WO2003020504A1 - Infusion of cyclic olefin resins into porous materials - Google Patents
Infusion of cyclic olefin resins into porous materials Download PDFInfo
- Publication number
- WO2003020504A1 WO2003020504A1 PCT/US2002/027654 US0227654W WO03020504A1 WO 2003020504 A1 WO2003020504 A1 WO 2003020504A1 US 0227654 W US0227654 W US 0227654W WO 03020504 A1 WO03020504 A1 WO 03020504A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- wood
- catalyst
- resin
- metathesis
- group
- Prior art date
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- 239000011148 porous material Substances 0.000 title claims abstract description 52
- 238000001802 infusion Methods 0.000 title abstract description 35
- 229920005672 polyolefin resin Polymers 0.000 title abstract description 16
- 125000004122 cyclic group Chemical group 0.000 title abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 84
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000009472 formulation Methods 0.000 claims abstract description 41
- 239000000178 monomer Substances 0.000 claims abstract description 41
- 238000005649 metathesis reaction Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims abstract description 19
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 11
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims abstract description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 9
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 9
- 238000010535 acyclic diene metathesis reaction Methods 0.000 claims abstract description 5
- 230000035495 ADMET Effects 0.000 claims abstract 2
- 229920005989 resin Polymers 0.000 claims description 135
- 239000011347 resin Substances 0.000 claims description 135
- 239000002023 wood Substances 0.000 claims description 87
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 47
- 150000001336 alkenes Chemical class 0.000 claims description 38
- 241000288673 Chiroptera Species 0.000 claims description 28
- 239000004567 concrete Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 20
- 229920000098 polyolefin Polymers 0.000 claims description 13
- 239000007822 coupling agent Substances 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 10
- 239000004568 cement Substances 0.000 claims description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 8
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical class C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 claims description 4
- DRMGVASVGXJWQV-UHFFFAOYSA-N 1-(cyclohexen-1-yl)bicyclo[2.2.1]hept-2-ene Chemical class C1C(C=C2)CCC21C1=CCCCC1 DRMGVASVGXJWQV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 239000011111 cardboard Substances 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000011368 organic material Substances 0.000 claims description 4
- 239000000123 paper Substances 0.000 claims description 4
- 241000333074 Eucalyptus occidentalis Species 0.000 claims description 3
- 229920001247 Reticulated foam Polymers 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical class C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 claims description 3
- 239000003818 cinder Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 150000001931 cyclobutenes Chemical class 0.000 claims description 3
- 125000001162 cycloheptenyl group Chemical class C1(=CCCCCC1)* 0.000 claims description 3
- 150000001935 cyclohexenes Chemical class 0.000 claims description 3
- 150000001939 cyclooctenes Chemical class 0.000 claims description 3
- 150000001941 cyclopentenes Chemical class 0.000 claims description 3
- 150000001943 cyclopropenes Chemical class 0.000 claims description 3
- 238000009408 flooring Methods 0.000 claims description 3
- 239000011505 plaster Substances 0.000 claims description 3
- 150000004756 silanes Chemical class 0.000 claims description 3
- 229920002994 synthetic fiber Polymers 0.000 claims description 3
- 239000012209 synthetic fiber Substances 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- 235000009854 Cucurbita moschata Nutrition 0.000 claims description 2
- 240000001980 Cucurbita pepo Species 0.000 claims description 2
- 235000009852 Cucurbita pepo Nutrition 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 238000007596 consolidation process Methods 0.000 claims description 2
- 210000003195 fascia Anatomy 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000011178 precast concrete Substances 0.000 claims description 2
- 235000020354 squash Nutrition 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims 2
- 229920001153 Polydicyclopentadiene Polymers 0.000 claims 1
- 239000012615 aggregate Substances 0.000 claims 1
- 150000002846 norbornadienes Chemical class 0.000 claims 1
- 238000011417 postcuring Methods 0.000 claims 1
- 238000005507 spraying Methods 0.000 claims 1
- -1 cyclic olefin Chemical class 0.000 abstract description 27
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 36
- 241001588281 Eucalyptus fraxinoides Species 0.000 description 30
- 238000011282 treatment Methods 0.000 description 20
- 239000000758 substrate Substances 0.000 description 19
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 16
- 239000003963 antioxidant agent Substances 0.000 description 15
- 239000000654 additive Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 230000003078 antioxidant effect Effects 0.000 description 11
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 11
- RIZMRRKBZQXFOY-UHFFFAOYSA-N ethion Chemical compound CCOP(=S)(OCC)SCSP(=S)(OCC)OCC RIZMRRKBZQXFOY-UHFFFAOYSA-N 0.000 description 11
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 9
- 239000003112 inhibitor Substances 0.000 description 9
- 239000003607 modifier Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000006096 absorbing agent Substances 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- JCYWCSGERIELPG-UHFFFAOYSA-N imes Chemical compound CC1=CC(C)=CC(C)=C1N1C=CN(C=2C(=CC(C)=CC=2C)C)[C]1 JCYWCSGERIELPG-UHFFFAOYSA-N 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000000038 blue colorant Substances 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 150000003568 thioethers Chemical class 0.000 description 4
- 238000012800 visualization Methods 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 238000005865 alkene metathesis reaction Methods 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001718 carbodiimides Chemical class 0.000 description 3
- 150000001925 cycloalkenes Chemical class 0.000 description 3
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 3
- 239000004913 cyclooctene Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 150000004820 halides Chemical group 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- LJDZFAPLPVPTBD-UHFFFAOYSA-N nitroformic acid Chemical compound OC(=O)[N+]([O-])=O LJDZFAPLPVPTBD-UHFFFAOYSA-N 0.000 description 3
- 230000000269 nucleophilic effect Effects 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004634 thermosetting polymer Substances 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- 239000010875 treated wood Substances 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 241000219000 Populus Species 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical group [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 description 2
- 125000005228 aryl sulfonate group Chemical group 0.000 description 2
- 150000001504 aryl thiols Chemical class 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012229 microporous material Substances 0.000 description 2
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000003348 petrochemical agent Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000002577 pseudohalo group Chemical group 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- ATQUFXWBVZUTKO-UHFFFAOYSA-N 1-methylcyclopentene Chemical compound CC1=CCCC1 ATQUFXWBVZUTKO-UHFFFAOYSA-N 0.000 description 1
- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 description 1
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- XUKLTPZEKXTPBT-UHFFFAOYSA-N 3-oxatricyclo[5.2.1.01,5]dec-5-ene-2,4-dione Chemical compound C1CC2C=C3C(=O)OC(=O)C13C2 XUKLTPZEKXTPBT-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- VEEKCIOFMIAGSF-UHFFFAOYSA-N 4-butylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(CCCC)C2 VEEKCIOFMIAGSF-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/48—Macromolecular compounds
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/62—Coating or impregnation with organic materials
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/249925—Fiber-containing wood product [e.g., hardboard, lumber, or wood board, etc.]
Definitions
- the invention is directed generally to methods and systems for the infusion of cyclic olefin resins into free standing porous materials, together with ring opening metathesis polymerization (ROMP) catalysts to effect the polymerization of such olefins within the porous materials to yield specific composite structures and novel derivatives.
- REP ring opening metathesis polymerization
- a wide variety of both natural and synthetic structural materials have a porous nature. Common examples include wood, cement and concrete, open-cell foams and sponges, paper and cardboard, and various sintered materials.
- the porosity of these materials may be an unintended consequence of their mode of origin or may be a deliberate design feature. Depending upon the intended use of a given material, such porosity may offer advantages such as decreased weight, absorbency, breathability, or unique conductivity or insulative characteristics. However, for many applications, porosity can also lead to problems such as decreased mechanical performance and durability. As a common example, water or moisture routinely enters and exits the pores of porous materials. Aside from affecting the resulting mechanical properties of the material, this moisture often also accelerates degradation by chemical and/or mechanical action.
- thermoset resin chemistries may be incompatible with moieties present in the interstices or surfaces of porous materials
- thermoset resins yielding tough, moisture-resistant polymers would seem to be ideal candidates for infusion into porous materials as protectants and mechanical performance enhancers.
- Such polymers may be obtained by the ring-opening metathesis polymerization (ROMP) of cyclic olefin monomers.
- ROMP ring-opening metathesis polymerization
- the resulting ROMP polymers possess non-hydrolyzable hydrocarbon backbones and are generally very tough.
- ROMP typically depends upon transition metal catalysts that are extremely sensitive to air, moisture, and functional groups that may be present in the monomers or the porous materials. Thus, ROMP polymers are not commonly considered as candidate impregnants for porous materials.
- Figure 1 shows a preferred method of infusing baseball bats with DCPD resin.
- the present invention encompasses novel compositions comprising porous materials infused with polymers obtained from metathesis reactions, for example ROMP derived polymers and ADMET derived polymers.
- Another embodiment of the invention is cyclic olefin monomer formulations, including ruthenium or osmium carbene metathesis catalysts, useful for the infusion of porous materials.
- a further embodiment of the invention includes methods for preparing the porous materials infused with cyclic olefin resin formulations.
- Other embodiments of the present invention are specific composite structures and articles fabricated from porous materials infused with cyclic olefin polymers.
- a number of catalysts have been developed recently for initiating olefin metathesis reactions, including ring-opening metathesis polymerization (ROMP) of cyclic olefins, ring-closing metathesis (RCM) of dienes to form ring-closed products, acyclic diene metathesis polymerization (ADMET), depolymerization of unsaturated polymers to form the depolymerized products, synthesis of telechelic polymers by reaction of a cyclic olefin with a functionalized olefin, and synthesis of cyclic olefins by self-metathesis of an acyclic olefin or cross-metathesis of two acyclic olefins.
- ROMP ring-opening metathesis polymerization
- RCM ring-closing metathesis
- ADMET acyclic diene metathesis polymerization
- depolymerization of unsaturated polymers to form the depolymerized
- metathesis catalysts include, but are not limited to, neutral ruthenium or osmium metal carbene complexes that possess metal centers that are formally in the +2 oxidation state, have an electron count of 16, are penta-coordinated, and are of the general formula I.
- Other preferred metathesis catalysts include, but are not limited to, cationic ruthenium or osmium metal carbene complexes that possess metal centers that are formally in the +2 oxidation state, have an electron count of 14, are tetra-coordinated, and are of the general formula II.
- Still other preferred metathesis catalysts include, but are not limited to, neutral ruthenium or osmium metal carbene comlexes that possess metal centers that are formally in the +2 oxidation state, have an electron count of 18, are hexa-coordinated, and are of the general formula III.
- M is ruthenium or osmium; n is an integer between 0-5;
- L, L 1 and L 2 are each independently any neutral electron donor ligand; R, and R 1 are each independently hydrogen or any hydrocarbyl or silyl moiety;
- X and X 1 are each independently any anionic ligand
- Y is any noncoordinating anion
- any two or more of X, X , L, L ,L , Z, Z , R, R , and R may be optionally joined together to form a multidentate ligand and wherein any one or more of X, X 1 , L, L',L 2 , Z, Z 1 , R, and R 1 may be optionally linked chemically to a solid or glassy support.
- L, L 1 and L 2 are each independently selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carbonyl, carboxyl, isocyanide, nitrosyl, pyridine, quinoline, thioether, and nucleophilic carbenes of the general formula IV or V:
- A is either carbon or nitrogen
- R 3 , R 4 , R 5 , and R 6 are each independently hydrogen or any hydrocarbyl moiety, except that in the case where A is nitrogen R 5 is nil;
- Z 2 , Z 3 , R 4 , and R 5 together may optionally form a cyclic optionally substituted with one or more moieties selected from the group consisting of -Cio alkyl, Ct-Cio alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.
- moieties selected from the group consisting of -Cio alkyl, Ct-Cio alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, dis
- L and L 1 are each a phosphine of the formula PR 7 R R , where R 7 , R 8 , and R 9 are each independently any hydrocarbyl moiety, particularly aryl, primary Cj-Cio alkyl, secondary alkyl or cycloalkyl.
- L and L 1 are selected from the group consisting of -P(cyclohexyl) 3 , -P(cyclopentyl) 3 , -P(isopropyl) 3 , -P(butyl) 3 , and -P(phenyl) 3 .
- L is a phosphine and L 1 is a nucleophilic carbene of the general formula III.
- L is selected from the group consisting of -P(cyclohexyl) 3 , -P(cyclopentyl) 3 ,
- -P(isopropyl) 3 , -P(butyl) 3 , and -P(phenyl) 3 and L 1 is selected from the group consisting of structures VI, VII, or VIII (wherein m is an integer between 0 and 5):
- L is a phosphine or a nucleophilic carbene of the general
- formula IV and L and L are each independently a pyridine or substituted pyridine ligand or L 1 and L 2 together form a chelating bispyridine or phenanthroline ligand, either of which may be substituted or unsubstituted.
- hydrocarbyl moieties include, but are not limited to, the group consisting of C ⁇ -C 20 alkyl, C 3 -C 2 o cycloalkyl, C -C 20 alkenyl, C 2 -C 0 alkynyl, aryl, heteroaryl, aralkyl, or arylalkyl.
- silyl moieties include, but are not limited to, the group consisting of tri(hydrocarbyl)silyl, tri(hydrocarbyloxy)silyl, or mixed (hydrocarbyl)(hydrocarbyloxy)silyl.
- each of the R, R or R substituent groups may be substituted with one or more hydrocarbyl or silyl moieties, which, in turn, may each be further substituted with one or more groups selected from a halogen, a Cj-Cs alkyl, C 1 -C 5 alkoxy, and phenyl.
- any of the catalyst ligands may further include one or more functional groups.
- Suitable functional groups include but are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and hhaallcogen.
- R ⁇ may be joined together to form a bridging or cyclic structure.
- the R substituent is hydrogen and the R 1 substituent is selected from the group consisting C ⁇ -C 20 alkyl, C -C 20 alkenyl, aryl, alkaryl, aralkyl, trialkylsilyl, and trialkoxysilyl.
- n equals 0, 1 or 2 and the R 1 substituent is phenyl, /-butyl or vinyl, optionally substituted with one or more moieties selected from the group consisting of Cj-Cs alkyl, Cj-Cs alkoxy, phenyl, and a functional group.
- n 0 or 1 and R 1 is phenyl, /-butyl, or vinyl substituted with one or more moieties selected from the group consisting of chloride, bromide, iodide, fluoride, -NO 2 , -NMe , methyl, methoxy and phenyl.
- X and X 1 are each independently hydrogen, halide, or one of the following groups: C ⁇ -C 20 alkyl, aryl, C ⁇ -C 20 alkoxide, aryloxide, C 3 - C 20 alkyldiketonate, aryldiketonate, C 1 -C 20 carboxylate, arylsulfonate, C ⁇ -C 20 alkylsulfonate, C ⁇ -C 20 alkylthiol, aryl thiol, C1-C20 alkylsulfonyl, or C ⁇ -C 20 alkylsulfinyl.
- X and X 1 may be substituted with one or more moieties selected from the group consisting of C ⁇ -C 10 alkyl, C J -C JO alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from halogen, C ⁇ -C 5 alkyl, C C 5 alkoxy, and phenyl.
- X and X 1 are halide, benzoate, Cj- C 5 carboxylate, C 1 -C 5 alkyl, phenoxy, -C 5 alkoxy, C1-C 5 alkylthiol, aryl thiol, aryl, and Cj-Cs alkyl sulfonate.
- X and X 1 are each halide, CF 3 CO 2 , CH 3 CO 2 , CFH 2 CO 2 , (CH 3 ) 3 CO, (CF 3 ) 2 (CH 3 )CO, (CF 3 )(CH 3 ) 2 CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethanesulfonate.
- X and X 1 are each chloride, bromide, or iodide.
- the X and X 1 together may comprise a bidentate ligand.
- Y may be derived from any tetracoordinated boron compound or any hexacoordinated phosphorus compound.
- Preferred boron compounds include BF 4 " , BPl f, and fluorinated derivatives of BPh ⁇ f.
- Preferred phosphorous compounds include PF ⁇ and PO 4 ⁇ .
- the noncoordinating anion may be also any one of the following: ClO 4 ⁇ , SO 4 ⁇ , NO ⁇ , OTeF 5 - F 3 CSO 3 " , H 3 CSO 3 " , CF 3 COO " , PhSO 3 " , or (CH 3 )C 6 H 5 SO 3 _ .
- Y may be also derived from carboranes, fullerides, and aluminoxanes.
- the catalyst:olefin monomer ratio in the invention is preferably between about 1 :5 and about 1 :1,000,000. More preferably, the catalyst:olefin ratio is between about 1 :100 and about 1 :100,000 and, most preferably, is between about 1:1,000 and about 1 :30,000.
- Particularly preferred metal catalysts include, but are not limited to:
- the inventive formulation resins include any olefin monomer and metathesis catalyst.
- the olefin monomers may be used alone or mixed with each other in various combinations to adjust the properties of the olefin monomer composition.
- mixtures of cyclopentadiene oligomers offer a reduced melting point and yield cured olefin copolymers with increased mechanical strength and stiffness relative to pure poly- DCPD.
- incorporation of COD, norbornene, or alkyl norbornene comonomers tend to yield cured olefin copolymers that are relatively soft and rubbery.
- the polyolefin resins of the invention are amenable to thermosetting and are tolerant of various additives, stabilizers, rate modifiers, hardness and/or toughness modifiers, viscosity modifiers, adhesion or coupling agents, and fillers.
- Any suitable cyclic olefin monomer can be used with the present invention.
- olefin monomers for infusion include at least one of all "tight" cycloolefins as described in US 6,001,909; and at least one of all cycloolefins as described in US 5,840,238 and US 5,922,802; and at least one of all Diels-Alder adducts as described in US 6,100,323.
- the most preferred olefin monomer for use in the invention is dicyclopentadiene (DCPD).
- DCPD dicyclopentadiene
- Various DCPD suppliers and purities may be used such as Lyondell 108 (94.6% purity), Velsicol UHP (99+% purity), Cymetech Ultrene ® (97% and 99% purities), and Hitachi (99+% purity).
- High-purity grades of DCPD such as Ultrene ® 99, are preferred.
- the DCPD resin may optionally contain other cyclopentadiene oligomers, including trimers, tetramers, pentamers, and the like. Such oligomers may be introduced into DCPD by heat treatment of DCPD as described in U.S.
- the oligomer content may be controlled by varying the heat treatment conditions or by blending oligomer mixtures of known composition with DCPD until the desired oligomer concentration is obtained. Advantages of using such oligomer mixtures include decreased melting point of the monomer mixture and increased mechanical properties and glass transition temperature of the cured resin.
- olefin monomers include cyclooctadiene (COD; DuPont); cyclooctene (COE); cyclohexenylnorbornene; norbornene; norbornene dicarboxylic anhydride (nadic anhydride); norbornadiene (Elf Atochem); and substituted norbornenes including ethylidene norbornene (ENB), butyl norbornene, hexyl norbornene, octyl norbornene, decyl norbornene, and the like.
- COD cyclooctadiene
- COE cyclooctene
- COE cyclohexenylnorbornene
- norbornene norbornene dicarboxylic anhydride
- norbornadiene Elf Atochem
- substituted norbornenes including ethylidene norbornene (ENB), butyl norbornene,
- the olefinic moieties include mono-or disubstituted olefins and cycloolefins containing between 3 and 200 carbons.
- metathesis-active olefinic moieties include cyclic or multicyclic olefins, for example, cyclopropenes, cyclobutenes, cycloheptenes, cyclooctenes, [2.2.1]bicycloheptenes, [2.2.2]bicyclooctenes, benzocyclobutenes, cyclopentenes, cyclopentadiene oligomers including trimers, tetramers, pentamers, and the like; cyclohexenes.
- compositions include frameworks in which one or more of the carbon atoms carry substituents derived from radical fragments including halogens, pseudohalogens, alkyl, aryl, acyl, carboxyl, alkoxy, alkyl- and arylthiolate, amino, aminoalkyl, and the like, or in which one or more carbon atoms have been replaced by, for example, silicon, oxygen, sulfur, nitrogen, phosphorus, antimony, or boron.
- radical fragments including halogens, pseudohalogens, alkyl, aryl, acyl, carboxyl, alkoxy, alkyl- and arylthiolate, amino, aminoalkyl, and the like, or in which one or more carbon atoms have been replaced by, for example, silicon, oxygen, sulfur, nitrogen, phosphorus, antimony, or boron.
- the olefin may be substituted with one or more groups such as thiol, thioether, ketone, aldehyde, ester, ether, amine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, phosphate, phosphite, sulfate, sulfite, sulfonyl, carbodiimide, carboalkoxy, carbamate, halogen, or pseudohalogen.
- groups such as thiol, thioether, ketone, aldehyde, ester, ether, amine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, phosphate, phosphite, sulfate, sulfite, sulfonyl, carbodiimide, carboalkoxy, carbamate, halogen, or pseudohalogen.
- the olefin may be substituted with one or more groups such as alkyl, aryl, acyl, Ci-C 2 o alkoxide, aryloxide, C 3 -C 20 alkyldiketonate, aryldiketonate, C ⁇ -C 20 carboxylate, arylsulfonate, C!-C 2 o alkylsulfonate, C1-C20 alkylthio, arylthio, d-C 20 alkylsulfonyl, and C 1 -C 20 alkylsulfinyl, C ! -C 2 o alkylphosphate, arylphosphate, wherein the moiety may be substituted or unsubstituted.
- groups such as alkyl, aryl, acyl, Ci-C 2 o alkoxide, aryloxide, C 3 -C 20 alkyldiketonate, aryldiketonate, C ⁇ -C 20
- the viscosity of the formulated olefin monomers is typically less than about 500 centipoise at temperatures near room temperature (e.g., from about 25-35°C).
- the viscosity of the formulated olefin monomers is less than about 200 centipoise, more preferably is less than about 75 centipoise, and most preferably, is less than about 50 centipoise. In many circumstances, the viscosity is less than 25 centipoise to promote facile infusion.
- the viscosity of the formulated olefin monomers can be controlled by selection of the combination of monomers and additives, stabilizers, and modifiers used.
- the viscosity of the formulated resin may be increased or decreased by varying the temperature or by the use of additives such as thixotropes, thickeners, or dilutents.
- Preferred hardness modulators include, for example, elastomeric additives such as polybutadienes, polyisoprenes, and the like.
- Polybutadienes and polyisoprenes of various sources, as well as various number-average molecular weights (M n ) or weight- average molecular weights (M w ), may be utilized in the invention as rubber-like hardness modulators.
- M n number-average molecular weights
- M w weight- average molecular weights
- the poly-DCPD resins of the invention allow compositions containing polybutadiene to be clear rather than opaque.
- the hardness modulators of the invention when added to a polyolefin resin composition, alter the hardness, toughness and/or surface "feel" of the composition compared to the unmodified or native polyolefin.
- hardness modulators include plasticizers such as dioctyl phthalate and various molecular weight hydrocarbon and the like jellies, greases and waxes, carboxylic acids and salts thereof, and co-monomers such as norbornene, cyclooctadiene, cyclooctene, cyclohexenylnorbornene, norbornadiene, cyclopentene and/or methylcyclopentene.
- the amount of hardness modulator included in the polyolefin compositions of the invention is preferably about 0.1%-20% by weight of the olefin monomer to which it is added. More preferably, the amount of hardness modulator is about 1%-10% by weight of the olefin monomer and, most preferably, is about 2.5%-7.5%.
- Especially preferred toughness modulators are rubber triblock copolymers such as styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene/butylenes-styrene, styrene-ethylene/propylene-styrene, and the like.
- An example of such toughness modulators is the commercially available Kraton polymers.
- Other preferred toughness modulators include polysiloxanes, because the resulting polyolefin compositions possess significantly increased toughness properties without significant concomitant losses in heat distortion temperature (HDT).
- HDT heat distortion temperature
- the amount of toughness modulator included in the polyolefin compositions of the invention is preferably about 0.1%- 10% by weight of the olefin monomer to which it is added. More preferably, the amount of toughness modulator is about 0.5%-6% by weight of the olefin monomer and, most preferably, is about 2%-4%.
- poly-DCPD resins containing 3 parts per hundred low molecular weight (MW) poly(dimethylsiloxane) (Shin Etsu DMF-50) possess notched Izod impact values in excess of 4 ft.-lb./in. and HDT values above 130°C. Hardness and toughness modulators are further described in PCT Publication No. WO 99/60030, the contents of which are incorporated herein by reference.
- the UV and oxidative resistance of the polyolefin compositions of the invention may be enhanced by the addition of various stabilizing additives such as primary antioxidants (e.g., sterically hindered phenols and the like), secondary antioxidants (e.g., organophosphites, thioesters, and the like), light stabilizers (e.g., hindered amine light stabilizers or HALS), and UV light absorbers (e.g., hydroxy benzophenone absorbers, hydroxyphenylbenzotriazole absorbers, and the like).
- one or more stabilizing additives are included in the polyolefin resin composition at a level from about 0.01-15 phr.
- the antioxidant(s) are present at a level of about 0.05-10 phr and, most preferably, 0.1-8 phr.
- Exemplary primary antioxidants include, for example, 4,4'- methylenebis (2,6-di-tertiary-butylphenol) (Ethanox 702 ® ; Albemarle Corporation), l,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (Ethanox 330 ® ;
- antioxidants include tris(2,4-ditert-butylphenyl)phosphite (Irgafos ® 168; Ciba-Geigy), l:l l(3,6,9-trioxaudecyl)bis(dodecylthio)propionate (Wingstay ® SN-1; Goodyear), and the like.
- Exemplary light stabilizers and absorbers include bis(l,2,2,6,6-pentamethyl-4- piperidinyl)-[[3,5-bis(l , 1 -dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate
- Tivin ® 328 absorber Ciba-Geigy
- 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2- yl)phenyl Teuvin ® 327 absorber; Ciba-Geigy), 2-hydroxy-4-(octyloxy)benzophenone
- a suitable rate modifier such as, for example, triphenylphosphine (TPP), tricyclopentylphosphine, tricyclohexylphosphine, triisopropylphosphine, trialkylphosphites, triarylphosphites, mixed phosphites, pyridine, or other Lewis base, may be added to the olefin monomer to retard or accelerate the rate of polymerization as required.
- TPP rate modifier it is preferably included in an amount of about 10-200 mg per 64 g olefin monomer.
- the amount of TPP is about 20- 100 mg per 64 g olefin monomer and, most preferably, is about 30-80 mg per 64 g olefin monomer.
- the amount of rate modifier is preferably about 0.1-50 mg per 64 g olefin monomer, more preferably about 1-40 mg per 64 g olefin monomer, and most preferably is about 1-30 mg per 64 g olefin monomer.
- rate modifiers can be seen in U.S. Patent No. 5,939,504 and U.S. Application No. 09/130,586, the contents of each of which are incorporated herein by reference.
- various pigments or dyes may be included in the polyolefin resin compositions of the invention for applications where color is desired. Preferred pigments include Ferro and Dayglo products, in an amount of about 0.05-2 parts per hundred of polyolefin resin.
- the cyclic olefin resin formulation may also contain coupling agents or adhesion agents that promote bonding between the walls of the substrate and the infused resin.
- Examples of such compounds include tetra(2,2- diallyloxymethyl)butyl di(ditridecyl)phosphito titanate (Ken-React ® KR 55), tetra(2,2- diallyloxymethyl)butyl di(ditridecyl)phosphito zirconate (Ken-React ® KZ 55), and cyclo[dineopentyl(diallyl)]pyrophosphato dineopentyl(diallyl) zirconate (Ken-React KZ
- Especially preferred metathesis active adhesion agents are olefin-containing silanes such as allyltrimethoxysilane, butenyltriethoxysilane, hexenyltriethoxysilane, octenyltriethoxysilane, norbomenyltriethoxysilane, norbomenylethyltriethoxysilane, and the like.
- porous materials may be used in the present invention so long as such materials are pervious to the unpolymerized cyclic olefin resin formulation and do not contain chemical groups that are incompatible with the olefin metathesis catalyst.
- Such porous materials include but are not limited to wood, cement, concrete, open-cell and reticulated foams and sponges, papers, cardboards, felts, ropes or braids of natural or synthetic fibers, and various sintered materials.
- Preferred non-organic materials include unglazed porous ceramics, compacted free standing metal powder objects, and porous concrete aggregates such as cinder blocks.
- Preferred organic materials include wood, wood products and related cellulosic materials in various forms. These include but are not limited to monolithic wood objects as well as laminated wood, plywood, particleboard and chipboard objects and products. The most preferred porous materials are various types of wood.
- Portland cement or concrete has an open pore structure that is interwoven and interconnected.
- One particular form of cement called Enhanced Porosity Cement (EPC) uses little or no sand and has a 20-25% void volume.
- EPC Enhanced Porosity Cement
- the markedly porous structure of all cements and related materials allows for the ready diffusion of air, other gases and water vapor. This porous structure also facilitates moisture migration and the wicking of water.
- Such processes are capable of incorporating destructive pollutants such as nitrate, sulfate and chloride salts into the concrete. At various rates, these salts weaken the concrete structure, promote rusting of embedded steel reinforcing materials, which expand on oxidation and promote the formation of hairline cracks and fissures.
- infused composites of the present invention Catalyzed cyclic olefin monomer formulations effectively infuse into the pore structure, cracks and fissures of concrete, and related materials, to provide chemically stable ROMP polymers that provide a barrier to water, water vapor and dissolved salts as well as a reduced permeability to corrosive gases such as NO x and SO 2 .
- the infused concrete can also exhibit up to a three to four times increase in compressive strength, flexural strength and durability along with a 50- 100% increase in the modulus of elasticity.
- the high reactivity and functional group tolerance of the preferred metathesis catalysts allow for polymerization within the porous structures of a wide variety of porous materials. These catalysts are effective at relatively low loading in resins, they operate at relatively low temperature, and are tolerant of reactive molecules surface absorbed in the porous stmcture and reactive functional groups on such surfaces, as well as such reactive functional groups in the resin materials.
- the initiation and polymerization rates of the cyclic olefin monomers may be controlled over a wide range by judicious choice of the chemical stmcture of the preferred metathesis catalyst and/or the use of rate-modifying additives as is well known in the art.
- the low viscosity of the preferred cyclic olefin resin formulations facilitates the infusion of the porous materials.
- DCPD has a much lower resin viscosity than other polymeric starting materials such as epoxy resins.
- the low viscosity of DCPD resins allows for a greater degree of infusion into porous and microporous stmctures characteristic of porous materials such as wood.
- ROMP catalysts together with the low viscosity of the DCPD resin allows the resins to cure without the extreme temperatures and pressures required for other polymers derived from phenols, polyesters, epoxies, resorcinols or ureas that can cause breakdown of the porous material stmcture, especially for sensitive organic substrates such as wood.
- polymers derived from metathesis polymerization of cyclic olefin monomers are stable to hydrolysis and are insoluble in polar organic solvents and therefore yield infused products that are stable to leaching and polymer decomposition.
- the preferred resins are also compatible with and will accommodate a variety of additional additives and fillers to impart additional properties to the infused composites.
- the resulting infused composites are generally tougher, harder, more dense, and more rigid than the starting porous substrate alone.
- less expensive softer woods are, therefore, able to replace more expensive harder woods in various applications such as sporting equipment, tool handles, furniture, flooring, railings, window frames, stairs, decking, etc; and marine applications such as boats, piers and pilings.
- Such infused and treated wood will be resistant to the uptake of water and resistant to rot and insect damage. The surface wear characteristics will be greatly improved for such applications.
- ROMP catalysts and resins are available to use within wood with various amounts of absorbed water in order to stabilize the wood to loss of such water.
- the resulting compositions exhibit unique properties of the composite for the portion of the material that is infused, while the shape of the final product is determined by that of the starting free-standing object.
- the invention allows for a wide variety of infused products to be manufactured without the use of complex molds.
- polyolefin-infused compositions of the invention are useful in the production of a variety of products in the areas of sports and recreation equipment, marine infrastmcture, and constmction and consumer goods where enhanced mechanical performance, durability, and/or moisture-resistance are required.
- sports and recreation products and applications include, but are not limited to, the following: golf tees, clubs (including weighted club heads), shafts, and gradient shafts (where the formulation or density varies along the length of the club shaft); basketball backboards; tennis rackets, squash rackets, racquetball rackets, and badminton racquets; snow boards, surfboards, boogie boards, skis, backboards, sleds, toboggans; baseball and cricket bats; hockey sticks; pool cues; archery bows and arrows; rifle butts; polo and croquet mallets; and tent stakes.
- Examples of marine infrastmcture applications include, but are not limited to, the following: piers, docks, posts, decking, hulls, oars, propellers, mdders, keels, masts, boat fascia, kayaks, canoes, and ferro-cement boats.
- constmction and consumer goods applications include, but are not limited to, the following: hand-tool handles, knife handles, ladders, wood flooring panels, deck lumber, treated concrete or cinder blocks, door and window frames, office furniture, concrete bridge decks, parking stmcture ramps, post-tensional beams and slabs, treated concrete pipes and channel liners for aggressive and acidic fluids, sewer pipes, containment stmctures, pavers, stone consolidation (e.g., James R. Clifton, National Bureau of Standards, Technical Note 1118, May 1980, Government Documents C 13.46:1118), plaster or concrete ornamental objects, and other pre-cast concrete objects.
- hand-tool handles e.g., knife handles, ladders, wood flooring panels, deck lumber, treated concrete or cinder blocks, door and window frames, office furniture, concrete bridge decks, parking stmcture ramps, post-tensional beams and slabs, treated concrete pipes and channel liners for aggressive and acidic fluids, sewer pipes, containment stmctures,
- porous materials infused with ROMP polymers to provide new composites with improved physical properties include unglazed sintered ceramics of all types including but not limited to ceramic magnets, superconducting ceramic materials, ceramic capacitors, and capacitors from reconstituted mica paper.
- Various open cell plastic foams including but not limited to those derived from polyurethane, provide new compositions with a wide variety of applications.
- Graphite foams with continuous porous stmctures have a variety of novel applications as heat sinks and in thermal management technology. This material has the thermal conductivity of aluminum with approximately 20% of its weight.
- applications of graphite foam are limited by the inherently brittle and friable nature of this material and corresponding incidental damage in use. Infusing ROMP polymers into graphite foam provide an effective means to mggedize the structures and objects as formed and to yield new composites.
- a variety of processing techniques may be utilized to prepare the resin-infused composites of the present invention.
- highly porous materials it may be sufficient to place the porous substrate in a container and simply pour in the formulated resin.
- medium-porosity materials a simple dipping or soaking process may be feasible.
- pressure or a combination of vacuum and pressure may be required to get the formulated resin to completely permeate the porous substrate. This may be accomplished by variations of standard processing techniques such as resin-transfer molding (RTM) or vacuum-assisted RTM (VARTM or SCRIMP ® , Seemann Composite Resin Infusion Molding Process).
- a mold or container such mold may be constructed of various materials including, for example, aluminum, teflon, delrin, high- and low-density polyethylenes (HDPE and LDPE, respectively), silicone, epoxy, aluminum-filled epoxy, polyurethane and aluminum-filled polyurethane, plaster, polyvinylchloride (PVC), and various alloys of stainless steel.
- the mold temperature is preferably about 20-150°C, more preferably about 30-100°C, and most preferably about 40-60°C.
- the infused part or article of the invention may also be subjected to a post-cure heating step.
- the post-cure involves heating to about 60-200°C for about 10 minutes - 3 hours. More preferably, the post-cure involves heating to about 80-160°C for about 30 minutes - 2 hours and, and most preferably, heating to about 140°C for about 1 hour.
- a vacuum/pressure process is preferred to achieve good infusion with the cyclic olefin resin formulation.
- the vacuum process helps to remove air and water vapor from the pores of the substrate. After evacuation of the substrate, the resin formulation is applied and is drawn into the empty pores.
- Application of moderate pressure typically between about 5 and 200 psi and preferably between about 40-60 psi helps to push the resin fully into the pores of the substrate.
- moderate pressure typically between about 5 and 200 psi and preferably between about 40-60 psi
- the time required to fully infuse the particular article can vary widely based on the shape and pore stmcture of the article and the viscosity of the resin formulation but will typically vary from about 30 seconds to several hours.
- the progress of the infusion may be determined and/or controlled by monitoring the weight of the substrate.
- Pressure alone may be effective in the infusion of microporous substrates if their internal stmcture and/or the infusion methodology is such that any gas displaced by the infused resin can escape rather than becoming pressurized. If pressurization occurs, then the typically low- viscosity (at least before they are cured) cyclic olefin resin formulations may be at least partially expelled from the pores of the substrate upon the release of the externally applied pressure due to the backpressure exerted by the compressed gasses trapped within the pores.
- porous substrates may require chemical or mechanical pretreatment prior to the resin infusion process.
- the pores of pre-shaped (e.g., machined) wood billets tend to be at least partially clogged by sawdust and other particulate impurities that hinder the ingress of resin during infusion.
- Careful mechanical cleaning of the surface of such wood billets with a wire bmsh has been found to be an effective, albeit labor intensive, pretreatment process.
- a high- pressure water spray treatment which may clean and wet an object, followed by careful drying serves as an excellent pretreatment method for wood substrates.
- this methodology more deeply opens the pores of water-swellable substrates such as wood due to both the mechanical cleaning action of the impinging water droplets at the surface of the substrate as well as the bulk expansion and contraction of the substrate during the overall wetting and drying process.
- This methodology also has the advantages that it is amenable to automation and that adhesion or coupling agents, that will facilitate chemical bonding between the resin and substrate, can be easily incorporated into the water treatment rather than as a separate step.
- adhesion or coupling agents that will facilitate chemical bonding between the resin and substrate, can be easily incorporated into the water treatment rather than as a separate step.
- the pressure was released and the dowel removed from the mold and heated in an oven at 60°C for eight hours to cure the resin. After curing, the surface of the dowel was lightly sanded to remove excess resin. The sanded dowel was then post-cured in an oven for one hour at 140°C. The density of the dowel increased from 40.77 pcf to 45.95 pcf due to the infused resin.
- the mold was sealed, evacuated to degas the resin and the pores of the dowel, and then pressurized to 60 psi for one hour.
- the pressure was released and the dowel removed from the mold and heated in an oven at 60°C for 6.5 hours to cure the resin.
- the dowel was then post-cured in an oven for one hour at 140°C.
- the density of the dowel increased from 40.96 pcf to 49.72 pcf due to the infused resin.
- the stiffness of the treated wood also increased as evidenced by the decrease in the measured deflection from 0.013 inches before treatment to 0.011 inches after treatment.
- the mold was sealed, evacuated to degas the resin and the pores of the dowel, and then pressurized to 60 psi for seven hours.
- the pressure was released and the dowel removed from the mold and heated in an oven at 60°C for eight hours to cure the resin. After light sanding to remove excess resin, the dowel was then post-cured in an oven for one hour at 140°C.
- the density of the dowel increased from 37.55 pcf to 45.90 pcf due to the infused resin.
- the stiffness of the treated wood also increased as evidenced by the decrease in the measured deflection from 0.026 inches before treatment to 0.013 inches after treatment.
- Example 3 The stiffness and impact resistance of the DCPD-infused white ash dowels of Example 3 - Example 6 were measured as described in Example 1. The data are summarized in Table 3, compared with untreated samples IB and 40B from Example 1, and demonstrate the increased impact performance of the infused wood.
- the adhesion between resin and wood can be measured using a 1" long wood dowel (1.125" diameter) with a V2" diameter hole drilled down through its center.
- the specimen can be optionally conditioned before the desired resin formulation is poured into the bore and cured into place.
- the adhesion between the wood and the resin is then evaluated by determining the force required to push the cast resin plug out of the bore.
- a baseline DCPD resin formulation comprising approximately 3.5% of trimeric CPD isomers along with smaller amounts of higher oligomers was prepared by blending 1,759 grams of Ultrene -99 DCPD with 241 grams of CM15T (heat-treated DCPD containing approximately 29% trimeric CPD and smaller amounts of higher oligomers obtained from BF Goodrich).
- Example 8 Five white ash wood specimens as described in Example 8 were soaked in a solution of 2 phr allyltriethoxysilane (Gelest) in 0.6 millimolar aqueous acetic acid for 20 minutes. The specimens were then dried for 3 hours at 60°C in an oven. The resin mixture of Example 8 was poured into the bore and cured for 1 hour at 40°C to form a solid plug within the wood dowel. After 5 hours, the specimens were post-cured at 140°C for 1 hour. Results for these specimens averaged 2,721 ⁇ 176 psi.
- Gelst 2 phr allyltriethoxysilane
- Example 8 Two white ash wood specimens as described in Example 8 were soaked in a solution of 0.6 millimolar aqueous acetic acid for 20 minutes. The specimens were then dried for 3 hours at 60°C in an oven. The resin mixture of Example 8 was poured into the bore and cured for 1 hour at 40°C to form a solid plug within the wood dowel. After 5 hours, the specimens were post-cured at 140°C for 1 hour. Results for these specimens averaged 2,593 ⁇ 11 psi.
- Example 11 Water Treatment of Wood to Improve Wood-Resin Adhesion
- Example 8 Five white ash wood specimens described in Example 8 were soaked in deionized water for 20 minutes. The specimens were then dried for 3 hours at 60°C in an oven. The resin mixture of Example 8 was poured into the bore and cured for 1 hour at 40°C to form a solid plug within the wood dowel. Results for these specimens averaged 2,606 ⁇ 193 psi.
- Example 12 Aqueous Isopropanol Treatment of Wood to Improve Wood-Resin Adhesion
- Example 8 Two white ash wood specimens as described in Example 8 were soaked in 50% isopropanol for 20 minutes. The specimens were then dried for 3 hours at 60°C in an oven. The resin mixture of Example 8 was poured into the bore and cured for 1 hour at 40°C to form a solid plug within the wood dowel. Results for these specimens averaged 2,526 ⁇ 44 psi.
- Example 8 Two white ash wood specimens as described in Example 8 were soaked in a solution of 0.2 grams of mono-memyl-c s-5-norbomene-er ⁇ fo-2,3-dicarboxylate (Sigma- Aldrich) in 10 grams of 50% isopropanol for 20 minutes. The specimens were then dried for 3 hours at 60°C in an oven. The resin mixture of Example 8 was poured into the bore and cured for 1 hour at 40°C to form a solid plug within the wood dowel. Results for these specimens averaged 2,308 ⁇ 184 psi.
- Example 14 Two white ash wood specimens as described in Example 8 were soaked in a solution of 0.2 grams of mono-memyl-c s-5-norbomene-er ⁇ fo-2,3-dicarboxylate (Sigma- Aldrich) in 10 grams of 50% isopropanol for 20 minutes. The specimens were then dried for 3 hours at 60°C in an oven. The resin mixture of Example
- Example 8 Specimens as described in Example 8 were prepared using low-grade white ash wood dowels, within the density range indicated in Example 14, wherein the resin mixture was modified by the addition of 1 phr of various titanate and zirconate coupling agents available from Kenrich Petrochemicals, Inc.
- Specimens as described in Example 8 were prepared using pine and poplar along with white ash. Both the standard resin formulation as well as a modified formulation containing 0.5 phr Ken-React ® KR 55 coupling agent were used. The results are summarized in Table 5 and show that these woods behave similarly to white ash.
- Example 17 DCPD Resin Uptake By White Ash Baseball Bats Resin uptake for a series often net-shape white ash bats is shown in Chart 2. Even though encompassing results involving many different parameter variations, the data appear to suggest that less resin can be infused into higher density wood. Although not totally unexpected, there does, perhaps, appear to be a preferred weight for the infused wood (around 1 ,000 grams - a little heavy for bat application) suggesting that it may be possible to upgrade a wide range of wood densities to a more consistent final product density.
- Chart 3 summarizes the results obtained for variations in infusion time. All of these experiments were performed using net-shape bats with 60-psi infusion pressure. Data for high-density (e.g., over 800 grams) and low-density (e.g., under 800 grams) bats were analyzed separately. The data suggest that infusion occurs fairly quickly, likely aided by the very low viscosity of the DCPD resins, although somewhat higher resin loadings might be attained with extended infusion times.
- Pre-shaped wood baseball bat blanks, with a cupped end, of minor grade white ash were weighed and then subjected to a high-pressure water spray treatment with ordinary municipal tap water under pressure of approximately 50 PSI across the bat from the knob to the handle to the barrel of the bat, as the bat was manually turned in order to completely cover the long axis and along the grain of the bat for approximately 30 seconds.
- the cupped end of the bat barrel and the knob end of the bat and across the grain of the wood were given particular attention with approximately 15 seconds of wash.
- This water spray treatment appeared to mechanically remove loose material, sand or saw dust and to open the end grain of the wood.
- the weight of the bat blanks before the water treatment varied from approximately 700 to 800 grams and from approximately 725 to 825 grams after the water wash.
- each bat was then allowed to air dry for approximately 24 hours at ambient temperature and humidity during which the weight of the bat dropped to a range of approximately 710 to 810 grams.
- the bats were then placed into an oven at 60° C for 30 minutes. The oven temperature was then increased over a five-minute period to 100° C and maintained there for an additional 60 minutes. After cooling, the bats then weighed near or slightly below the original range of 700-800 grams.
- a goal of the infusion process is to bring each wood bat up to a weight of 900 grams regardless of the starting weight of the bat.
- the stepwise process utilizing the equipment as shown in Figure 1 achieves this goal using a system of two separate metal chambers that are connected by high-pressure flexible tubing.
- One chamber is used to perform the infusion process (the "Mold") and the other is used to store the DCPD resin formulation (the “Resin Chamber”).
- the process allows a variety of DCPD resin formulations to be introduced to the free standing porous wooden bat under vacuum in order to completely coat or cover the bat, followed by raising the pressure of the liquid resin to facilitate its infusion into voids of the wood.
- wood bat blanks of low-medium grade ash and with a cupped end are weighed and then subjected to a high-pressure water spray treatment as described in Example 18. After complete drying, each bat is then placed into the Mold of cylindrical dimensions sufficient to closely and completely enclose the bat and with a removable end to allow the bat to be placed in the vessel.
- the Mold is mounted vertically to allow the bat to be completely submerged in resin with the removable end at the top of the cylinder.
- the removable end of the Mold is equipped with two valves (V3 and V4) with removable tubing fittings with one to allow the chamber to be placed under vacuum and the other to allow the introduction of a gas under pressure to flush the resin from the chamber.
- a third pressure fitting and valve (V2) on the bottom of the Mold allows the introduction of DCPD resin formulations from the separate Resin Chamber.
- the Resin Chamber has a removable top equipped with a dip tube (VI) to allow resin from the bottom of the chamber to be introduced into the bottom of the infusion chamber through a flexible pressure tube. Additional valves (V5 and V6) are used for applying or venting pressure to the resin chamber.
- the Resin Chamber may be periodically refilled with freshly mixed DCPD resin formulation through valve V7.
- the mold, containing a bat, and the resin transfer tube are evacuated through valve V3, with valve V2 open and valves VI and V4 closed, with a mechanical pump to approximately 10 " atmospheres, which results in removal of air from the pores of the wood.
- the vacuum valve V3 is then closed, and the weighing mechanism is tared.
- the Mold is then completely backfilled with resin from the Resin Chamber by opening valves VI and V5.
- the infusion pressure is controlled by the pressure of the inlet gas at valve V5 and is usually 55 psi or more to promote the infusion of the formulated DCPD resin into the porous stmcture of the wood.
- the total weight of the mold is continuously monitored until the uptake of resin is sufficient to bring the total weight of each bat up to a weight of 900 grams. This can be easily calculated for each bat if the Mold volume and the bat volume and weight are known. The time that this can take typically varies from as short as 10 seconds to as long as 7 minutes.
- the Mold is then opened, the infused bat is removed to a curing oven, and the next bat is placed into the Mold so that the cycle can be repeated. If required, additional DCPD resin formulation can also be added to the Resin Chamber at this time.
- the resin curing process is promoted by placing the infused bat in an oven at 60° C for 30 minutes, followed by 2 hours at room temperature, and then a final post-cure at 140° C for 1 hour. After cooling back to room temperature, the bat is then ready for finishing to a commercial product by a final sanding, painting and/or the addition of graphics, and application of a polyurethane top-coat for UV protection and improved appearance.
- a sampling of pre-shaped but otherwise unfinished wooden bats were obtained and sorted into three grades according to the number of grains counted at the knob. Longstanding experience with baseball bats indicates that lower grain counts correspond to increased durability. Therefore, high-grade bats had grain counts of about 16 or less, medium-grade bats had grain counts from about 17 to 28, and low-grade bats had grain counts of about 29 or greater.
- Half of the bats were finished normally with a polyurethane top coat while the other half were infused with DCPD resin as described in Example 19.
- Chart 4 shows the number of "hits-to-failure" for these untreated and DCPD-infused wood bats relative to the grain count.
- untreated high-grade baseball bats would typically be expected to exhibit approximately 200-250 hits to failure while low-grade or medium- grade bats would typically fail after fewer hits.
- the infused bats typically exhibit greater durability (usually greater than 300 hits-to-failure) than comparable untreated bats and allow a much lower grade of wood to perform as well or better than untreated bats made of high-grade wood.
- Chart 5 shows the depth of dents measured in both untreated and DCPD-infused baseball bats relative to the number of hits sustained. These measurements were done with a baseball impinging at 136 miles per hour, 5 inches from the barrel end and with the wood grain parallel to the point of impact. The data demonstrate the significant resistance to denting by the infused wood. Chart 5
- a DCPD resin formulation comprising approximately 3.5% of trimeric CPD isomers along with smaller amounts of higher oligomers was prepared by blending an 88/12 mixture of Ultrene ® -99 DCPD and CM15T (heat-treated DCPD containing approximately 29% trimeric CPD and smaller amounts of higher oligomers obtained from BF Goodrich), with 3 phr of Ethanox®-702 (Albemarle) primary antioxidant, 0.1 phr of triphenylphosphine inhibitor, and metathesis catalyst. This resin mixture was poured over small pieces of porous concrete block in a mold. The mold was sealed and then pressurized to 55 psi. The pressure was released and the infused pieces removed from the mold and allowed to cure overnight at room temperature.
- Samples of birch, cherry, douglas fir, maple, poplar, red oak, southern yellow pine, and white ash woods were cut into 1" x 1" x 12" rectangular dowels.
- the cut samples were washed using pressurized tap water (90 psi) for 1 minute and then air-dried for 48 hours at room temperature (20-24°C).
- the specimens were further dried in a vacuum oven for
- the weight of each of the dowels after this treatment ranged from 4-6% less that its starting weight.
- Table 7 The compression properties were tested for each piece parallel to the direction of the grain and are summarized in Table 8.
- the Shore D hardness was measured for a specimen of each wood and is summarized in Table 9.
- a resin formulation comprising DCPD with 10% trimeric CPD content, 3 phr Ethanox - 702 antioxidant, 0.2 phr triphenylphosophine inhibitor, 1 phr Ken-React ® KR 55 organotitanate, and metathesis catalyst was applied to pieces of 0.010" thick predried cardstock cut into a dogbone shape suitable for tensile testing. The resin appeared to quickly wet into the porous web. The sheet was then cured for 1 hour at 40°C, 2 hours at room temperature, and then post-cured for 1 hour at 140°C. Using this methodology, a series of 6 specimens picked up an average of 3.37 ⁇ 0.54 % resin.
- the dry, but untreated, cardstock exhibited the following tensile properties: 5,979 psi tensile strength, 313,597 tensile modulus, and 3.60 % strain-to- break.
- the treated cardstock exhibited the following improved tensile properties: 6,663 psi tensile strength, 375,936 psi tensile modulus, and 3.20 % strain-to-break.
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Abstract
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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EP02766184A EP1446284B1 (en) | 2001-08-30 | 2002-08-30 | Infusion of cyclic olefin resins into porous materials |
BRPI0212392A BRPI0212392B1 (en) | 2001-08-30 | 2002-08-30 | A process for preparing a polyolefin-infused porous material and manufactured article. |
NZ531455A NZ531455A (en) | 2001-08-30 | 2002-08-30 | Infusion of cyclic olefin resins into porous materials |
CA2458904A CA2458904C (en) | 2001-08-30 | 2002-08-30 | Infusion of cyclic olefin resins into porous materials |
DE60229158T DE60229158D1 (en) | 2001-08-30 | 2002-08-30 | INFUSION OF CYCLIC OLEFIN RESINS IN POROUS MATERIALS |
BRPI0216123-0A BRPI0216123B1 (en) | 2001-08-30 | 2002-08-30 | COMPOSITION COMPOSING COMPOSITION OF POROUS MATERIAL INFUSED WITH POLYOLEFIN |
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US31629001P | 2001-08-30 | 2001-08-30 | |
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EP (1) | EP1446284B1 (en) |
CN (2) | CN1281405C (en) |
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BR (1) | BRPI0212392B1 (en) |
CA (1) | CA2458904C (en) |
DE (1) | DE60229158D1 (en) |
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- 2002-08-30 WO PCT/US2002/027654 patent/WO2003020504A1/en not_active Application Discontinuation
- 2002-08-30 CN CNB028217551A patent/CN1281405C/en not_active Expired - Lifetime
- 2002-08-30 BR BRPI0212392A patent/BRPI0212392B1/en not_active IP Right Cessation
- 2002-08-30 US US10/233,066 patent/US20030186035A1/en not_active Abandoned
- 2002-08-30 AT AT02766184T patent/ATE409581T1/en not_active IP Right Cessation
- 2002-08-30 CA CA2458904A patent/CA2458904C/en not_active Expired - Lifetime
- 2002-08-30 NZ NZ531455A patent/NZ531455A/en not_active IP Right Cessation
- 2002-08-30 CN CN200610121447XA patent/CN101338062B/en not_active Expired - Fee Related
- 2002-08-30 DE DE60229158T patent/DE60229158D1/en not_active Expired - Lifetime
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EP2608949B1 (en) | 2010-08-23 | 2023-03-29 | Materia, Inc. | Vartm flow modifications for low viscosity resin systems |
WO2018072891A1 (en) | 2016-10-18 | 2018-04-26 | Covestro Deutschland Ag | Method for producing a foam body having an internal structure |
US10946569B2 (en) | 2016-10-18 | 2021-03-16 | Covestro Deutschiand AG | Method for producing a foam body having an internal structure |
Also Published As
Publication number | Publication date |
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US20060052487A1 (en) | 2006-03-09 |
CN1578726A (en) | 2005-02-09 |
CN101338062B (en) | 2012-09-05 |
NZ531455A (en) | 2007-06-29 |
DE60229158D1 (en) | 2008-11-13 |
ATE409581T1 (en) | 2008-10-15 |
US20030186035A1 (en) | 2003-10-02 |
CA2458904A1 (en) | 2003-03-13 |
CA2458904C (en) | 2012-07-17 |
EP1446284B1 (en) | 2008-10-01 |
EP1446284A4 (en) | 2005-12-07 |
CN101338062A (en) | 2009-01-07 |
BRPI0212392B1 (en) | 2015-09-15 |
CN1281405C (en) | 2006-10-25 |
BR0212392A (en) | 2004-08-17 |
EP1446284A1 (en) | 2004-08-18 |
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