CN105579495A - 纤维纸浆及其在复合材料中的用途 - Google Patents
纤维纸浆及其在复合材料中的用途 Download PDFInfo
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- CN105579495A CN105579495A CN201480052615.7A CN201480052615A CN105579495A CN 105579495 A CN105579495 A CN 105579495A CN 201480052615 A CN201480052615 A CN 201480052615A CN 105579495 A CN105579495 A CN 105579495A
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- 239000002131 composite material Substances 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 239000000835 fiber Substances 0.000 claims abstract description 37
- -1 needles Substances 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 8
- 229920003235 aromatic polyamide Polymers 0.000 claims description 20
- 229920001131 Pulp (paper) Polymers 0.000 claims description 15
- 239000004760 aramid Substances 0.000 claims description 14
- 229920000728 polyester Polymers 0.000 claims description 12
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 229960001866 silicon dioxide Drugs 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 235000019241 carbon black Nutrition 0.000 claims description 2
- 229920006037 cross link polymer Polymers 0.000 claims description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920005594 polymer fiber Polymers 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 235000012222 talc Nutrition 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 18
- 239000000806 elastomer Substances 0.000 abstract description 2
- 239000005060 rubber Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 150000003851 azoles Chemical class 0.000 description 10
- 239000000654 additive Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 150000004985 diamines Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920000271 Kevlar® Polymers 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 239000004761 kevlar Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
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- 229920001519 homopolymer Polymers 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 229920002577 polybenzoxazole Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
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- 229920006389 polyphenyl polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 3
- 239000004953 Aliphatic polyamide Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000004113 Sepiolite Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229920003231 aliphatic polyamide Polymers 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
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- 238000001816 cooling Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- UHPJWJRERDJHOJ-UHFFFAOYSA-N ethene;naphthalene-1-carboxylic acid Chemical compound C=C.C1=CC=C2C(C(=O)O)=CC=CC2=C1 UHPJWJRERDJHOJ-UHFFFAOYSA-N 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- MMQJZQKFTWIATR-UHFFFAOYSA-N 1h-pyrazole;1h-pyrrole Chemical class C=1C=CNC=1.C=1C=NNC=1 MMQJZQKFTWIATR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000428352 Amma Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 1
- 229920012306 M5 Rigid-Rod Polymer Fiber Polymers 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
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- 125000005647 linker group Chemical group 0.000 description 1
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- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000015927 pasta Nutrition 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- 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
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
-
- 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
- B60C15/00—Tyre beads, e.g. ply turn-up or overlap
- B60C15/06—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
- C08J3/212—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase and solid additives
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
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- Dispersion Chemistry (AREA)
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Abstract
本发明公开了一种组合物，其包含(i)弹性体，(ii)1至5体积％的纤维纸浆，所述纸浆具有7至11sq.m./g的比表面积，并且所述纤维具有0.5至1.1mm的纤维长度，2.5至130GPa的拉伸模量，和1至3GPa的拉伸强度，以及(iii)5至14体积％呈纤维、针状物、粉末或片状物形式的屈服应变促进剂，其中所述组合物具有至少70％的屈服应变，至少200％的断裂伸长率和至少4MPa的屈服应力。
Description
背景技术
1.技术领域
本发明涉及一种组合物，所述组合物可以为用于制备工业橡胶制品诸如轮胎和带的化合物的组分。本发明尤其适用于遇到高应变环境的应用中。
2.相关领域说明
授予Frances的美国专利4,514,541涉及颗粒状弹性体组合物，其具有0.1至0.4的密度比，包含按重量计5-75％的弹性体、按重量计15-65％的填料和按重量计10-60％的芳族聚酰胺纸浆，以及用于其制备的溶液法。所述组合物可用作将芳族聚酰胺纸浆引入弹性体制品中的母料。
授予Levit和Amma的美国专利8,211,272涉及包含间位芳族聚酰胺沉析纤维的对位芳族聚酰胺纸浆，其用作产品中的增强材料，所述产品包括例如摩擦材料、液体密封材料和纸材。本发明还涉及制备此类纸浆的方法。
存在对具有橡胶-纤维纸浆复合材料的持续需要，所述复合材料具有至少70％的屈服应变，至少4MPa的屈服应力和至少200％或甚至300％的伸长率。高度期望在高应变轮胎中使用此类复合材料。
通过使用较高芳族聚酰胺纸浆浓度、纤维分散剂和界面改性剂来实现该期望的先前的尝试导致减小的屈服应变。Ming等人，(J.Appl.PolymerSei.120，1439，2011)研究了使用不同类型的橡胶、纤维和原纤化二氧化硅制成的复合材料。其结果示出小于50％的屈服应变。
发明内容
本发明涉及一种组合物，所述组合物包含：
(i)弹性体，
(ii)1至5体积％的纤维纸浆，所述纸浆具有7至11sq.m./g的比表面积，并且所述纤维具有0.5至1.1mm的纤维长度，6至130GPa的拉伸模量，和1至3GPa的拉伸强度，以及
(iii)5至14体积％的呈纤维、针状物、粉末或片状物形式的屈服应变促进剂，
其中所述组合物具有至少70％的屈服应变、至少200％的断裂伸长率、以及至少4MPa的屈服应力。
具体实施方式
弹性体
如本文所用，术语“橡胶”和“弹性体”可以互换使用，除非另有说明。术语“橡胶组合物”、“复合橡胶”和“橡胶化合物”可以互换使用，是指“与多种成分和材料共混或混合的橡胶”，此类术语是橡胶混合或橡胶配混领域的技术人员所熟知的。
本发明的弹性体包括天然橡胶、合成天然橡胶和合成橡胶。合成橡胶化合物可以为被常用有机溶剂溶解的任何橡胶化合物，并可以包括(除了许多别的以外)聚氯丁二烯和硫改性的氯丁二烯、烃橡胶、丁二烯-丙烯腈共聚物、丁苯橡胶、氯磺化聚乙烯、含氟弹性体、聚丁二烯橡胶、聚异戊二烯橡胶、丁基橡胶和卤化丁基橡胶等。天然橡胶、丁苯橡胶、聚异戊二烯橡胶和聚丁二烯橡胶是优选的。还可以利用橡胶的混合物。
短纤维
具有0.5至1.1mm的纤维长度和7至11sq.m./g的比表面积的短纤维增强材料可以呈絮凝物或纸浆的形式。分散于水中的纸浆是优选的形式。纤维以1至5体积％，更优选地1.5至3体积％的量存在。
合适的纤维为具有6至130GPa的特定拉伸模量和1至3GPa的特定拉伸强度的那些。纤维可以为玻璃、碳、纤维素、芳族聚酰胺、芳族共聚酰胺、脂族聚酰胺、聚酰亚胺、聚酯、聚烯烃或聚唑。可使用不同纤维的共混物。一些纤维可以呈纳米管的形式。单壁纳米管和多壁纳米管两者均是合适的。
当聚合物为聚酰胺时，在一些实施例中，优选芳族聚酰胺。术语“芳族聚酰胺”是指其中至少85％的酰胺键(-CONH-)直接连接到两个芳族环的聚酰胺。合适的芳族聚酰胺纤维包括(均得自TeijinAramid)、HeraconTM(得自KolonIndustriesInc.)或(得自DuPont)。芳族聚酰胺纤维在Man-MadeFibres-ScienceandTechnology第2卷(IntersciencePublishers，1968年)的标题为“Fibre-FormingAromaticPolyamides”的章节中(第297页，W.Black等人)有所描述。芳族聚酰胺纤维以及它们的生产在美国专利3,767,756、4,172,938、3,869,429、3,869,430、3,819,587、3,673,143、3,354,127和3,094,511中也有所公开。
在一些实施例中，优选的芳族聚酰胺为对位芳族聚酰胺。一种优选的对位芳族聚酰胺是被称为PPD-T的聚(对苯二甲酰对苯二胺)。所谓PPD-T，是指由对苯二胺与对苯二甲酰氯的等摩尔比聚合反应产生的均聚物，以及由少量其它二胺与对苯二胺结合、少量其它二酰氯与对苯二甲酰氯结合所得的共聚物。作为一般原则，其它二胺和其它二酰氯的使用量可至多多达对苯二胺或对苯二甲酰氯的约10摩尔％，或者可能略高，前提条件是仅其它二胺和二酰氯不含干扰聚合反应的反应性基团。PPD-T也指其它芳族二胺和其它芳族二酰氯结合所得的共聚物，诸如例如2，6-萘亚甲基酰氯或氯代对苯二甲酰氯或二氯对苯二甲酰氯或3，4’-二氨基二苯醚。添加剂可与芳族聚酰胺一起使用，并且已发现，按重量计至多多达10％或更多的其它聚合材料可与芳族聚酰胺共混。可使用共聚物，所述共聚物具有多达10％或更多的其它二胺(替代了芳族聚酰胺的二胺)或者多达10％或更多的其它二酰氯(替代了芳族聚酰胺的二酰氯)。
另一种合适的纤维为基于芳族共聚酰胺的纤维，诸如通过对苯二甲酰氯(TPA)与50/50摩尔比的对亚苯基二胺(PPD)和3，4′-二氨基二苯醚(DPE)的反应制备的。另一种合适的纤维为通过如下方式形成的纤维：两种二胺即对亚苯基二胺和5-氨基-2-(对氨基苯基)苯并咪唑与这些单体的对苯二甲酸衍生物或酸酐衍生物或酰氯衍生物进行缩聚反应。
脂族聚酰胺的示例为聚酰胺-6、聚酰胺-6，6、聚酰胺-6，10、聚酰胺-6，12、聚酰胺-11、聚酰胺-12。
当纤维为聚烯烃时，在一些实施例中，优选聚乙烯或聚丙烯。当配混纤维与弹性体以压延或挤出化合物或者固化轮胎组合件中的化合物所要求的加工温度低于聚烯烃的熔点时，只可以使用聚烯烃纤维。术语“聚乙烯”是指分子量优选地大于一百万的主要为线性的聚乙烯材料，其可以包含微量的支链或每100个主链碳原子中不超过5个改性单元的共聚单体，其还可以包含与其混合在一起的不超过约50重量百分比的一种或多种聚合物添加剂，诸如烯烃-1-聚合物，具体地讲是低密度聚乙烯、丙烯等，或低分子量添加剂，诸如通常掺入的抗氧化剂、润滑剂、紫外线遮蔽剂、着色剂等。此类聚乙烯通常被称为伸展链聚乙烯(ECPE)或超高分子量聚乙烯(UHMWPE)。聚乙烯纤维的制备在美国专利4,478,083、4,228,118、4,276,348和4,344,908中有所讨论。高分子量线性聚烯烃纤维可以商购获得。聚烯烃纤维的制备在美国专利4,457,985中有所讨论。
在一些实施例中，聚唑纤维为聚芳唑，诸如聚苯唑和聚吡啶并唑。合适的聚唑包括均聚物和共聚物。添加剂可与聚唑一起使用，并且至多多达按重量计10％的其它聚合材料可与聚唑共混。还可使用的共聚物具有多达10％或更多的替代了聚唑单体的其它单体。合适的聚唑均聚物和共聚物可通过已知的工序制备，诸如描述于或源自美国专利4,533,693、4,703,103、5,089,591、4,772,678、4,847,350和5,276,128的那些工序。
优选的聚苯并唑包括聚苯并咪唑、聚苯并噻唑和聚苯并唑，更优选的是可以形成具有30克/分特(gpd)或更大的纱线韧度的纤维的此类聚合物。在一些实施例中，如果聚苯并唑为聚苯并噻唑，则它优选地为聚(对亚苯基苯并二噻唑)。在一些实施例中，如果聚苯并唑为聚苯并唑，则它优选地为聚(对亚苯基苯并二唑)，更优选地为被称为PBO的聚(对亚苯基-2，6-苯并二唑)。
优选的聚吡啶并唑包括聚吡啶并咪唑、聚吡啶并噻唑和聚吡啶并唑，更优选的是可以形成具有30克/分特或更大的纱线韧度的纤维的此类聚合物。在一些实施例中，优选的聚吡啶并唑为聚吡啶并二唑。一种优选的聚(吡啶并二氧杂唑)为聚(1，4-(2，5-二羟基)亚苯基-2，6-吡啶并[2，3-d：5，6-d′]二咪唑，其被称为PIPD。包括聚吡啶并二唑在内的合适的聚吡啶并唑可通过已知的工序制备，如美国专利5,674,969中所述的那些工序。
如本文所用，术语“聚酯”旨在包括其中至少85％的重复单元为二羧酸和二羟醇的缩合产物的聚合物，其中缩合产物具有通过酯单元的形成而生成的键。这包括芳族、脂族、饱和的和不饱和的二酸和二醇。如本文所用，术语“聚酯”还包括它们的共聚物(诸如嵌段、接枝、无规和间规共聚物)、共混物和改性形式。在一些实施例中，优选的聚酯包括聚(对苯二甲酸乙二醇酯)、聚(萘二甲酸乙二醇酯)和液晶聚酯。聚(对苯二甲酸乙二醇酯)(PET)可包含多种共聚单体，包括二甘醇、环己烷二甲醇、聚乙二醇、戊二酸、壬二酸、癸二酸和间苯二甲酸等。除了这些共聚单体之外，也可以使用支化剂，如均苯三甲酸、均苯四甲酸、三羟甲基丙烷和三羟甲基乙烷以及季戊四醇。可通过已知的聚合技术从对苯二甲酸或其低级烷基酯(如对苯二甲酸二甲酯)和乙二醇或者它们的共混物或混合物获得聚(对苯二甲酸乙二醇酯)。另一种可能有用的聚酯为聚(萘二甲酸乙二醇酯)(PEN)。PEN可通过已知的聚合技术由2，6-萘二甲酸和乙二醇获得。另一种合适的聚酯为聚对苯二甲酸丁二醇酯。
本发明中也可以使用液晶聚酯。本文中所谓“液晶聚酯”(LCP)是指当使用TOT测试或其任何合理变型进行测试时具有各向异性的聚酯，如美国专利4,118,372中所述。液晶聚酯的一种优选形式为“全芳族”；即，聚合物主链中的所有基团都是芳族的(除了诸如酯基的连接基团之外)，但可存在不是芳族的侧基。
E-玻璃是可商购获得的低碱玻璃。一种典型的组合物由54重量％SiO2、14重量％AI2O3、22重量％CaO/MgO、10重量％B2O3和小于2重量％Na2O/K2O组成。还可以存在杂质含量的一些其它材料。
S-玻璃是可商购获得的氧化镁-氧化铝-硅酸盐玻璃。该组合物比E-玻璃更硬、更坚固、也更贵，其通常用于聚合物基体复合材料中。
碳纤维是可商购获得的，并且是本领域的技术人员所熟知的。在一些实施例中，这些纤维的直径为约0.005至0.010mm，并主要由碳原子构成。
可以通过对纤维素酯(纤维素甲酸酯和纤维素乙酸酯)的液晶溶液进行纺丝、随后进行皂化以生成再生纤维素纤维来制备纤维素纤维。
屈服应变促进剂
屈服应变促进剂是能够增加复合材料的屈服应变的添加剂，并且通常占所述组合物的5至14体积％。在一些实施例中，屈服应变促进剂占所述组合物的6至13体积％或甚至8至12体积％。屈服应变促进剂延伸了应力-应变曲线的颈部区域，提高了应变硬化的起点从而增加了断裂伸长率和断裂应力。屈服应变促进剂的优选形式为纤维、针状物、粉末或片状物。合适的屈服应变促进剂材料为具有2.5至130GPa模量的粘土、二氧化硅、滑石、炭黑、对位芳族聚酰胺粉末、交联聚合物粉末或聚合物纤维。还可使用这些材料的共混物。粘土的示例为硅酸镁如海泡石和页硅酸盐，诸如蒙脱石或绿坡缕石。
组合物的机械特性
所述组合物具有至少70％的屈服应变、至少200％或甚至300％的断裂伸长率、以及至少4MPa的屈服应力。在一些实施例中，组合物具有至少80％的屈服应变，或甚至具有至少95％的屈服应变。
组合物的用途
本发明的组合物可用于多种弹性体组合物中以制备轮胎、传送带、动力传动带和其它工业橡胶制品的组分。提供组合物的方便的方式是以弹性体预混物的形式，诸如工程化弹性体，其购自E.I.duPontdeNemoursandCompany(Wilmington，DE(DuPont))。标题为EngineeredElastomer-CompoundDevelopmentGuideandProcessingGuide的技术公报提供了该技术的进一步信息。
测试方法
根据ASTMD412-06A(2013年重新确认)测量复合材料的机械特性。
实例
以下给出的实例是对本发明进行说明，不应解释为以任何方式限制本发明。所有份数和百分比均按体积百分比计，除非另外指明。根据本发明制备的实例用数值来指示。对照实例或比较例用字母来指示。与比较例和本发明实例相关的数据和测试结果示于表1至表2中。
用于以下实例中的材料为：
纸浆是得自DuPont的merge1F361。工程化弹性体(KEE)是merge1F722，也由DuPont供应。将KEE与不同量的天然橡胶混合以产生如实例中所示的体积％纸浆。海泡石为PangelS9等级，购自Tolsa(Suwanee，GA)。绿坡缕石是208等级，购自ActiveMineralsInternational(Cockeysville，MD)。NylonSF(以3旦尼尔/长丝)购自MiniFibersInc.(JohnsonCity，TN)。蒙脱石是得自SouthernClayProducts(Gonzales，TX)的材料。
纸浆-弹性体样品的实验室制备
将36.4g的Kevlar纸浆(DuPont1F361；干重20.00g)浸入1000g温水中。在室温下，将所得的溶液在高剪切混合器中搅拌15分钟。将10.6g分散剂Alcogum6940(干重1.03g)和0.62g分散剂AlcogumSL-70(干重0.10g)加入混合物。在室温下，将所得的溶液在高剪切混合器中搅拌15分钟。将108.9g胶乳弹性体、2.04g抗氧化剂Aquamix125和2.02g抗氧化剂Aquamix549(干重0.31g)加入混合物。在室温下，将所得的溶液在高剪切混合器中搅拌15分钟。通过完全脱水从水中回收该产品。
脱水通过加入乙酸和氯化钙直至材料凝结成乳状生面团外观来进行。然后将材料转移至辊磨机并将水挤出。将样品移除并空气干燥，并且然后转移至真空烘箱(80-90C)过夜以进一步干燥。将干燥的产品切割成小片。在其商业生产时该终产物被称为“KEE1F722”，在其在实验室中制备时，将其称为“LabEE”。
“KEE”或“LABEE”与所有添加剂(抗氧化剂、固化剂、促进剂)的熔融混合在低于96℃的Brabender中以110-120RPM进行10分钟。将经干燥成分加入Brabender共混机并且桨叶速度从10rpm增加以加载至100-120rpm。如果温度超过96℃，则停止共混，并且在冷却至70℃之后，恢复搅拌。十分钟之后，加入固化剂或交联添加剂(硬脂酸、氧化锌、硫磺)并再持续搅拌一分钟。在混合时间结束时，减小RPM并且在冷却之后，回收产品并切割成小片。将这些片夹置在钢板之间并引入预热(160C)的液压机中并在10000psi下压制并保持3分钟以进行软化。然后以25000psi将样品压制5分钟。冷却样品，移除膜(10密耳)，并且冲压出狗骨形状以用于在Instron万能测试机上测试机械强度。
进行表1中所示的一系列实验以示出仅通过加入橡胶的纸浆量来调节组合物不足以实现大于70％的屈服应变。
所有纸浆和应变促进剂浓度表示为体积百分比，除了纸浆含量按纸浆混合物的重量百分比计的比较例E之外。
表1：
增大纸浆的量增加了屈服应力并减小了屈服应变、断裂伸长率和断裂应力。
添加无机应变促进剂的影响由表2中的实例示出。
表2：
比较例E具有65％的屈服应变，然而包含应变促进剂的实例1至7的相应值是88％至112％，这是显著的改善。表2中的数据示出屈服应变增加至88％至150％的范围。
Claims (10)
1.一种组合物，所述组合物包含：
(i)弹性体，
(ii)1体积％至5体积％的纤维纸浆，所述纸浆具有7sq.m./g至11sq.m./g的比表面积，并且所述纤维具有0.5mm至1.1mm的纤维长度，2.5GPa至130GPa的拉伸模量，和1GPa至3GPa的拉伸强度，以及
(iii)5体积％至14体积％的呈纤维、针状物、粉末或片状物的形式的屈服应变促进剂，
其中所述组合物具有至少70％的屈服应变、至少200％的断裂伸长率、以及至少4MPa的屈服应力。
2.根据权利要求1所述的组合物，其中所述屈服应变促进剂占所述组合物的6体积％至13体积％。
3.根据权利要求1所述的组合物，其中所述组合物的屈服应变为至少80体积％。
4.根据权利要求1所述的组合物，其中所述屈服应变促进剂为具有6GPa至130GPa的模量的粘土、二氧化硅、滑石、炭黑、对位芳族聚酰胺粉末、交联聚合物粉末或聚合物纤维。
5.根据权利要求1所述的组合物，其中所述纤维为玻璃、石墨、芳族聚酰胺、芳族共聚酰胺、聚酰亚胺、聚酯、聚乙烯、聚唑或聚对苯二甲酸丁二醇酯。
6.根据权利要求2所述的组合物，其中所述屈服应变促进剂占所述组合物的8体积％至12体积％。
7.根据权利要求3所述的组合物，其中所述组合物的屈服应变为至少95体积％。
8.根据权利要求6所述的组合物，其中所述芳族聚酰胺为对位芳族聚酰胺。
9.根据权利要求1所述的组合物在轮胎中的用途。
10.一种轮胎、传送带或动力传动带，其包含根据权利要求1所述的组合物。
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| US14/034,662 US9074321B2 (en) | 2013-09-24 | 2013-09-24 | Fibrous pulp and use thereof in a composite |
| US14/034662 | 2013-09-24 | ||
| PCT/US2014/056458 WO2015047887A1 (en) | 2013-09-24 | 2014-09-19 | Fibrous pulp and use thereof in a composite |
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| Publication number | Publication date |
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| JP6539260B2 (ja) | 2019-07-03 |
| JP2016535107A (ja) | 2016-11-10 |
| CN105579495B (zh) | 2017-11-21 |
| US20150083355A1 (en) | 2015-03-26 |
| US9074321B2 (en) | 2015-07-07 |
| EP3049463A1 (en) | 2016-08-03 |
| KR20160058800A (ko) | 2016-05-25 |
| WO2015047887A1 (en) | 2015-04-02 |
| KR102292296B1 (ko) | 2021-08-24 |
| EP3049463B1 (en) | 2018-09-12 |
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