (Component A) of the invention.
It will be understood that the polyol used may comprise polyester polyol and/or polyether polyol, or combinations thereof.
, The minimum molecular weight of the polyol is 3000 is required. Molecular weights under this value may lead to the formation of very soft elastomers. The preferred polyol molecular weight is 6000 to 7000. Higher molecular weight polyol will give better compatibility with extender oil content. 17.
Pre-polymer Polyol Component A Avr % (w/w) based on the total weight of the resultant polyol Component A Minimum % (w/w) based on the total weight of the resultant polyol Component A Maximum % (w/w) based on the total weight of the resultant polyol Component A Polyol 87 75 95 Extender Oil 10 5 40 Catalyst 0.1 0.01 1 Polyethylene fiber 1 0.1 7 Zeolite Paste 0.2 0 2 Water 0.2 0 2 Chain Extender 1 0.1 7 Surfactant 0.2 0 2 Antioxidant 0.2 0 2 Zinc oxide 0 2.5 Ideally, the amount of polyol used in the manufacture of the pre-polymer is from approximately 50% to 70% w/w based on the total weight of the resultant pre-polymer Component A.
Ideally, the amount of extender oil used in the manufacture of the pre-polymer is from approximately 5% to 60% % w/w based on the total weight of the resultant pre-polymer.
Component A. The extender oil with reduced levels of polycyclic aromatic hydrocarbons (PAH), as defined above, is used in the preparation of the polyol pre-polymer (Component A).
Further additives may be used in the manufacture of the polyol pre-polymer (Component A) including, but not limited to a catalyst which accelerates the reaction between the polyol and isocyanate; polyethylene fibers which increase the flexural strength of the resulting elastomer; Zeolite (preferably in the form of a paste) which absorbs excess water which would, if present, react with the isocyanate and produce large amounts of carbon dioxide; water (which in the absence of the Zeolite paste may be used to accelerate the reaction; antioxidant which prevents photo or thermal oxidation of the resulting elastomers; and surfactant and/or chain extenders which increase the crosslinking density of the elastomers. These materials are used in formulating the polyurethane elastomers of the present invention so as to produce the desired properties such as the desired hardness needed depending on application/use.
Suitable catalysts include tin based amine catalysts. Ideally, the amount of catalyst used is from 0.01% to 2.00% (w/w) based on the weight of the resultant pre-polymer Component A. The catalyst is vital in the formulation as it accelerates the reaction between the polyol and the isocyanate through the promotion of gel formation and accelerating tack free time.
Polyethylene fibers may be used. These fibers are manufactured from high density polyurethane (HDPE) and have a crystalline melting point of 132 deg C. These long chain polymer fibres serve to transfer load more effectively to the backbone of the polymer by strengthening the intermolecular interactions resulting in a more tough material and are commonly used in rubber manufacture. Ideally, the amount of polyethylene fibers used is from 0.5% to 5.0% (w/w) based on the weight of the polyol pre-polymer (Component A).
Zeolite paste may be used. Ideally, the amount of Zeolite used is from 0.0% to 2.0% (w/w) based on the weight of the polyol pre-polymer (Component A).
Water may be used. Ideally, the amount of water used is from 0% to 2.0% (w/w) based on the weight of the polyol pre-polymer (Component A). It will be understood that water is only used when Zeolite paste is absent. Water and Zeolite paste are mutually exclusive components.
Recycled polyurethane or polyisocyanurate powder (commonly found in fridges and cold stores etc) may be used as a cost effective filler to increase the hardness of the elastomers. The preferred particle size of the recycled polyurethane or polyisocyanurate powder is between 500 to 1000 microns. The addition of this material produces rigid elastomers with a Shore A hardness of 33. These elastomers may find use in tyre fill applications where maximum compression strength is required (i.e. quarry vehicles).
Recycled polyurethane or polyisocyanurate powder may be used in an amount from 0.5% to 6.92 % (w/w). The preferable addition level is 2.9% to 3.0% (w/w).
Recycled rubber crumb as obtained from used vehicle tyres may also be used as cost effective filler. The benefit offered by this material is that it is a cheap easily available and otherwise is a difficult to dispose of material. The preferred particle size of the recycled rubber crumb is from 0.5 mm to 1.5 mm. Most preferably, the particle size of the recycled rubber crumb is 1.0 mm.
Recycled rubber crumb may be used in amounts from 1% to 7% (w/w). The most preferred addition level is 5.77% (w/w).
Suitable antioxidants include a Potassium-calcium-sodium alumino-silicate type Zeolite in Castor Oil. Ideally, the amount of antioxidant used is from 0% to 2.0% (w/w) on the weight of the polyol pre-polymer (Component A).
Suitable surfactants include Polysiloxane resins in hydrocarbon. Ideally, the amount of surfactant used is from 0% to 2.0% (w/w) based on the weight of the polyol pre-polymer (Component A).
Suitable chain extenders include a diamine extender such as metaphenylamine diamine, ideally, the amount of chain extender used is between 0.1% and 2.0% (w/w) based on the weight of the polyol pre-polymer (Component A).
Zinc oxide may be used. Ideally, the amount of zinc oxide used is from 0 to 5.0% based on the weight of the polyol pre-polymer (Component A). The function of the Zinc Oxide is to absorb excess carbon dioxide which, if left in the polyurethane elastomers, would produce soft foam.
ISOCYANATE - COMPONENT B Isocyanates with two or more functional groups are ideally used in the present invention.
Ideally, aromatic TDl based isocyanates are used. Aromatic isocyanates are ideal for the present purposes as they are more reactive and more economical.
However, mixes of isocyanates with both aromatic and aliphatic groups may also be used.
Preferably, the isocyanate is selected from polymeric diphenylmethane-4-4 Diisocyanate. 5 Other organic polyisocyanates which could be used in the invention include hexamethylene Diisocyanate, polymethylene polyphenyl isocyanate, m-phenylene Diisocyanate, p-phenylene Diisocyanate, 3,3-dimethyl - 4-4 diphenyl Diisocyanate, 3,3dimethoxy-4-4 biphenylene Diisocyanate, 2-2,4-4 tetra methyl-4-4 biphenyiene Diisocyanate, 3,3-dimethyl-4-4 diphenylamine Diisocyanate, 4’4-diphenyl isopropylidene and/or polymethylene polyphenyl isocyanate.
Pre-polymer Isocyanate Component B Avr % (w/w) based on the total weight of the resultant isocyanate Component B Minimum %(w/w) based on the total weight of the resultant isocyanate Component B Maximum % (w/w) based on the total weight of the resultant isocyanate Component B isocyanate 10 5 25 Extender Oil 89 80 95 Monofunctional Isocyanate 0.5 0.1 5 Preferably, the amount of isocyanate used is from approximately 2 to 15% w/w based on the total composition of isocyanate prepolymer Component B. It will be understood that increasing the percentage of isocyanate will increase the cross-linking of the elastomer and the resultant hardness.
The extender oil with relatively low levels of polycyclic aromatic hydrocarbons (PAH), as defined above, is used in the preparation of isocyanate prepolymer (Component B).
Ideally, the amount of extender oil used is from approximately 5.0% to 60% w/w based on the total weight of combined Component A and Component B.
Ideally, the ratio of isocyanate to extender oil is approximately 1:9. The preferred ratio of 25 extender oil to isocyanate is 100:6.5 and 100:13.0.
Monofunctional isocyanate may also be used at a level of from approximately 0.1 to 5% w/w based on the total weight of the isocyanate pre-polymer (Component B).
Further additives may be used in the manufacture of the isocyanate pre-polymer (Component B) including, but not limited to, surfactants, antifoams, defoamers, solvents etc.
POLYURETHANE ELASTOMER MANUFACTURING PROCESS According to a general embodiment of this aspect of the invention, the method for producing polyurethane elastomer of the invention comprises the preparation of polyol pre-polymer, the preparation of isocyanate pre-polymer followed by combining the polyol pre-polymer and isocyanate pre-polymer to form a polyurethane elastomer.
It will be understood that the step of combining the polyol pre-polymer and isocyanate prepolymer to form the polyurethane elastomer may occur in situ in the tyre filling application. As such, the two component prepolymers are combined either in a tyre or in a two component static mixer just before being injected into a tyre. The two component pre20 polymers are subjected to the appropriate conditions for curing to form a polyurethane elastomer to take place.
The use of the specific extender oil with relatively low levels of polycyclic aromatic hydrocarbons (PAH), as defined above, results in an environmentally friendly polyurethane elastomer. Furthermore, the specific formulation of the polyurethane elastomers of the present invention permits the addition of a substantial amount of extender oil whilst retaining an acceptable level of hardness. This is desirable for commercial purposes to result in an environmentally acceptable elastomer, which is costeffective yet retains the desirable physical characteristics that permit it for use in tyre filling applications.
Pre-polymer Isocyanate Component B Avr % (w/w) based on the total weight of the polyurethane elastomer Minimum % (w/w) based on the total weight of the polyurethane elastomer Maximum % (w/w) based on the total weight of the polyurethane elastomer Pre-polymer Isocyanate Component B 50 25 75 Pre-polymer Polyol Component A 50 25 75 According to one specific embodiment of the invention, the method for producing polyurethane elastomer of the invention comprises the following general process steps: a) The preparation of the Polyol pre-polymer comprising: (i) Charging the mixer with the oil extender of the invention and heating to approximately 25 deg C; (ii) Charging the mixer with a polyol pre-polymer and mixing for approximately five minutes: (iii) Adding at least one catalyst; (iv) Adding Zeolite paste or water; (v) Adding at least one antioxidant, surfactant and at least one chain extender to form a polyol pre-polymer; (vi) Adding inert filler such as recycled powdered polyurethane or polyisocyanurate foam or recycled rubber crumb; b) The preparation of the Isocyanate pre-poiymer comprising (I) Charging the mixer with the oil extender of the invention and heating to approximately 25 deg C; (ii) Adding an isocyanate; (iii) Adding a monofunctional isocyanate (this may or may not be applicable, depending on the humidity of the environment in which the resins are blended) thereby forming an isocyanate pre-polymer; and c) Combining the Polyol pre-polymer and Isocyanate pre-polymer to form a polyurethane elastomer.
APPLICATIONS Ideally, the polyurethane elastomers of the invention are used in the manufacture of deflation proof filled tyres. Though it is to be understood that other uses for the polyurethane elastomers of the present invention are aiso envisaged and are possible within the scope of the invention.
We have found that the use of the extender oil of the invention with an aromatic content of approximately 40% and 80% and a polar content of approximately 1% to 4.0% in the generation of the pre-polymer components, provides a suitable elastomer for use in the manufacture of deflation proof tyres. Ideally, the extender oil used in the manufacture of the prepolymer components of the present invention has the following properties: a polycyclic aromatic hydrocarbons content of less than 10%, more preferably less than 5% and most preferably, about 3% by weight; - a kinematics viscosity at 40 degrees C of approximately 175 mm2/s; a flash point of 240 degrees C or more; and a polar compound content between 1% and 4% (w/w).
This is the first time that this particular extender oil type has been used in the manufacture of an elastomeric tyre fill composition. It is important to note that many elastomers are used in the manufacture of rubber for tyre treads, however, these elastomeric rubber are not suitable for use as tyre fill composition. The desirable physical properties of rubber tyre treads and tyre fill compositions are very different.
For this particular use, the pre-polymer components are stored separately and are combined ΐη-situ in a tyre. Thus, the pre-polymer components which form the polyurethane are introduced into a tyre under pressure and cured to form essentially voidfree tyre filler.
Ideally, the tyre fill polyurethane elastomer composition is injected into the tyre through the valve stem via a pumping unit, ensuring the correct mixing ratio of the respective prepolymers and the appropriate final tyre pressure.
Curing takes place in under 10 hours to cure into a soft, yet resilient elastomer which ensures that the interior of the tyre is completely void free, thereby eliminating any deflations caused by penetrations of the tread or sidewall. We have found that this soft resilient inner core gives the same ride and performance characteristics as air filled tyres but eliminates punctures and under inflation for the life ofthe tyre.
Hence, the resultant polyurethane elastomer filled tyre is deflation proof and substantially void-free. We have surprisingly found that this tyre fill composition maintains pressure during use and has excellent physical and thermal properties.
Ideally, a deflation proof tyre manufactured in accordance with the present invention has a Durometer hardness in the range, Shore A scale, of 5 to 60. For example, a golf buggy tyre or a ride-on lawn mower vehicle would use a tyre having relatively low Durometer, whereas a high Durometer is needed on heavy mining equipment vehicles. The actual hardness of the tyre depends on the size of the vehicle on which the tyre will be used and its application. For example, a 40 tonne vehicle may need tyres of hardness 35 shore whereas an 80 tonne vehicle may need a tyre having hardness of 55 shore.
The extender oil as well as the M.W. (molecular weight) of the polyol and the polyol/isocyanate ratio in the formulation, influence the final Durometer hardness of the polyurethane elastomer so as to produce the desired hardness as appropriate.
EXAMPLES The invention will now be illustrated by reference to the following non-limiting Examples which are provided, by way of example only, of a number of embodiments of the compositions of the present invention.
Process Mixing Equipment Steel mixing vessel with a ‘Greaves' type dispersion head 205 L drums with drum taps and a base drum heater or drum jacket Digital balances Brookfield Viscometer for viscosity determination Vacuum pump Vent driers Standard Pumping Unit Raw Materials Polyol and isocyanate Compounds including their Chemical Function Tradename Supplier Chemical Function Lupranol ™ 2095 Elastogran GmbH Polyol Desmophen1M 5031 BT Bayer Polyol LupranatT80A Elastogran GmbH isocyanate Desmodur ™ CD Bayer Isocyanate Cellacast,M 24.743 IFS Chemicals Polyol Cellanaite ™ M28 IPS Chemicals Isocyanate Additive Compounds including their Chemical Function Tradename Supplier Chemical Function STW™910T Sparkford Chemicals UK Polyethelene fibres STWw760T Sparkford Chemicals UK Polyethelene fibres Additive T1 Whitchem UK Monofunctional isocyanate Dabco T - 12N Honeywell & Stein UK Catalyst UOP ,M L Paste Whitchem UK Zeolite paste Butylated hydroxyl toluene Sparkford Chemicals UK Antioxidant Byk ,M A530 National Chemicals Surfactant Purcell1* 55P Q8 Petroleum UK Aromatic oil Bristol,u 400 Petrochem UK Aromatic oil Bristol m475 Petrochem UK Aromatic oil CatenexSNR Univar Europe Extender oil · Metaphenylene diamine Air Products Chain extender General Method Manufacturing Process of Polyol (Component A) - General Procedure The aromatic oils were mixed at 60 RPM and heated to 25 °C. The polyol was added to the mixture and stirred for 5 min followed by the addition of the catalyst and a further 5 min stirring. The polyethylene fibers were slowly added and the mixture was stirred at 120 RPM. The recycled PU or PIR powder, or recycled crumb rubber are added (if applicable).
The Zeolite paste or water was added to the mixture and stirred at 180 RPM whereupon the antioxidant and surfactant were added. Using a filter the mixture was decanted into a clean, dry drum and dry nitrogen gas was blanketed over the top of the mixture and the drum was sealed.
Manufacturing Process of Isocyanate (Component B) - General Procedure The aromatic oils were mixed at 60 RPM and heated to 25 °C for 5 min. The isocyanate was added to the mixture and stirred for 2 min followed by the addition of the multifunctional isocyanate. The drum was sealed immediately and the area above the mixture was blanketed with dry nitrogen gas and stirred for a further 10 min. The mixture was decanted using a filter into a clean, dry drum and dry nitrogen gas was blanketed over the top of the mixture and the drum was sealed.
Manufacturing Process of the Elastomer (General Procedure) Components A and B are mixed together, typically a 6:4 or 7:3 ratio (polyokisocyanate) depending on the required density of the elastomer. The elastomer will cure within 10 hours and form soft, resilient, durable foam.
COMPARATIVE EXAMPLES Example 1 Materials POLYOL - COMPONENT A ISOCYANATE - COMPONENT B . Compound %(w/w) Compound % (w/w) Lupranol ™ 2095 90.3 Lupranate T 80 A 6.5 Dabco^WN 0.1 Catenex SNR 93.0 STW!M760T 1.0 Additive Ti 0.5 Catenex w SNR 7.0 OOP11* L Paste " 0.2 BHT lh 0.2 ByklMA530 0.2 Metaphenylene Diamine 1.0 SHORE‘A’HARDNESS 3 H Example 2 Materials POLYOL - COMPONENT A ISOCYANATE - COMPONENT B Compound % (w/w) Compound %(w/w) Lupranolw 2095 90.3 Lupranate T 80 A 6.5 OabcoT12N 0.1 Catenex SNR 93.0 STW1Xfl760T 1.0 Additive TI 0.5 Catenex ,M SNR 7.0 Water 0.2 BHT 0.2 Byk^AMO 0.2 Metaphenylene Diamine 1.0 SHORE ‘A’ HARDNESS 26 Example 3 Materials POLYOL - COMPONENT A ISOCYANATE - COMPONENT B Compound % (w/w) Compound % (w/w) Desmophen ™ 5031 BT 83.8 Desmodur CD 13.0 Dabco ™T12N 0.1 Catenex ,MSNR 865 STW'760T 1.0 Additive TI 0.5 Catenex1M SNR 13.5 UOP™L Paste 0.2 BHT™ 0.2 Byk™A530 0.2 Metaphenylene Diamine 1.0 SHORE Ά* HARDNESS 27 Example 4 Materials POLYOL - COMPONENT A ISOCYANATE - COMPONENT B Compound %(w/w) Compound %(w/w) Desmophen ™ 5031 BT B3.8 Desmodur1** CD 13.0 Dabco ,MT12N 0.1 Catenex ™ SNR 86.5 STWiM760T 1.0 Additive TI 0.5 Catenex1** SNR 13.5 Water 0.2 BHT™ 0.2 Byk'*AS30 0.2 Metaphenylene Diamine 1.0 SHORE W HARDNESS 24 Example S 10 Materials POLYOL - COMPONENT A ISOCYANATE - COMPONENT B Compound (%) (w/w) Compound (%) (w/w) Cellacast,M 24.743 59.29 Cellanate1MM28 10.68 Dabco ™T12N 0.39 CatenexSNR 29.64 SHORE ‘A’ HARDNESS 27 Examples Materials POLYOL - COMPONENT A ISOCYANATE - COMPONENT B Compound (%) (w/w) Compound (%) (w/w) Cellacast™ 24.743 69.29 Cellanate M28 12.47 Dabco ™T12N 2.93 Catenex SNR 17.32 SHORE ‘A’ HARDNESS 29.9 Example 7 (2/65AI Materials POLYOL - COMPONENT A ISOCYANATE - COMPONENT B Compound (%) (w/w) Compound (%) (w/w) Cellacast ™ 24.743 67.54 Cellanate M28 12.15 Dabco 'mT12N 0.53 Catenex SNR 16.88 Recycled PLI Powder 2.90 SHORE *A* HARDNESS 2 »3 Example 8 (2/65B) Materials POLYOL - COMPONENT A ISOCYANATE - COMPONENT B Compound (%) (w/w) Compound (%) (w/w) Cellacast™ 24.743 65.59 Cellanate M28 11.80 Dabco 1MT12N 0.45 Catenex SNR 16.39 Recycled Rubber 5.77 SHORE W HARDNESS 5 10 Example 9 (2/650 15 Materials POLYOL - COMPONENT A ISOCYANATE - COMPONENT B Compound (%)(w/w) Compound (%) (W/W) Cellacast™ 24.743 64.18 Cellanate M28 11.55 Dabco ™T12N 0.46 Catenex SNR 16.89 Recycled PU Powder 6.92 SHORE *A’ HARDNESS 2 I7 Example 10(2/68A) Materials POLYOL - COMPONENT A ISOCYANATE - COMPONENT B Compound (%)(w/w) Compound (%) (w/w) Cellacast ™ 24.743 59.29 Cellanate M28 10.67 Dabco T12N 0.40 Catenex SNR 29.64 SHORE ‘A’ HARDNESS 27 Use of the Elastomer as a Tyre Fill (General Procedure) Components A and B are injected into a tyre through the valve stem via a specially designed pumping unit.
The pumping unit measures the predetermined mixing ratio of the components, typically a 1:1 ratio (but may be 6:4 or 7:3 potyol:isocyanate) depending on the density required for the elastomer, and mixes the components just prior to injection into the tyre, as well as ensuring the final tyre pressure.
Once injected into the tyre, the elastomer requires 4 hours to cure into a soft, yet resilient elastomer. The interior ofthe tyre is completely void free.
Although the polyurethane elastomers of the present invention are referred to and described throughout this specification primarily in relation to use as tyre fill compositions, it is to be understood that the polyurethane elastomers of the present invention are also suitable for other uses such as manufacture of car bumpers and motorway safety bollards, for instance.
It will of course be understood that the invention is not limited to the specific details described herein, which are given by way of example only, and that various modifications and alterations are possible within the scope of the invention as defined in the appended claims.
Claims (52)
1. A polyurethane (PU) elastomer for use as a deflation proof tyre fill composition, the polyurethane elastomer produced from a polyol pre-polymer (Component A) and an 5 isocyanate pre-polymer (Component B), the polyol pre-polymer (Component A) comprising a polyol and the isocyanate pre-polymer (Component B) comprising an isocyanate; the polyol pre-polymer and/or the isocyanate pre-polymer comprising an extender oil having a relatively low polycyclic aromatic hydrocarbons content of less than 10% (w/w) of polycyclic aromatic hydrocarbons.
2. A polyurethane elastomer as claimed in Claim 1, wherein the polyol pre-polymer comprises polyester polyol and/or polyether polyol, or combinations thereof.
3. A polyurethane elastomer as claimed in Claim 1 or Claim 2, wherein the polyol 15 has a molecular weight of at least 3000 and preferably, has a molecular weight in the range from 6000 to 7000,
4. A polyurethane elastomer as claimed in any preceding claim, wherein the isocyanate is selected from any one or more of the following group: 20 polymeric diphenylmethane-4-4 Diisocyanate, hexamethylene Diisocyanate, polymethylene polyphenyl isocyanate, m-phenylene Diisocyanate, p-phenylene Diisocyanate, 3,3-dimethyl - 4-4 diphenyl Diisocyanate, 3,3-dimethoxy-4-4 biphenylene Diisocyanate, 2-2,4-4 tetramethyl-4-4 biphenylene Diisocyanate, 3,3-dimethyl-4-4 diphenylamine Diisocyanate, 4’4-diphenyl isopropylidene and/or potymethylene 25 polypheny! isocyanate.
5. A polyurethane elastomer as claimed in any preceding claim, wherein the extender oil is an extender oil having relatively low levels of polycyclic aromatic hydrocarbons (PAH) of less than 5% (w/w).
6. A polyurethane elastomer as claimed in any preceding claim, wherein the extender oil has an aromatic content of less than 60%, preferably between 40-60% and most preferably between 40-45%.
7. A polyurethane elastomer as claimed in any preceding claim, wherein the extender oil has a polar content of between 1% and 4.0% (w/w).
8. A polyurethane elastomer as claimed in Claim 7, wherein the polar content is 5 between 1.0 and 2.5% (w/w).
9. A polyurethane elastomer as claimed in any preceding claim, wherein the extender oil is included in an amount in the range from 5% to 60% (w/w).
10. 10. A polyurethane elastomer as claimed in any preceding claim, including a tin based amine catalyst, preferably included in an amount in the range from 0.01% to 2.00% (w/w).
11. A polyurethane elastomer as claimed in any preceding claim, wherein the polyurethane elastomer includes high density polyethylene (HDPE) having a crystalline 15 melting point of 132 degrees Celsius and preferably, the HDPE is included in an amount in the range from 0.5% to 5.0% (w/w) based on the weight of the poiyol pre-polymer (Component A).
12. A polyurethane elastomer as claimed in any preceding claim comprising a Zeolite 20 in an amount up to 2.0% (w/w) based on the weight of the polyol pre-polymer (Component A).
13. A polyurethane elastomer as claimed in Claim 12, wherein the Zeolite comprises a Potassium-calcium-sodium alumino-silicate type Zeolite in Castor Oil.
14. A polyurethane elastomer as claimed in any preceding claim, wherein an antioxidant is included; preferably the amount of antioxidant included is up to 2.0% (w/w) based on the weight of the polyol pre-polymer (Component A). 30
15. A polyurethane elastomer as claimed in any preceding claim comprising water in an amount up to 2.0% (w/w) based on the weight of the poiyol pre-polymer (Component A),
16. A polyurethane elastomer as claimed in any preceding claim, comprising recycled polyurethane or polyisocyanurate powder, preferably in an amount from 0.5% to 6.92 % (w/w) and most preferably in an amount from 2.9% to 3.0% (w/w), 5
17. A polyurethane elastomer as claimed in any preceding claim comprising recycled rubber crumb, preferably having a particle size in the range from 0.5 mm to 1.5 mm, and most preferably, having a particle size of 1.0 mm.
18. A polyurethane elastomer as claimed in any preceding claim comprising recycled 10 rubber crumb in an amount in the range from 1 % to 7% (w/w)·
19. A polyurethane elastomer as claimed in any preceding claim comprising a Polysiloxane based surfactant in hydrocarbon in an amount up to 2.0% (w/w) based on the weight of the polyol pre-polymer (Component A).
20. A polyurethane elastomer as claimed in any preceding claim comprising an amine extender such as metaphenylamine diamine, preferably, the amine extender is included in an amount from 0.1% and 2.0% (wfw) based on the weight of the polyol pre-polymer (Component A).
21. A polyurethane elastomer as claimed in any preceding claim comprising a compound which absorbs Carbon Dioxide.
22. A polyurethane elastomer as claimed in claim 21, wherein the carbon dioxide 25 absorbing compound comprises Zinc oxide.
23. A polyurethane elastomer as claimed in Claim 21, wherein the carbon dioxide absorbing compound is included in an amount up to 5.0% (w/w) based on the weight of the polyol pre-polymer (Component A).
24. A polyurethane elastomer as claimed in any preceding claim further including an additive comprising Monofunctional isocyanate; preferably included in an amount from 0.1 to 5% (w/w) based on the total weight of the isocyanate pre-polymer (Component B).
25. A method for producing a polyurethane elastomer for use as deflation proof tyre fill compositions, the method comprising the following steps: (a) preparing a polyol pre-polymer {Component A); (b) preparing an isocyanate pre-polymer (Component 8); and (c) combining the polyol pre-polymer (Component A) with the isocyanate pre-polymer (Component B) and curing to form the polyurethane elastomer, and wherein the polyol pre-polymer and/or the isocyanate pre-polymer comprise an extender oil having a relatively low polycyclic aromatic hydrocarbons content of less than 10% (w/w) of polycyclic aromatic hydrocarbons.
26. A method as claimed in Claim 25, wherein the polyol pre-polymer comprises polyester polyol and/or polyether polyol, or combinations thereof.
27. A method as claimed in Claim 25 or Claim 26, wherein, the polyol pre-polymer has a molecular weight of at least 3000 and preferably has a molecular weight in the range from 6000 to 7000. 20
28. A method as claimed in any one of Claims 25 to 27, wherein, the isocyanate prepolymer is selected from any one or more of the following group: polymeric diphenylmethane-4-4 Diisocyanate, hexamethylene Diisocyanate, polymethylene polyphenyl isocyanate, m-phenylene Diisocyanate, p-phenylene Diisocyanate, 3,3-dimethyl - 4-4 diphenyl Diisocyanate, 3,3-dimethoxy-4-4 biphenylene 25 Diisocyanate, 2-2,4-4 tetramethyl-4-4 biphenylene Diisocyanate, 3,3-dimethyl-4-4 djphenylamine Diisocyanate, 4’4-diphenyl isopropylidene and/or potymethylene polypheny) Isocyanate.
29. A method as claimed in any one of Claims 25 to 26, wherein, the extender oil is an 30 extender oil having relatively low levels of polycyclic aromatic hydrocarbons (PAHs or PCAs) of less than 5% (w/w).
30. A method as claimed in any one of Claims 25 to 29, wherein the extender oil has an aromatic content of less than 60% and preferably has an aromatic content in the range 35 of 40-45%.
31. A method as claimed in any one of Claims 25 to 30, wherein the extender off has a polar content in the range of 1-4.0% (w/w). preferably in the range of 1-2.5% (w/w). 5
32. A method as claimed in any one of Claims 25 to 31, wherein the extender oil is included in an amount from 5% to 60% (w/w).
33. A method as claimed in any one of Claims 25 to 32, wherein the method comprises the step of including a tin based amine catalyst; preferably included in an 10 amount in the range from 0.01% to 2.00% (w/w).
34. A method as claimed in any one of Claims 25 to 33, wherein the polyurethane elastomer includes high density polyethylene (HDPE) having a crystalline melting point of 132 degrees Celsius and preferably, is included in an amount of 0.5% to 5.0% (w/w) 15. Based on the weight of the polyol pre-polymer (Component A).
35. A method as claimed in any one of Claims 25 to 34, wherein the polyurethane elastomer comprises a zeolite in an amount in the range up to 2.0% (w/w) based on the weight of the poiyol pre-polymer (Component A).
36. A method as claimed in Claim 35, wherein the Zeolite comprising a Potassiumcalcium-sodium alumino-silicate type Zeolite in Castor Oil.
37. A method as claimed in any one of Claims 25 to 36, wherein the method includes 25 the step of including an anti-oxidant, and preferably, the amount of antioxidant used is up to 2.0% (w/w) based on the weight of the poiyol pre-polymer (Component A).
38. A method as claimed in any one of Claims 25 to 37, wherein the method includes the step of adding water to the polyol pre-polymer (Component A), the water being added 30 in an amount up to 2.0% (w/w) based on the weight of the polyol pre-polymer (Component A).
39. A method as claimed in any one of Claims 25 to 38, wherein the method includes the step of including recycled polyurethane or polyisocyanurate powder in an amount from 35 0.5% to 6.92 % (w/w) and preferably, in an amount from 2.9% to 3.0% (w/w).
40. A method as claimed in any one of Claims 25 to 39, wherein the method includes the step of adding recycled rubber crumb, preferably, having a particle size of 0.5 mm to 1.5 mm, and most preferably having a particle size of 1.0 mm.
41. A method as claimed in Claim 40, wherein recycled rubber crumb is added in an amount from 1% to 7% (w/w).
42. A method as claimed in Claim 41, wherein the rubber crumb is added in an 10 amount of 5.77% (w/w).
43. A method as claimed in any one of Claims 25 to 42, wherein the method includes the step of including a Polysftoxane based surfactant in hydrocarbon in an amount up to 2.0% (w/w) based on the weight of the polyol pre-polymer (Component A).
44. A method as claimed in any one of Claims 25 to 43, wherein the method includes the step of including an amine extender such as metaphenylamine diamine, preferably in an amount from 0.1% and 2.0% (w/w) based on the weight of the polyol pre-polymer (Component A).
45. A method as claimed in any one of Claims 25 to 44, wherein the method includes the step of including a compound which absorbs Carbon Dioxide.
46. A method as claimed in Claim 45, wherein the carbon dioxide absorbing 25 compound comprises Zinc oxide.
47. A method as claimed in Claim 45 or Claim 46, wherein the carbon dioxideabsorbing compound is included in an amount up to 5.0% (w/w) based on the weight of the polyol pre-polymer (Component A).
48. A method as claimed in any one of Claims 25 to 47, wherein the method includes the step of further including an additive comprising a Monofunctional isocyanate, preferably included in an amount in the range of 0.1 to 5% (w/w) based on the total weight of the isocyanate pre-polymer (Component B).
49. A deflation proof tyre fitted with a polyurethane elastomer as claimed in any of Claims 1 to 24.
50. A polyurethane elastomer as claimed in Claim 1, for use as a deflation proof tyre 5 fill composition, substantially as herein described, and particularly as herein described in the Examples.
51. A method tor producing a polyurethane elastomer as claimed in Claim 25 for use as a deflation proof tyre fill composition, substantially as herein described, particularly as 10 herein described in the Examples.
52. A deflation proof tyre filled with a polyurethane elastomer as claimed In Claim 1, substantially as herein described and particularly as herein described in the Examples.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IE20100115A IE86186B1 (en) | 2009-03-02 | 2010-03-02 | Polyurethane elastomers and methods of manufacture thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IES20090161 | 2009-03-02 | ||
| IE20100115A IE86186B1 (en) | 2009-03-02 | 2010-03-02 | Polyurethane elastomers and methods of manufacture thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE20100115A1 IE20100115A1 (en) | 2010-09-29 |
| IE86186B1 true IE86186B1 (en) | 2013-05-08 |
Family
ID=48222402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE20100115A IE86186B1 (en) | 2009-03-02 | 2010-03-02 | Polyurethane elastomers and methods of manufacture thereof |
Country Status (3)
| Country | Link |
|---|---|
| GB (1) | GB2468574B (en) |
| IE (1) | IE86186B1 (en) |
| WO (1) | WO2010100155A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102017221098A1 (en) * | 2017-11-24 | 2019-05-29 | Continental Reifen Deutschland Gmbh | Automatically sealing tire sealant and pneumatic vehicle tire containing the tire sealant |
| RU2713156C1 (en) | 2019-11-07 | 2020-02-04 | Акционерное общество "Управляющая компания "Биохимического холдинга "Оргхим" | Method for obtaining low-viscous high-aromatic non-carcinogenic process oil |
| CN115057983B (en) * | 2022-08-18 | 2022-12-13 | 山东一诺威聚氨酯股份有限公司 | Polyurethane elastomer for CT slip ring and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2137642B (en) * | 1980-12-23 | 1985-09-04 | Ransome J Wyman | Deflation-proof pneumatic tire and elastomeric fillings thereof |
| ES2181178T3 (en) * | 1997-01-06 | 2003-02-16 | Kraton Polymers Res Bv | PRESSURE SENSITIVE ADHESIVES INCLUDING THERMOPLASTIC POLYURETHANS. |
| US6187125B1 (en) * | 1997-09-05 | 2001-02-13 | Arnco | Method for producing a deflation-proof pneumatic tire and tire filling composition having high resilience |
| AU8679998A (en) * | 1997-09-05 | 1999-03-29 | Arnco | Pneumatic tire filling composition and filling method |
| US20060287428A1 (en) * | 2005-06-15 | 2006-12-21 | Marc Weydert | Oil extended rubber and composition containing low PCA oil |
| US20090000718A1 (en) * | 2007-06-28 | 2009-01-01 | Dirk Frans Rouckhout | Air barrier composition |
-
2010
- 2010-03-02 WO PCT/EP2010/052630 patent/WO2010100155A1/en active Application Filing
- 2010-03-02 GB GB1003453.6A patent/GB2468574B/en not_active Expired - Fee Related
- 2010-03-02 IE IE20100115A patent/IE86186B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010100155A1 (en) | 2010-09-10 |
| IE20100115A1 (en) | 2010-09-29 |
| GB201003453D0 (en) | 2010-04-14 |
| GB2468574B (en) | 2012-03-07 |
| GB2468574A (en) | 2010-09-15 |
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| Date | Code | Title | Description |
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| MM4A | Patent lapsed |