CN1315948C - 聚合物改性沥青组合物 - Google Patents
聚合物改性沥青组合物 Download PDFInfo
- Publication number
- CN1315948C CN1315948C CNB038075040A CN03807504A CN1315948C CN 1315948 C CN1315948 C CN 1315948C CN B038075040 A CNB038075040 A CN B038075040A CN 03807504 A CN03807504 A CN 03807504A CN 1315948 C CN1315948 C CN 1315948C
- Authority
- CN
- China
- Prior art keywords
- block
- alkenyl arene
- bituminous composition
- copolymer
- pitch
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 80
- 229920000642 polymer Polymers 0.000 title claims abstract description 33
- 239000010426 asphalt Substances 0.000 title abstract description 30
- 238000009826 distribution Methods 0.000 claims abstract description 52
- 229920001577 copolymer Polymers 0.000 claims abstract description 48
- 150000001993 dienes Chemical class 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 239000012528 membrane Substances 0.000 claims abstract description 6
- -1 alkenyl arene Chemical class 0.000 claims description 50
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 32
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 230000035515 penetration Effects 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 10
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 8
- 229920001519 homopolymer Polymers 0.000 claims description 6
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 6
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- XZKRXPZXQLARHH-XVNBXDOJSA-N [(1e)-buta-1,3-dienyl]benzene Chemical compound C=C\C=C\C1=CC=CC=C1 XZKRXPZXQLARHH-XVNBXDOJSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 claims description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003440 styrenes Chemical class 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 abstract description 25
- 125000000129 anionic group Chemical group 0.000 abstract description 12
- 230000032683 aging Effects 0.000 abstract description 11
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 58
- 239000011295 pitch Substances 0.000 description 40
- 230000006872 improvement Effects 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 238000005984 hydrogenation reaction Methods 0.000 description 14
- 239000004568 cement Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 229920000428 triblock copolymer Polymers 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000004291 polyenes Chemical class 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000007868 post-polymerization treatment Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 229920003046 tetrablock copolymer Polymers 0.000 description 2
- 238000003878 thermal aging Methods 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 108700015862 A-B-A triblock copolymer Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000002897 diene group Chemical group 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XHEDLZYGAQSNTR-UHFFFAOYSA-N ethene;hexanedioic acid Chemical compound C=C.C=C.OC(=O)CCCCC(O)=O XHEDLZYGAQSNTR-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011339 hard pitch Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000018984 mastication Effects 0.000 description 1
- 238000010077 mastication Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D153/02—Vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D153/02—Vinyl aromatic monomers and conjugated dienes
- C09D153/025—Vinyl aromatic monomers and conjugated dienes modified
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
- C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
本发明是具有改进相稳定性,热老化和粘度特性的聚合物改性沥青组合物。沥青组合物是包括沥青和0.5-25%新颖阴离子嵌段共聚物的共混物,其中嵌段之一是在共聚物嵌段中具有单体特定排列的共轭二烯烃和单烯基芳烃的受控分布共聚物。本发明的组合物用于铺路、油毡纸、防水隔膜、粘合剂、涂抹沥青、地毯衬垫和管涂料应用。
Description
发明领域
本发明涉及具有改进的相稳定性、热老化和粘度特性的聚合物改性沥青组合物。特别地,本发明涉及含有一种新颖阴离子嵌段共聚物的组合,其中嵌段之一是在共聚物嵌段中具有单体特定排列的共轭二烯烃和单烯基芳烃的受控分布共聚物。
发明背景
天然或石油衍生的沥青是许多应用的有用材料。然而,沥青自身通常不能满足应用如铺路、油毡纸或防水隔膜的性能要求。因此,已经开发方案,从而将聚合物加入到沥青中以增加性能如低温柔韧性和高温软化点。低温或高温性能的改进导致实际使用的温度范围增加。在一些聚合物改性沥青组合物中,聚合物特别有效和同时发生这些性能增加。除使用温度范围的改进以外,可以达到抗疲劳性耐热断裂和凹陷性能的改进。
在聚合物改性沥青组合物领域中有特别功用的是阴离子乙烯基芳族-共轭二烯烃嵌段共聚物。U.S.专利4129541教导了使用星形苯乙烯-丁二烯嵌段共聚物以改进沥青的低温柔韧性和耐应力开裂性,用于冷温度涂敷应用。
然而,聚合物与沥青组分的有限相容性经常导致不稳定的共混物和因此导致可变和/或较差的性能。
已经采取各种方案以改进阴离子嵌段共聚物与沥青的相容性。在U.S.专利4145322中公开的技术教导了与阴离子嵌段共聚物结合使用硫交联剂。交联的组合物显示优异的高温和低温特性。重要地,阴离子三嵌段共聚物的加入将沥青的固有特征从粘性改变成粘弹性。
硫交联方案的进一步改进教导于U.S.专利5773496,其中阴离子嵌段和星形、或多臂共聚物的结合用于与沥青的共混物。由于二嵌段共聚物的相对高数量,由硫的交联是必须的以达到性能改进,特别地是力延性的改进。在U.S.专利6429241中,教导了达到改进性能的方案,从而由采用共聚物和交联剂增量加入的方法,达到阴离子三嵌段共聚物/沥青共混物硫交联的相对高数量。
尽管导致性能改进,交联以稳定阴离子嵌段共聚物/沥青共混物的方案,仍具有要求额外材料(即交联剂)和引入这些试剂的额外工艺步骤的缺点。当不合适地使用交联剂时,此方法具有导致不合格产物或高度胶凝化产物的进一步缺点。硫交联的进一步不希望的特征是加工期间硫化氢的产生,它呈现环境和健康危险。
通过稳定聚合物改性沥青组合物的形成达到改进性能组的另一种方案是使用增容剂。U.S.专利5331028教导使用缩水甘油化乙烯共聚物作为SBS/沥青共混物的增容剂。在此技术中,官能化乙烯共聚物与沥青反应以形成更易于接收阴离子嵌段共聚物共混的沥青组分。
可用作嵌段共聚物-沥青增容剂的其它官能化聚合物如环氧化聚二烯烃已经教导于U.S.专利5451619和极性聚合物如官能化聚乙烯教导于U.S.专利6100317。
引入增容聚合物以稳定阴离子嵌段共聚物-沥青共混物导致显著的性能改进。然而,此方案要求加入通常昂贵的第三组分。此外,由于生产增容剂所要求的步骤或用于共混入沥青组合物中所要求的那些,共混物的制备方法可能一般是复杂的。
借此在它的初始制造期间改性阴离子嵌段共聚物组合物或结构的更简单方案从工艺和成本观察来看是有吸收力的。U.S.专利4530652和U.S.专利5854335教导了阴离子嵌段共聚物的丁二烯橡胶嵌段改性以达到增强的相容性和性能。特别地,改性橡胶中间嵌段以增加聚合期间丁二烯的1,2-加成。由此方案达到的增加相容性导致在热老化之后增加的性能保持,增加的柔韧性和改进的耐高温流动性能。
现在已经发现含有受控分布橡胶嵌段的阴离子嵌段共聚物具有与沥青的优异相容性,该受控分布橡胶嵌段包括烯基芳烃和共轭二烯烃单体单元。这样的嵌段共聚物及其制备方法描述于以上提及的在先未决、通常拥有的专利申请系列号60/335210。此外,这样组合物的性能特性对于如下各种应用是有吸收力的:铺路、油毡纸、防水隔膜、沥青粘合剂、涂抹沥青、地毯衬垫、消音材料和涂料。
发明概述
本发明是一种沥青组合物,该组合物包括:
(I)75%-99.5%沥青;和
(II)0.5wt%-25wt%含有至少一个A嵌段和至少一个B嵌段的嵌段共聚,其中:
(a)每个A嵌段独立地是单烯基芳烃均聚物嵌段和每个B嵌段独立地是至少一种共轭二烯烃和至少一种单烯基芳烃的受控分布共聚物嵌段;
(b)每个A嵌段的数均分子量为3,000-60,000和每个B嵌段的数均分子量为30,000-300,000;
(c)每个B嵌段包括邻近A嵌段、富含共轭二烯烃单元的末端区域和一个或多个不邻近A嵌段、富含单烯基芳烃单元的区域;
(d)嵌段共聚物中单烯基芳烃的总数量是20-80wt%;和
(e)每个B嵌段中单烯基芳烃的重量百分比是10-75%。
本发明的嵌段共聚物可以是不饱和的或由于氢化反应是选择性、部分或完全饱和的。本发明的优点是具有改进热老化特性和宽使用温度的增加相容性的沥青组合物。此组合物的具体应用是铺路配制剂、油毡纸、防水隔膜、沥青粘合剂、涂抹沥青、管涂料和地毯衬垫。
本发明的详细描述
本发明提供包括新颖阴离子嵌段共聚物的沥青组合物。新颖阴离子嵌段共聚物来自烯基芳烃和二烯烃的共聚,该烯基芳烃和二烯烃作为单烯基芳烃/共轭二烯烃嵌段共聚物的一部分。令人惊奇地,(1)单体加入的独特控制和(2)乙醚或其它改性剂作为溶剂组分(它以下称为“分布剂”)的使用的结合导致两种单体(在此称为“受控分布”聚合,即导致“受控分布”结构的聚合)的某些特性分布,和也导致在聚合物嵌段中某些单烯基芳烃富集区域和某些共轭二烯烃富集区域的存在。对于在此的目的,“受控分布”定义为表示具有如下属性的分子结构:(1)邻近单烯基芳烃均聚物(“A”)嵌段的末端区域,该区域富含共轭二烯烃单元;(2)一个或多个不邻近A嵌段的区域,该区域富含单烯基芳烃单元;和(3)具有相对低嵌段度的总体结构。对于在此的目的,“富含”定义为大于平均数量,优选大于平均数量5%。此受控分布(“B”)嵌段的相对低嵌段度可以由该受控分布嵌段中间体的单一(“Tg”)的存在表现出,当使用差示扫描量热法(“DSC”)(热)方法或通过机械方法分析时,该单一Tg在单独的任一单体的Tg之间,或如通过质子核磁共振(“H-NMR”)方法表现出。也可以在B嵌段聚合期间适于聚苯乙烯基锂端基检测的波长范围内,从UV-可见吸光度的测量推断嵌段度的可能性。此数值的急剧和显著增加表示聚苯乙烯基锂链端的显著增加。在此方法中,这仅在共轭二烯烃浓度下降到保持受控分布聚合所需的临界水平以下才发生。在此点存在的任何苯乙烯单体以嵌段的形式加入。由本领域技术人员使用质子NMR测量的术语“苯乙烯嵌段度”定义为在聚合物链上含有两个S最近邻接部分的聚合物中S单元的比例。在使用H-1 NMR测量两个试验数量之后测量苯乙烯嵌段如下:
首先,通过在7.5-6.2ppm的H-1 NMR光谱中积分总苯乙烯芳族信号和将此数量除以5以解释每个苯乙烯芳族环上的5个芳族氢,测定苯乙烯单元(即当成比例时抵消的任意仪器单元)的总数目。
其次,通过从6.88和6.80之间的信号最小值到6.2ppm的H-1 NMR光谱中积分芳族信号部分和将此数量除以2以解释每个嵌段苯乙烯芳族环上的2个邻位氢,测定嵌段苯乙烯单元。此信号对那些苯乙烯单元的环上两个邻位氢的指定报导于F.A.Bovey,大分子的高分辨率NMR(Academic Press,纽约和伦敦,1972),第6章,该苯乙烯单元含有两个苯乙烯最近邻接部分。
苯乙烯嵌段度简单地是嵌段苯乙烯对总苯乙烯单元的百分比:
嵌段%=100乘(嵌段苯乙烯单元/总苯乙烯单元)
这样表达的聚合物-Bd-S-(S)n-S-Bd-聚合物,其中n大于零,定义为嵌段苯乙烯。例如,如果在以上例子中n等于8,则嵌段度指数是80%。优选嵌段度指数小于40。对于苯乙烯含量为10wt%-40wt%的一些聚合物,优选嵌段度指数小于10。
在此使用的“热塑性嵌段共聚物”定义为含有如下嵌段的嵌段共聚物:至少一种或多种单烯基芳烃,如苯乙烯的第一嵌段(A嵌段)及二烯烃和单烯基芳烃受控分布共聚物的第二嵌段(B嵌段)。制备此热塑性嵌段共聚物的方法是通过对于嵌段聚合一般已知的任何方法。本发明包括作为实施方案的热塑性共聚物组合物,它们可以是二嵌段共聚物、三嵌段共聚物、四嵌段共聚物或多嵌段共聚物组合物。在二嵌段共聚物组合物的情况下,一个嵌段是烯基芳烃基均聚物嵌段和与其聚合的是二烯烃和烯基芳烃受控分布共聚物的第二嵌段。在三嵌段共聚物组合物的情况下,它包括作为端嵌段的玻璃性烯基芳烃基均聚物和作为中间嵌段的二烯烃和烯基芳烃受控分布共聚物。在制备三嵌段共聚物组合物的情况下,受控分布二烯烃/烯基芳烃共聚物可以在此指定为“B”和烯基芳烃基均聚物指定为“A”。A-B-A三嵌段共聚物组合物可以由顺序聚合或偶合制备。在顺序溶液聚合技术中,首先将单烯基芳烃引入以生产相对硬的芳族嵌段,随后引入受控分布二烯烃/烯基芳烃混合物以形成中间嵌段,和然后随后引入单烯基芳烃以形成末端嵌段。除线性A-B-A构型以外,可以构造嵌段以形成星形(支化)聚合物(A-B)nX,或可以在混合物中结合两种类型的结构。一些A-B二嵌段聚合物可以存在,但优选至少约70wt%嵌段共聚物是A-B-A或星形的(或另外支化的以每个分子含有2个或更多末端树脂性嵌段)以赋予强度。
受控分布结构在控制所得热塑性弹性体的强度和Tg中非常重要。在受控分布结构中,苯乙烯嵌段度低和这保证实质上没有两种单体的相分离。这与如下的共聚物形成对照:其中单体实际保持为具有单独“微相”并从而具有单独和不同的Tg。由于在受控分布共聚物中仅存在一个Tg,所得共聚物的热性能是可预测的和事实上是预先确定的。
本发明热塑性弹性体二嵌段、三嵌段、多嵌段和星形嵌段共聚物的重要特征是A和B嵌段的单独Tg,该共聚物包括一个或多个受控分布二烯烃/烯基芳烃共聚物嵌段(B嵌段)和一个或多个单烯基芳烃嵌段(A嵌段)。烯基芳烃A嵌段的Tg高于受控分布共聚物B嵌段的Tg。受控分布嵌段的Tg优选是至少-60℃,更优选-40~+30℃,和更优选-40~+10℃。烯基芳烃A嵌段的更高Tg优选+80~+110℃,更优选+80~+105℃。
当这样的受控分布结构用作二嵌段、三嵌段或多嵌段共聚物中的一个嵌段时,通过适当构成的受控分布共聚物区域的存在变为可能的相对更高Tg倾向于改进流动和加工性能。此外,可能的是尽管共轭二烯烃橡胶嵌段中单烯基芳烃的引入导致阴离子嵌段的升高芳族含量,同时保持此嵌段的橡胶性特征。当制备与高度芳族材料如沥青的共混物时,此升高的芳族含量是特别有用的。在此状况下,升高的芳族含量提供共混物的增强相容性,从而允许新结合和/或改进的表现性能。也可达到阴离子嵌段共聚物自身以及与其它材料的共混物的某些其它性能的改进。
在本发明的优选实施方案中,主题受控分布共聚物嵌段含有两个不同的区域:在嵌段端部的共轭二烯烃富集区域和靠近嵌段中间或中心的单烯基芳烃富集区域。希望的是单烯基芳烃/共轭二烯烃受控分布共聚物嵌段,其中单烯基芳烃单元的比例逐渐增加到靠近嵌段中间或中心的最大值。此结构是显著的和不同于现有技术中讨论的渐变和/或无规结构。
如上所讨论的那样,受控分布聚合物嵌段含有邻近A嵌段的二烯烃富集区域和不邻近A嵌段、和典型地靠近B嵌段中心的芳烃富集区域。典型地邻近A嵌段的区域包括嵌段的前15-25%和包括二烯烃富集区域,及剩余部分被认为富集芳烃。术语“二烯烃富集”表示与芳烃富集区域相比,区域具有可测量地高的二烯烃对芳烃比例。表达此的另一种方式是单烯基芳烃单元的比例沿聚合物链逐渐增加到靠近嵌段中间或中心的最大值(如果我们描述ABA结构)和然后逐渐降低直到聚合物嵌段完全聚合。对于受控分布嵌段B,单烯基芳烃的重量百分比是10-75%。
用于制备本发明新颖共聚物的聚合条件典型地相似于一般用于阴离子聚合的那些。用于受控分布嵌段合成的具体聚合过程是一种方法,其中(1)独特地控制单体加入和(2)采用分布剂。可以使用一个双反应器或单一反应器聚合方案制备受控分布嵌段共聚物。本领域技术人员理解的是精确的聚合条件依赖于采用哪个方案。
受控分布嵌段共聚物的烯基芳烃单体可以选自苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、乙烯基甲苯、乙烯基萘、和对丁基苯乙烯或其混合物。在这些物质中,苯乙烯是最优选的和可购自各个制造商和相对便宜。在此使用的共轭二烯烃是1,3-丁二烯和取代丁二烯如异戊二烯、戊间二烯、2,3-二甲基-1,3-丁二烯、和1-苯基-1,3-丁二烯、或其混合物。在这些物质中,最优选是1,3-丁二烯。在此使用的和在权利要求中使用的“丁二烯”具体地表示“1,3-丁二烯”。
对于受控分布或B嵌段,对于选择性氢化聚合物,每个B嵌段中单烯基芳烃的重量百分比是10-75wt%,优选25-50wt%。
也重要的是控制各个嵌段的分子量。对于AB二嵌段,所需的嵌段重量对于单烯基芳烃A嵌段为3,000-60,000,和对于受控分布共轭二烯烃/单烯基芳烃B嵌段为30,000-300,000。优选的范围对于A嵌段为5000-45,000和对于B嵌段为50,000-250,000。对于三嵌段,它可以是顺序ABA或偶合(AB)2X嵌段共聚物,A嵌段应当是3,000-60,000,优选5000-45,000,而对于顺序嵌段的B嵌段应当是30,000-300,000,和对于偶合聚合物的B嵌段(两个)为该数量的一半。三嵌段共聚物的总平均分子量应当为40,000-400,000,和对于星形共聚物为60,000-600,000。对于四嵌段共聚物ABAB,末端B嵌段的嵌段尺寸应当是2,000-40,000,和其它嵌段可以类似于顺序三嵌段的尺寸。这些分子量最精确地由光散射测量测定。
本发明的另一个重要方面是控制受控分布共聚物嵌段中共轭二烯烃的微结构或乙烯基含量。术语“乙烯基含量”表示通过1,2-加成(在丁二烯的情况下-在异戊二烯的情况下它是3,4-加成)聚合共轭二烯烃。尽管纯“乙烯基”仅在1,3-丁二烯的1,2-加聚情况下形成,异戊二烯3,4-加聚(和对于其它共轭二烯烃的相似加成)对嵌段共聚物最终性能的影响相似。术语“乙烯基”表示聚合物链上侧乙烯基的存在。当指丁二烯作为共轭二烯烃应用时,优选共聚物嵌段中20-80mol%的缩合丁二烯单元具有由质子NMR分析测定的1,2乙烯基构型。对于选择性氢化的嵌段共聚物,优选地30-70mol%的缩合丁二烯单元应当具有1,2构型。对于不饱和嵌段共聚物,优选地20-40mol%的缩合丁二烯单元应当具有1,2乙烯基构型。这有效地通过改变分布剂的相对数量而控制。聚合期间使用的分布剂典型地是非螯合性醚诸如乙醚或邻二甲氧基苯。如理解的那样,分布剂起两个目的-它产生单烯基芳烃和共轭二烯烃的受控分布,和也控制共轭二烯烃的微结构。分布剂对锂的合适比例公开和教导于US Pat.Re27145,它的公开内容引入作为参考。
星形(支化)聚合物的制备要求称为“偶合”的聚合后步骤。在以上星形通式中,n是2-30,优选2-15的整数,和X是偶合剂的剩余部分或残基。各种偶合剂是本领域已知的和包括例如二卤代烷烃、卤化硅、硅氧烷、多官能环氧化物、二氧化硅化合物、一元醇与羧酸的酯、和环氧化油。星型聚合物采用多烯基偶合剂制备,如例如在U.S.专利号3985830、4391949、和4444953,加拿大专利号716645中公开的那样。合适的多烯基偶合剂包括二乙烯基苯,和优选间二乙烯基苯。优选是四烷氧基硅烷如四乙氧基硅烷(TEOS),脂族二酯如己二酸二甲酯和己二酸二乙酯,和二缩水甘油基芳族环氧化合物如衍生自双酚A和环氧氯丙烷反应的二缩水甘油醚。
可用于进一步改性聚合物构型和因此改进它们性能的另外可能的聚合后处理包括封端和链终止。封端剂,如环氧乙烷、二氧化碳、或其混合物用于向链末端加入官能团,其中它们然后可用作进一步性能改进反应的反应部位。相反,链终止简单地阻止进一步的聚合和因此阻止分子量生长超过所需的点。或者,活性共聚物可简单地氢化以失活金属部位。
应当注意到,在本发明的仍然另一个实施方案中,可以通过仍然另一个聚合后处理,通过嵌段共聚物氢化达到其组合物的另外性能改进。优选的氢化是最终嵌段共聚物二烯烃部分的选择性氢化。或者可以氢化B嵌段和A嵌段两者,或可以仅氢化一部分B嵌段。氢化一般改进最终聚合物的热稳定性,紫外光稳定性,氧化稳定性,和由此的耐侯性。本发明的主要优点在于分布剂,如非螯合单醚,它在初始聚合工艺期间存在,不干扰或另外“毒害”氢化催化剂,和因此避免任何附加脱除步骤的需要。
可以通过本领域已知的任何几种氢化或选择性氢化方法进行氢化。例如,使用方法如在例如如下文献中教导的那些完成这样的氢化:U.S.专利3595942、3634549、3670054、3700633、和Re.27145,该文献的公开内容在此引入作为参考。
氢化可以在一定的条件下进行使得减少至少90%的共轭二烯烃双键,和减少0-10%的芳烃双键。优选的范围是减少至少95%的共轭二烯烃双键,和更优选减少至少98%的共轭二烯烃双键。或者,可以氢化聚合物使得芳族不饱和度也减少超过上述10%水平。这样的完全氢化作用通常在较高温度取得。在该情况下,共轭二烯烃和芳烃两者的双键可以减少90%或更多。
另外,可以采用许多方式官能化本发明的嵌段共聚物。一种方式是采用含有一个或多个官能团或它们的衍生物,如羧酸基团和它们的盐、酸酐、酯、酰亚胺基团、酰胺基团、和酰氯的不饱和单体处理。要接枝到嵌段共聚物上的优选单体是马来酸酐、马来酸、富马酸、和它们的衍生物。官能化这样的嵌段共聚物的进一步描述可以发现于Gergen等人,U.S.Pat.No.4578429和发现于U.S.Pat.No.5506299。在另一种方式中,可以通过接枝含硅或硼化合物到聚合物上官能化本发明的选择性氢化嵌段共聚物,如在U.S.Pat.No.4882384中教导的那样。在仍然另一种方式中,可以将本发明的嵌段共聚物与烷氧基硅烷化合物接触,以形成硅烷改性的嵌段共聚物。在仍然另一种方式中,可以通过接枝至少一个环氧乙烷分子到聚合物上,如在U.S.Pa t.No.4898914中教导的那样,或通过聚合物与二氧化碳反应,如在U.S.Pat.No.4970265中教导的那样官能化本发明的嵌段共聚物。仍然进一步地,可以金属化本发明的嵌段共聚物,如在U.S.Pat.No.5206300和5276101中教导的那样,其中将聚合物与烷基碱金属,如烷基锂接触。和仍然进一步地,可以通过接枝磺酸类基团到聚合物上官能化本发明的嵌段共聚物,如在U.S.5516831中教导的那样。在此段落中提及的所有专利引入本申请作为参考。
在根据本发明的沥青组合物中存在的沥青组分,也称为沥青,可以是天然沥青或衍生自矿物油。同样由裂化工艺和煤焦油获得的石油沥青可以用作沥青组分以及各种沥青材料的共混物。合适组分的例子包括蒸馏或“直馏沥青”、沉淀沥青,如丙烷沥青、吹制沥青,如催化吹制沥青或“Multiphalt”、及其混合物。其它合适的沥青组分包括一种或多种这些沥青与填充剂(稀释剂)如石油提取物,如芳族提取物、馏出物或残余物,或与油的混合物。合适的沥青组分(“直链沥青”或“加过稀释剂的沥青”)是在25℃下针入度为50-300dmm(“分毫米”或根据ASTMD-5的“单位”)的那些。在其中产物的柔韧性,粘性或粘合力具有高度重要性的应用中,特别使用25℃下针入度大于300dmm的加过稀释剂的沥青。本发明的聚合物可用于从硬质沥青到半液体沥青的宽范围。
聚合物改性剂在沥青组合物中的存在量合适地为0.5-25wt%。聚合物含量的下范围对于应用,如铺路是特别感兴趣的,它要求沥青特征从粘性向粘弹性的变化。性能的此变化一般随0.5%-8%的聚合物含量而发生。在到25%的更高聚合物含量下,可以达到柔韧性和弹性强度的显著增加。这对于油毡纸、粘合剂和防水隔膜应用是特别感兴趣的。
沥青组合物也可非必要地包含其它成分,如设想的最终用途要求的那些。因此可以包括填料,例如滑石、聚集体、碳酸钙和炭黑,或可以引入包括树脂、油、稳定剂或阻燃剂的其它组分。这样的填料和其它组分的含量可以为从0到多至90wt%。当然,如果有利的话,其它聚合物改性剂也可以包括在本发明的沥青组合物中。
与改进耐老化性结合的本发明聚合物-沥青共混物的有用低温和高温性能,使得这样的共混物在如下用途中具有显著的益处:其中将共混物曝露于外部气侯条件,如用于盖屋顶应用,例如作为油毡纸的组分。有用低的高温粘度不仅仅意味着聚合物-沥青共混物可以更容易地加工,而且也意味着它们能够在达到最大可允许加工粘度之前引入更大数量的填料,和因此在其中通常使用填料的那些应用中导致更便宜的产物。
本发明中固有的粘弹性特征能够实现作为热混合铺路水泥的应用。在热混合铺路水泥中,将沥青组合物与相对大数量聚集体混合。聚集体一般由沙子,岩石和细粒组成。沥青组合物一般构成总热混合铺路水泥的1-20wt%。
本发明的受控分布嵌段共聚物特别用于沥青粘合剂应用。沥青粘合剂应用包括3-20wt%聚合物,5-50wt%填料(如石灰石、碳酸钙、炭黑)和轻质的低粘度沥青组分。沥青粘合剂用于要求防潮性的室外应用,和一般具有良好的流动和高粘性与对其它沥青基材料和一般对建筑材料的特别良好粘合。
涂抹沥青是实施方案的一种特别有用的应用,其中受控分布嵌段共聚物由氢化饱和。由于饱和的受控分布嵌段共聚物特别耐热氧化降解,它们比涂抹沥青中的不饱和聚合物更稳定,该涂抹沥青被加热到高温,保持在高温下,和在高温下施涂。涂抹沥青一般包括5-15wt%沥青和85-95wt%聚合物。涂抹沥青的聚合物改性一般导致异常的粘性,在宽温度范围内稳定的软化点和异常的粘合强度,弹性恢复和拉伸伸长率。
其中本发明沥青组合物可能有用的其它应用是消声和振动衰减应用、密封剂或涂料应用、和管涂料和地毯衬垫。
实施例
用于这些实施例共混物的沥青材料在表1中表征。在这些实施例中与沥青共混的聚合物在表2中表征。表1中列出的本发明聚合物和对比聚合物两者由苯乙烯A嵌段组成。在本发明聚合物的情况下,B嵌段是由丁二烯和苯乙烯组成的受控分布共聚物嵌段。在对比聚合物的情况下,B嵌段仅由丁二烯组成。没有一种表1的聚合物是选择性氢化的。
根据如下过程制备展示本发明的聚合物改性沥青配制剂。采用Silverson L4R高剪切混合机制备沥青和聚合物的共混物。将沥青加热到150-180℃和随后在几分钟时间内加入聚合物。在混合时,温度增加到170-200℃,它由从混合机的机械能输入引起。在此温度下的共混持续到获得均匀的共混物。由共混物稠度的目测观察监测共混物的均匀性。在混合45-90分钟之后达到均匀性。
在表3中显示具有相对低聚合物含量的配制剂1-12。在表4中显示具有相对高聚合物含量的配制剂13-19。
根据ASTM D-5测量净沥青和聚合物改性沥青的针入度。根据ASTMD-36测量净沥青和聚合物改性沥青的环球软化点。根据ASTM D-5892测量静态贮存稳定性。
表1
沥青ID | 描述,公称 | 通用相容性 | 相对粘度 | 针入度(dmm) | 环球软化点(℃) |
沥青I | AC-30级沥青 | 相容 | 高 | 46 | 138 |
沥青II | AC-5级沥青 | 相容 | 低 | 111 | 125 |
沥青III | PG 64-22级沥青 | 中度不相容 | 高 | 56 | 131 |
PG=性能等级
表2
聚合物ID | 类型 | PSC(%) | MW A嵌段 | MW B嵌段 | B嵌段中 的%S | 1,2-丁二烯 | NMR嵌段度 | 计算的B嵌段度 | CE(%) |
聚合物29 | 星形 | 66 | 21.4 | 113 | 53 | 19 | 66 | 40 | 82 |
聚合物30 | 星形 | 49 | 21.2 | 114 | 28 | 19 | 74 | 37 | 81 |
对比A | 星形 | 30 | 21.0 | 98 | 0 | 8 | NA | NA | 84 |
聚合物16 | 线性 | 42 | 15.5 | 116 | 28 | 23.5 | 56 | 12 | >90 |
聚合物17 | 线性 | 63 | 15.6 | 100 | 50 | 24.6 | 45 | 11 | >90 |
聚合物18 | 线性 | 40 | 11.7 | 101 | 25 | 22.8 | 59 | 22 | 70 |
对比B | 线性 | 31 | 16.1 | 72 | 0 | 8 | NA | NA | 84 |
NA=不可应用,中间嵌段整个由丁二烯单体组成。
MW B嵌段=受控分布共聚物嵌段的总分子量。
B嵌段中的%S=由缩合苯乙烯单体组成的B嵌段的重量百分比。
CE=偶合效率
表3
配制剂 | ||||||||||||
组分 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 |
聚合物29 | 3 | 3 | ||||||||||
聚合物30 | 3 | 3 | ||||||||||
聚合物16 | 3 | |||||||||||
聚合物17 | 3 | |||||||||||
聚合物18 | 3 | |||||||||||
对比A | 3 | 3 | ||||||||||
对比B | 3 | |||||||||||
沥青I | 100 | 97 | 97 | 97 | 97 | 97 | 97 | 97 | ||||
沥青II | 100 | 97 | 97 | 97 |
数字表示所示组分的重量百分比。
表4
配制剂 | |||||||
组分 | 13 | 14 | 15 | 16 | 17 | 18 | 19 |
聚合物2 9 | 12 | ||||||
聚合物30 | 12 | ||||||
聚合物16 | 12 | ||||||
聚合物17 | 12 | ||||||
聚合物18 | 12 | ||||||
对比A | 12 | ||||||
对比B | 12 | ||||||
沥青I | |||||||
沥青II | 88 | 88 | 88 | 88 | 88 | 88 | 88 |
数字表示所示组分的重量百分比。
实施例1.
对配制剂14-19测量平均针入度和环球软化点并分别显示于表5和6。将配制剂在密闭容器中在70℃下老化指示的时间。在老化样品的顶部和底部区段上进行针入度和环球软化点两个测量。表中报告的测量值表示这些测量的平均值。采用沥青II制备所有这些配制剂。未改性沥青II在25℃下的针入度是111。未改性沥青II的环球软化点是125_。由降低的针入度数值证明针入度的改进。由增加的数值证明环球软化点的改进。表5和6的数值显示由受控分布嵌段共聚物的引入,针入度和环球软化点两者相对于未改性沥青得到改进。
表5
在25℃下的针入度(dmm)
配制剂 | ||||||
老化天数 | 14 | 15 | 16 | 17 | 18 | 19 |
0 | 44 | 49 | 43 | 49 | 55 | 49 |
28 | 23 | 26 | 17 | 25 | 30 | 28 |
42 | 22 | 19 | 41 | 24 | 26 | 25 |
63 | 29 | 45 | 55 | 47 | 36 | 50 |
表5的数据显示在63天热老化时间内保持针入度的改进。表6的数据显示在63天热老化时间内保持如由环球软化点证明的高温性能的改进。在热老化期间的改进保持说明聚合物与沥青的良好相容性。
表6
环球软化点(_)
配制剂 | |||||||
老化天数 | 13 | 14 | 15 | 16 | 17 | 18 | 19 |
0 | 256 | 221 | 242 | 240 | 236 | 221 | 197 |
28 | 246 | 224 | 236 | 223 | 224 | 206 | 198 |
42 | 246 | 212 | 236 | 220 | 232 | 208 | 196 |
63 | 210 | 230 | 244 | 241 | 228 | 216 | 195 |
实施例2
使用ASTM D-5892的静态贮存稳定性方法评价配制剂的相容性。配制剂在管中在163.5℃下老化48小时。然后将它们骤冷到-6.7℃下4小时。然后将管状样品切成三分之一和测量顶部和底部三分之一的环球软化点。在试验的热老化部分期间,聚合物改性的沥青倾向于分离成聚合物富集顶部层和沥青富集底部层。这发生的程度依赖于聚合物与沥青的相容性。当聚合物与沥青非常相容时,在顶部和底部层之间的性能差异小。在表7中列出在顶部和底部层环球软化点之间的差异。
表7
在升高的热老化之后的环球软化点
配制剂 ID | 沥青 | 聚合物 | 聚合物含量,(%) | 环球软化点,(_) | ||
顶部 | 底部 | 差异 | ||||
7 | III | 对比A | 3 | 208 | 139 | 69 |
4 | III | 聚合物30 | 3 | 153 | 140 | 13 |
3 | III | 聚合物29 | 3 | 143 | 135 | 8 |
8 | I | 对比A | 3 | 208 | 143 | 66 |
6 | I | 聚合物30 | 3 | 158 | 142 | 17 |
5 | I | 聚合物29 | 3 | 145 | 138 | 7 |
9 | I | 对比B | 3 | 190 | 143 | 48 |
10 | I | 聚合物16 | 3 | 193 | 144 | 50 |
12 | I | 聚合物18 | 3 | 172 | 146 | 27 |
11 | I | 聚合物17 | 3 | 162 | 145 | 17 |
16 | II | 对比B | 3 | 236 | 169 | 68 |
17 | II | 聚合物16 | 3 | 228 | 216 | 12 |
19 | II | 聚合物18 | 3 | 196 | 188 | 8 |
18 | II | 聚合物17 | 3 | 200 | 168 | 33 |
表7的数据显示对于包含对比聚合物的配制剂,存在顶部和底部测量值之间的相对大差异。对比聚合物不含有受控分布中间嵌段。在对比聚合物的橡胶嵌段中没有分散苯乙烯单体单元。采用含有受控分布嵌段的聚合物,根据本发明的相容性改进由顶部和底部测量值之间的较小差异证明。
实施例3(预示的)
为制备沥青粘合剂,将55重量份AC-3级沥青加热到150℃。使用表2中列出的本发明的任何一种未氢化聚合物。或者,可以使用表2中聚合物的氢化类似物。高剪切Silverson L4R混合机用于分散10重量份聚合物,同时在5分钟时间内将它加入到热沥青中。混合持续60分钟和在混合期间将温度保持在180℃。中断高剪切混合。将沥青-聚合物混合物保持在180℃下和将35重量份细粉碎的石灰石在低剪切混合条件下加入。低剪切混合持续直到石灰石均匀分散。一旦混合完成,使混合物冷却到室温。
根据ASTM D1970和ASTM D6135测试沥青粘合剂的性能。本发明沥青粘合剂的伸长率大于10%,柔韧性温度低于-29℃,在4.4℃下对胶合板的粘合力大于0.92kfg/30.5cm试样宽度,和水汽渗透率小于5.7ng/Pa.S.M2。
实施例4(预示的)
为制备涂抹沥青,将92重量份AC-10级沥青加热到180℃。在高剪切条件下使用Silverson L4R混合机,将8重量份星形或线性的氢化的受控分布嵌段共聚物加入到热沥青中。在5分钟时间内加入聚合物。将混合物混合和保持在200℃下60分钟。停止混合和使涂抹沥青配制剂冷却。
根据ASTM D 6152测试涂抹沥青的性能。本发明涂抹沥青的软化点为85-116℃,在热老化之后软化点变化为5℃或更小,在25℃下针入度为20-60dmm和在热老化之后针入度降低不大于5个单位或针入度增加不大于12个单位,在25℃下拉伸伸长率为750%和弹性恢复为80%。
Claims (10)
1.一种沥青组合物,包括:
(I)75%-99.5%沥青;和
(II)0.5wt%-25wt%含有至少一个A嵌段和至少一个B嵌段的嵌段共聚物,其中:
(a)每个A嵌段独立地是单烯基芳烃均聚物嵌段和每个B嵌段独立地是至少一种共轭二烯烃和至少一种单烯基芳烃的受控分布共聚物嵌段;
(b)每个A嵌段的数均分子量为3,000-60,000和每个B嵌段的数均分子量为30,000-300,000;
(c)每个B嵌段包括邻近A嵌段、富含共轭二烯烃单元的末端区域和一个或多个不邻近A嵌段、富含单烯基芳烃单元的区域;
(d)嵌段共聚物中单烯基芳烃的总数量是20-80wt%;
(e)每个B嵌段中单烯基芳烃的重量百分比是10-75%;和
(f)所述单烯基芳烃单体选自苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、乙烯基甲苯、乙烯基萘、和对丁基苯乙烯或其混合物,和所述共轭二烯烃单体选自1,3-丁二烯、异戊二烯、戊间二烯、2,3-二甲基-1,3-丁二烯和1-苯基-1,3-丁二烯或其混合物。
2.根据权利要求1的沥青组合物,其中该单烯基芳烃是苯乙烯和该共轭二烯烃是1,3-丁二烯,和其中嵌段B中20-80mol%的缩合丁二烯单元具有1,2-构型。
3.根据权利要求2的沥青组合物,其中嵌段B的苯乙烯嵌段度指数小于40mol%,该苯乙烯嵌段度指数定义为在聚合物链上含有两个苯乙烯邻接部分的嵌段B中苯乙烯单元的比例。
4.根据权利要求1-3任意一项的沥青组合物,其中嵌段共聚物具有通用构型(A-B)n、(A-B-A)n、(A-B)nX或(A-B-A)nX及其混合,其中X是偶合剂残基和n是1-30的整数。
5.根据权利要求1-3任意一项的沥青组合物,其中嵌段共聚物是选择性、部分或完全氢化的。
6.根据权利要求1-3任意一项的沥青组合物,其中嵌段共聚物是0.5-8wt%。
7.根据权利要求1-3任意一项的沥青组合物,其中嵌段共聚物是8wt%-25wt%。
8.根据权利要求1-3任意一项的沥青组合物,其中沥青在25℃下的针入度为40-120dmm。
9.根据权利要求1-3任意一项的沥青组合物,其中沥青的环球软化点是110-150℃。
10.铺路配制剂、油毡纸、防水隔膜、粘合剂、管涂料、地毯衬垫、或涂抹沥青,包括权利要求1-9任意一项的沥青组合物。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US35521002P | 2002-02-07 | 2002-02-07 | |
US60/355,210 | 2002-02-07 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1646632A CN1646632A (zh) | 2005-07-27 |
CN1315948C true CN1315948C (zh) | 2007-05-16 |
Family
ID=27734482
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB03807477XA Expired - Lifetime CN1288209C (zh) | 2002-02-07 | 2003-02-07 | 来自受控分布嵌段共聚物的凝胶 |
CN038074842A Expired - Lifetime CN1643016B (zh) | 2002-02-07 | 2003-02-07 | 新型嵌段共聚物及其制备方法 |
CNB038075040A Expired - Fee Related CN1315948C (zh) | 2002-02-07 | 2003-02-07 | 聚合物改性沥青组合物 |
CNB038074834A Expired - Lifetime CN1280323C (zh) | 2002-02-07 | 2003-02-07 | 来自受控分布嵌段共聚物的粘合剂 |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB03807477XA Expired - Lifetime CN1288209C (zh) | 2002-02-07 | 2003-02-07 | 来自受控分布嵌段共聚物的凝胶 |
CN038074842A Expired - Lifetime CN1643016B (zh) | 2002-02-07 | 2003-02-07 | 新型嵌段共聚物及其制备方法 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB038074834A Expired - Lifetime CN1280323C (zh) | 2002-02-07 | 2003-02-07 | 来自受控分布嵌段共聚物的粘合剂 |
Country Status (10)
Country | Link |
---|---|
US (11) | US6759454B2 (zh) |
EP (4) | EP1474481B1 (zh) |
CN (4) | CN1288209C (zh) |
AT (2) | ATE376563T1 (zh) |
AU (4) | AU2003208666A1 (zh) |
DE (3) | DE60327051D1 (zh) |
EA (1) | EA007542B1 (zh) |
ES (1) | ES2291615T3 (zh) |
TW (4) | TWI248962B (zh) |
WO (4) | WO2003066739A1 (zh) |
Families Citing this family (213)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7226484B2 (en) * | 1994-04-19 | 2007-06-05 | Applied Elastomerics, Inc. | Tear resistant gels and articles for every uses |
US7179860B2 (en) * | 2001-03-13 | 2007-02-20 | Liwei Cao | Crosslinked polymer electrolyte membranes for heat, ion and moisture exchange devices |
US7012118B2 (en) * | 2002-02-07 | 2006-03-14 | Kraton Polymers U.S. Llc | Photopolymerizable compositions and flexographic plates prepared from controlled distribution block copolymers |
US6759454B2 (en) * | 2002-02-07 | 2004-07-06 | Kraton Polymers U.S. Llc | Polymer modified bitumen compositions |
US20030181584A1 (en) * | 2002-02-07 | 2003-09-25 | Kraton Polymers U.S. Llc | Elastomeric articles prepared from controlled distribution block copolymers |
JP4530669B2 (ja) * | 2002-04-25 | 2010-08-25 | 旭化成ケミカルズ株式会社 | ブロック共重合体及びその組成物 |
EP1431348A1 (en) * | 2002-12-16 | 2004-06-23 | KRATON Polymers Research B.V. | Block copolymer modified bitumen felts |
US7795347B2 (en) * | 2003-03-14 | 2010-09-14 | Mitsui Chemicals, Inc. | Multi-branched polymer, process for producing the same, and applications thereof |
KR20050109993A (ko) * | 2003-03-14 | 2005-11-22 | 제이에스알 가부시끼가이샤 | 수소 첨가 디엔계 공중합체, 중합체 조성물 및 성형체 |
US7517932B2 (en) * | 2003-03-24 | 2009-04-14 | Kraton Polymers U.S. Llc | Poly(styrene-butadiene-styrene)polymers having a high vinyl content in the butadiene block and hot melt adhesive composition comprising said polymers |
DE112004000706T5 (de) * | 2003-05-01 | 2006-03-23 | Kraton Polymers Research B.V. | Färbbare Zusammensetzung |
TW200524971A (en) * | 2003-07-15 | 2005-08-01 | Denki Kagaku Kogyo Kk | Heat-shrinkable foam films |
JP2007506842A (ja) * | 2003-09-23 | 2007-03-22 | デイス−アナリティック コーポレーション | 新規なブロックコポリマー及びその製造方法 |
JP4776155B2 (ja) * | 2003-10-21 | 2011-09-21 | 旭化成ケミカルズ株式会社 | 水添共重合体 |
US7037980B2 (en) * | 2003-11-10 | 2006-05-02 | Chevron Phillips Chemical Company, Lp | Monovinylarene/conjugated diene copolymers having lower glass transition temperatures |
US20050119403A1 (en) * | 2003-12-01 | 2005-06-02 | St. Clair David J. | Solvent based, elastomeric coatings with lower VOC |
EP1566411B1 (en) * | 2004-02-19 | 2007-03-28 | Kraton Polymers Research B.V. | Coloured roofing felt |
CN100569849C (zh) * | 2004-03-03 | 2009-12-16 | 克拉通聚合物研究有限公司 | 包含具有高流动性的嵌段共聚物的弹性体双组分纤维 |
US7799854B2 (en) | 2004-04-01 | 2010-09-21 | Sabic Innovative Plastics Ip B.V. | Flame retardant thermoplastic composition and articles comprising the same |
US7417083B2 (en) | 2004-04-01 | 2008-08-26 | Sabic Innovative Plastics Ip B.V. | Flame retardant composition |
US7582692B2 (en) * | 2004-04-01 | 2009-09-01 | Sabic Innovative Plastics Ip B.V. | Flame retardant thermoplastic composition and articles comprising the same |
US7348076B2 (en) | 2004-04-08 | 2008-03-25 | Saint-Gobain Ceramics & Plastics, Inc. | Single crystals and methods for fabricating same |
US7905872B2 (en) | 2004-06-04 | 2011-03-15 | The Procter & Gamble Company | Absorbent articles comprising a slow recovery stretch laminate |
US7717893B2 (en) | 2004-06-04 | 2010-05-18 | The Procter & Gamble Company | Absorbent articles comprising a slow recovery elastomer |
MX2007001481A (es) * | 2004-08-05 | 2007-04-20 | Firestone Polymers Llc | Polimero funcional multibloques. |
FR2876141B1 (fr) * | 2004-10-06 | 2006-12-08 | Sandvik Tamrock Secoma Sas Soc | Dispositif de foration par rotopercussion |
US20060115613A1 (en) * | 2004-12-01 | 2006-06-01 | Cryovac, Inc. | Patch bag and barrier bag |
US7473473B2 (en) * | 2004-12-01 | 2009-01-06 | Cryovac, Inc. | Tear resistant shrink film |
US20060135695A1 (en) * | 2004-12-17 | 2006-06-22 | Hua Guo | Flexible poly(arylene ether) composition and articles thereof |
US7776441B2 (en) * | 2004-12-17 | 2010-08-17 | Sabic Innovative Plastics Ip B.V. | Flexible poly(arylene ether) composition and articles thereof |
US8419701B2 (en) | 2005-01-10 | 2013-04-16 | The Procter & Gamble Company | Absorbent articles with stretch zones comprising slow recovery elastic materials |
ATE539723T1 (de) | 2005-01-26 | 2012-01-15 | Procter & Gamble | Einwegwindel mit elastischer taille und geringer stärke sowie langer wiederherstellungszeit |
US7772322B2 (en) * | 2005-02-17 | 2010-08-10 | Sabic Innovative Plastics Ip B.V. | Poly(arylene ether) composition and articles |
US7531209B2 (en) * | 2005-02-24 | 2009-05-12 | Michael Raymond Ayers | Porous films and bodies with enhanced mechanical strength |
EP1858974B1 (en) | 2005-03-11 | 2012-08-22 | KRATON Polymers Research B.V. | Oil gels of controlled distribution block copolymers and ester oils |
US20060205904A1 (en) * | 2005-03-11 | 2006-09-14 | St Clair David J | Oil gels of controlled distribution block copolymers and ester oils |
EP1707596A1 (en) * | 2005-03-14 | 2006-10-04 | Kraton Polymers Research B.V. | Hydrogenated block copolymer composition for overmoulding onto thermoplastics |
US20060263596A1 (en) * | 2005-05-06 | 2006-11-23 | Bamborough Derek W | Pressure sensitive adhesives (PSA) laminates |
US20060251890A1 (en) * | 2005-05-06 | 2006-11-09 | Richard Lane | Pressure sensitive adhesive (PSA) laminates |
TWI326691B (en) * | 2005-07-22 | 2010-07-01 | Kraton Polymers Res Bv | Sulfonated block copolymers, method for making same, and various uses for such block copolymers |
US20070026251A1 (en) * | 2005-07-26 | 2007-02-01 | Kraton Polymers U.S. Llc | Flexible packaging laminate films including a block copolymer layer |
US20070055015A1 (en) * | 2005-09-02 | 2007-03-08 | Kraton Polymers U.S. Llc | Elastomeric fibers comprising controlled distribution block copolymers |
US20070066753A1 (en) * | 2005-09-16 | 2007-03-22 | Ehrlich Martin L | Highly processible compounds of high MW conventional block copolymers and controlled distribution block copolymers |
US20070078194A1 (en) * | 2005-10-04 | 2007-04-05 | St Clair David J | Flexographic printing plate and flexographic printing plate precursor composition for preparing same |
WO2007058994A2 (en) | 2005-11-14 | 2007-05-24 | Kraton Polymers Research B.V. | Process for preparing a bituminous binder composition |
EA013915B1 (ru) | 2005-11-28 | 2010-08-30 | Гала Индастриз, Инк. | Устройство и способ переработки с контролируемым гранулированием |
US20070130863A1 (en) * | 2005-12-01 | 2007-06-14 | Jones David R Iv | Roofing adhesive |
US7737216B2 (en) * | 2006-01-26 | 2010-06-15 | Chevron Phillips Chemical Company Lp | Monovinylarene conjugated diene block copolymer compositions for shrinkable films |
US7662528B2 (en) * | 2006-02-17 | 2010-02-16 | Xerox Corporation | Charge generating composition |
US7625851B2 (en) * | 2006-03-10 | 2009-12-01 | Kraton Polymers Us Llc | Viscosity index improver for lubricating oils |
US7592390B2 (en) | 2006-03-24 | 2009-09-22 | Kraton Polymers U.S. Llc | Hydrogenated block copolymer compositions |
US7585916B2 (en) | 2006-03-24 | 2009-09-08 | Kraton Polymers Us Llc | Block copolymer compositions |
US7582702B2 (en) * | 2006-03-24 | 2009-09-01 | Kraton Polymers U.S. Llc | Block copolymer compositons |
US7858693B2 (en) | 2006-03-24 | 2010-12-28 | Kratonpolymers U.S. Llc | Unhydrogenated block copolymer compositions |
RU2433152C2 (ru) * | 2006-03-24 | 2011-11-10 | КРЭЙТОН ПОЛИМЕРС Ю.Эс.ЭлЭлСи | Высокотемпературные блок-сополимеры и процесс их получения |
WO2007127155A2 (en) * | 2006-04-24 | 2007-11-08 | Kraton Polymers U.S Llc | Polymeric compositions and films formed therefrom |
US7990679B2 (en) * | 2006-07-14 | 2011-08-02 | Dais Analytic Corporation | Nanoparticle ultracapacitor |
DE102006037627A1 (de) * | 2006-08-10 | 2008-02-14 | Tesa Ag | Selbstklebemasse aus hydrierten Blockcopolymeren und daraus hergestellte Schutzfolie für glatte und raue Oberflächen |
US7685784B2 (en) * | 2006-08-25 | 2010-03-30 | Tremco Incorporated | Cool roof covering and adhesive therefor |
US8470071B2 (en) * | 2006-09-25 | 2013-06-25 | Dais Analytic Corporation | Enhanced HVAC system and method |
EP2087174B1 (en) * | 2006-11-13 | 2017-01-18 | Kraton Polymers U.S. LLC | Bituminous emulsions |
US20100075132A1 (en) * | 2006-12-07 | 2010-03-25 | 3M Innovative Properties Company | Blends of block copolymer and acrylic adhesives |
CN101547988B (zh) * | 2006-12-07 | 2014-01-29 | 3M创新有限公司 | 具有多种增粘剂的嵌段共聚物共混物粘合剂 |
US20080153970A1 (en) * | 2006-12-21 | 2008-06-26 | Kraton Polymers U.S. Llc | Solvent sprayable contact adhesive formulations from functionalized/controlled distribution block copolymers |
US7977432B2 (en) * | 2007-01-12 | 2011-07-12 | Kraton Polymers U.S. Llc | Functionalized block copolymers, method for making same, and various uses for such block copolymers |
CN101663334B (zh) * | 2007-01-19 | 2012-06-13 | 斯蒂潘公司 | 嵌段聚合物的磺化方法 |
CN103203185B (zh) * | 2007-01-20 | 2016-01-13 | 戴斯分析公司 | 具有包含经加热空气的干燥腔室的干燥器 |
US20080193755A1 (en) * | 2007-02-09 | 2008-08-14 | Olivier Guise | Extrusion die, methods of coating a wire core, and a coated wire by the extrusion die and methods |
MX2009011561A (es) * | 2007-05-01 | 2009-11-10 | Kraton Polymers Us Llc | Composicion aglutinante bituminosa y proceso para preparar la misma. |
DE102007027156A1 (de) | 2007-06-13 | 2008-12-24 | Kraiburg Tpe Gmbh & Co. Kg | Transparente, thermoplastisch verarbeitbare, elastomere Polymerzusammensetzung mit UV-Stabilität und guten Haftungseigenschaften |
CN101918487A (zh) * | 2007-06-26 | 2010-12-15 | 艺杰斯生物科学有限责任公司 | 稳定且相容的聚合物共混物 |
US20090062457A1 (en) * | 2007-09-04 | 2009-03-05 | Kraton Polymers U.S. Llc | Styrenic block copolymers and compositions containing the same |
US7923391B2 (en) * | 2007-10-16 | 2011-04-12 | Kimberly-Clark Worldwide, Inc. | Nonwoven web material containing crosslinked elastic component formed from a pentablock copolymer |
US7923392B2 (en) * | 2007-10-16 | 2011-04-12 | Kimberly-Clark Worldwide, Inc. | Crosslinked elastic material formed from a branched block copolymer |
US8349963B2 (en) * | 2007-10-16 | 2013-01-08 | Kimberly-Clark Worldwide, Inc. | Crosslinked elastic material formed from a linear block copolymer |
US8399368B2 (en) * | 2007-10-16 | 2013-03-19 | Kimberly-Clark Worldwide, Inc. | Nonwoven web material containing a crosslinked elastic component formed from a linear block copolymer |
US8323257B2 (en) | 2007-11-21 | 2012-12-04 | The Procter & Gamble Company | Absorbent articles comprising a slow recovery stretch laminate and method for making the same |
US8883927B2 (en) * | 2007-11-28 | 2014-11-11 | Dynasol Elastómeros, S.A. De C.V. | Radial multi-block copolymers |
CN101903455B (zh) * | 2007-12-21 | 2013-01-16 | 科腾聚合物美国有限责任公司 | 软质弹性体膜 |
US9453606B2 (en) * | 2007-12-26 | 2016-09-27 | Smart Pipe Company, Inc. | Movable factory for simultaneous mobile field manufacturing and installation of non-metallic pipe |
RU2501816C2 (ru) * | 2008-04-30 | 2013-12-20 | Стирон Юроп Гмбх | Стирол-бутадиеновые полимеры со стирольным градиентом и способы изготовления таковых |
US8084521B2 (en) | 2008-04-30 | 2011-12-27 | Wright Advanced Asphalt Systems | System and method for the pre-treatment of rubber-modified asphalt cement, and emulsions thereof |
US8012539B2 (en) | 2008-05-09 | 2011-09-06 | Kraton Polymers U.S. Llc | Method for making sulfonated block copolymers, method for making membranes from such block copolymers and membrane structures |
US9017791B2 (en) | 2008-05-13 | 2015-04-28 | Owens Corning Intellectual Capital, Llc | Shingle blank having formation of individual hip and ridge roofing shingles |
CN102099381B (zh) * | 2008-06-18 | 2013-10-02 | 思迪隆欧洲有限公司 | 低氯化物聚丁二烯 |
US20100010154A1 (en) * | 2008-07-08 | 2010-01-14 | Kraton Polymers U.S. Llc | Gels prepared from dpe containing block copolymers |
US20100010147A1 (en) * | 2008-07-08 | 2010-01-14 | Kraton Polymer U.S. Llc | Adhesives prepared from diphenylethylene containing block copolymers |
US20100010171A1 (en) * | 2008-07-11 | 2010-01-14 | Ruidong Ding | Thermoplastic polyurethane/block copolymer compositions |
US9732178B1 (en) | 2008-07-24 | 2017-08-15 | Bridgestone Corporation | Block copolymers including high vinyl segments |
JP5628803B2 (ja) * | 2008-08-05 | 2014-11-19 | フアイヤーストーン・ポリマース・エルエルシー | 凝集物でないスチレン−ブタジエンジブロック共重合体−含有配合物および製造方法 |
US20100056721A1 (en) * | 2008-09-03 | 2010-03-04 | Kathryn Wright | Articles prepared from certain hydrogenated block copolymers |
WO2010036341A1 (en) | 2008-09-24 | 2010-04-01 | Wright Asphalt Products Company | System and method for high throughput preparation of rubber-modified asphalt cements |
ES2654377T3 (es) | 2008-10-07 | 2018-02-13 | Ross Technology Corporation | Superficies resistentes a los derrames con fronteras hidrofóbicas y oleofóbicas |
US20100130670A1 (en) * | 2008-11-21 | 2010-05-27 | Kraton Polymers Us Llc | End use applications prepared from certain block copolymers |
US11313127B2 (en) | 2009-02-25 | 2022-04-26 | Owens Corning Intellectual Capital, Llc | Hip and ridge roofing material |
US9151055B2 (en) | 2009-02-25 | 2015-10-06 | Owens Corning Intellectual Capital, Llc | Hip and ridge roofing material |
US20100222464A1 (en) * | 2009-02-27 | 2010-09-02 | Semmaterials, L.P. | Emulsion of a polymer modified asphalt |
US20100222469A1 (en) * | 2009-02-27 | 2010-09-02 | Semmaterials, L.P. | A crack resistant layer with good binder fracture energy properties and method of selecting same |
US20100222467A1 (en) * | 2009-02-27 | 2010-09-02 | Semmaterials, L.P. | crack resistent layer with good mixture fracture energy made from an emulsion of a polymer modified bituminous binder and method of selecting same |
US20100222466A1 (en) * | 2009-02-27 | 2010-09-02 | Semmaterials, L.P. | Crack resistant layer with good beam fatigue properties made from an emulsion of a polymer modified bituminous binder and method of selecting same |
US20100222465A1 (en) * | 2009-02-27 | 2010-09-02 | Semmaterials, L.P. | Crack resistant layer with good mixture fracture energy and method of selecting same |
CN101508811A (zh) * | 2009-03-10 | 2009-08-19 | 叶孙勇 | 可注射可硫化苯乙烯系橡胶粒子及制备工艺 |
US9574350B2 (en) | 2009-03-20 | 2017-02-21 | Owens Corning Intellectual Capital, Llc | Sealant composition for releasable shingle |
US8445631B2 (en) | 2009-10-13 | 2013-05-21 | Kraton Polymers U.S. Llc | Metal-neutralized sulfonated block copolymers, process for making them and their use |
US8263713B2 (en) * | 2009-10-13 | 2012-09-11 | Kraton Polymers U.S. Llc | Amine neutralized sulfonated block copolymers and method for making same |
BR112012011124A2 (pt) * | 2009-11-12 | 2016-07-05 | Kraton Polymers Us Llc | composicao de copolímero em bloco |
US9013155B2 (en) | 2010-01-09 | 2015-04-21 | Dais Analytic Corporation | Energy storage devices including a solid multilayer electrolyte |
US9393557B2 (en) | 2010-01-09 | 2016-07-19 | Dais Analytic Corporation | Anionic exchange electrolyte polymer membranes |
US8299177B2 (en) * | 2010-01-27 | 2012-10-30 | Kranton Polymers U.S. LLC | Compositions containing styrene-isobutylene-styrene and controlled distribution block copolymers |
MX2011011384A (es) | 2010-01-29 | 2011-11-18 | Kraton Polymers Us Llc | Composicion termofusible para moldeo en hueco. |
US20140141233A1 (en) | 2012-07-03 | 2014-05-22 | Peterson Chemical Technology, Inc. | Surface Infusion of Flexible Cellular Foams With Novel Liquid Gel Mixture |
US9097020B2 (en) * | 2010-03-04 | 2015-08-04 | Owens Corning Intellectual Capital, Llc | Hip and ridge roofing shingle |
WO2011116005A1 (en) | 2010-03-15 | 2011-09-22 | Ross Technology Corporation | Plunger and methods of producing hydrophobic surfaces |
US20110262686A1 (en) * | 2010-04-22 | 2011-10-27 | Kathryn Wright | High Tensile Strength Article with Elastomeric Layer |
CN101870744A (zh) * | 2010-06-11 | 2010-10-27 | 北京化工大学 | 一种丁腈酯橡胶的加氢方法 |
US9394414B2 (en) | 2010-09-29 | 2016-07-19 | Kraton Polymers U.S. Llc | Elastic, moisture-vapor permeable films, their preparation and their use |
US9429366B2 (en) | 2010-09-29 | 2016-08-30 | Kraton Polymers U.S. Llc | Energy recovery ventilation sulfonated block copolymer laminate membrane |
BR112013007705A2 (pt) | 2010-10-18 | 2016-08-09 | Kraton Polymers Us Llc | solução tendo uma composição de copolímero em bloco sulfonado, película ou membrana, dispersão aquosa, compósito, composição de copolímeto em bloco sulfonado, processo, método para formar uma composição de copolímero em bloco sulfonado, e, célula eletrodialítica |
US9017305B2 (en) | 2010-11-12 | 2015-04-28 | The Procter Gamble Company | Elastomeric compositions that resist force loss and disintegration |
EP2648900A1 (en) | 2010-12-06 | 2013-10-16 | Colgate-Palmolive Company | Laminate tube having enhanced resiliency by a block copolymer |
KR20130135286A (ko) | 2010-12-23 | 2013-12-10 | 바스프 에스이 | 열가소성 엘라스토머 조성물 및 그의 제조 방법 |
CN108559288B (zh) * | 2011-01-30 | 2020-10-27 | 戴纳索尔伊莱斯托米罗斯公司 | 递变三嵌段共聚物 |
JP2014511411A (ja) | 2011-02-18 | 2014-05-15 | クレイトン・ポリマーズ・ユー・エス・エル・エル・シー | ケーブル充填用硬化性ポリマー組成物 |
PE20140834A1 (es) | 2011-02-21 | 2014-07-10 | Ross Technology Corp | Revestimiento superhidrofos y oleofobos con sistema aglutinantes con bajo contenido de cov |
CN102190957B (zh) * | 2011-03-21 | 2013-04-24 | 武汉理工大学 | 一种镁铝基层状双氢氧化物耐老化弹性体改性沥青涂盖料及其制备方法 |
JP2014511925A (ja) * | 2011-04-07 | 2014-05-19 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | 瀝青組成物 |
TWI512060B (zh) * | 2011-04-26 | 2015-12-11 | Chi Mei Corp | 防濕絕緣塗料及其應用 |
US8378453B2 (en) | 2011-04-29 | 2013-02-19 | Georgia Tech Research Corporation | Devices including composite thermal capacitors |
CN102277112B (zh) * | 2011-05-23 | 2014-11-05 | 波士胶芬得利(中国)粘合剂有限公司 | 含蜡热熔胶和一次性吸收制品 |
US9861941B2 (en) | 2011-07-12 | 2018-01-09 | Kraton Polymers U.S. Llc | Modified sulfonated block copolymers and the preparation thereof |
US20130101767A1 (en) | 2011-10-25 | 2013-04-25 | Kraton Polymers U.S. Llc | Method for melt processing sulfonated block copolymers and articles comprising optionally amine modified sulfonated block copolymers |
US11021559B2 (en) | 2011-10-31 | 2021-06-01 | Kraton Polymers Llc | Sulfonated block copolymer laminates with polar or active metal substrates |
US20130310492A1 (en) * | 2011-11-17 | 2013-11-21 | Baker Hughes Incorporated | Process for improving the physical properties of bitumen |
EP2791255B1 (en) | 2011-12-15 | 2017-11-01 | Ross Technology Corporation | Composition and coating for superhydrophobic performance |
US9290943B2 (en) | 2012-01-05 | 2016-03-22 | Owens Corning Intellectual Capital, Llc | Hip and ridge roofing shingle |
US9293269B2 (en) | 2012-02-08 | 2016-03-22 | Dais Analytic Corporation | Ultracapacitor tolerating electric field of sufficient strength |
US20130225020A1 (en) * | 2012-02-24 | 2013-08-29 | Kraton Polymers Us Llc | High flow, hydrogenated styrene-butadiene-styrene block copolymer and applications |
US9771473B2 (en) | 2012-02-24 | 2017-09-26 | Kraton Polymers U.S. Llc | High flow, hydrogenated styrene-butadiene-styrene block copolymers and applications |
CN104220152A (zh) | 2012-03-15 | 2014-12-17 | 科腾聚合物美国有限责任公司 | 磺化嵌段共聚物和微粒碳的共混物与包含它们的膜,薄膜和涂层 |
CN103382241B (zh) * | 2012-05-04 | 2016-06-08 | 中国石油天然气股份有限公司 | 星形异戊二烯-b-丁二烯苯乙烯三元共聚物及其制备方法 |
AU2013281220B2 (en) * | 2012-06-25 | 2017-03-16 | Ross Technology Corporation | Elastomeric coatings having hydrophobic and/or oleophobic properties |
US20140100310A1 (en) | 2012-10-08 | 2014-04-10 | Teknor Apex Company | Thermoplastic elastomer compositions having biorenewable content |
WO2014058823A1 (en) | 2012-10-08 | 2014-04-17 | Teknor Apex Company | Thermoplastic elastomer compositions having biorenewable content |
EP2759572A1 (en) | 2013-01-23 | 2014-07-30 | Teknor Apex Company | Thermoplastic elastomer compositions having biorenewable content |
US9938401B2 (en) | 2012-11-05 | 2018-04-10 | Kraton Polymers U.S. Llc | Fire retardant systems for polymers that enable flexibility and strength |
CN103804603B (zh) * | 2012-11-07 | 2016-03-02 | 中国石油化工股份有限公司 | 一种溶聚丁苯橡胶及其合成方法和酸酐的应用 |
EP2938666A4 (en) * | 2012-12-27 | 2016-06-29 | Peterson Chemical Technology Inc | SURFACE INFUSION OF FLEXIBLE CELLULAR FOAMS WITH A NOVEL LIQUID MIXTURE |
US10022680B2 (en) | 2013-01-14 | 2018-07-17 | Kraton Polymers U.S. Llc | Anion exchange block copolymers, their manufacture and their use |
US9061254B2 (en) * | 2013-01-14 | 2015-06-23 | Kraton Polymers U.S. Llc | Block copolymers, their manufacture and their use |
US20140202357A1 (en) * | 2013-01-18 | 2014-07-24 | Special Materials Company | Asphalt cutback formulations |
KR20150005424A (ko) * | 2013-07-05 | 2015-01-14 | 주식회사 엘지화학 | 혼련성이 개선된 아스팔트 개질제 및 이를 포함하는 아스팔트 조성물 |
US9127132B2 (en) | 2013-10-08 | 2015-09-08 | Katon Polymers U.S. LLC | Process for coagulating sulfonated block copolymers |
US10843401B2 (en) | 2013-11-01 | 2020-11-24 | Kraton Polymers U.S. Llc | Fuse molded three dimensional article and a method for making the same |
TWI512062B (zh) * | 2013-11-21 | 2015-12-11 | Chi Mei Corp | 防濕絕緣塗料及其應用 |
US20150148488A1 (en) * | 2013-11-25 | 2015-05-28 | Kraton Polymers U.S. Llc | Impact Resistant Compositions Of Thermoplastic Polyamides And Modified Block Copolymers For Use In Tubes, Pipes, And Hoses |
EP3083825B1 (de) * | 2013-12-18 | 2019-03-27 | INEOS Styrolution Group GmbH | Verwendung von formmassen basierend auf vinylaromat-dien-blockcopolymeren für den 3d druck |
WO2015108139A1 (ja) | 2014-01-17 | 2015-07-23 | 旭化成ケミカルズ株式会社 | 重合体及びアスファルト組成物 |
TWI555789B (zh) | 2014-01-17 | 2016-11-01 | Asahi Kasei Chemicals Corp | 聚合物及瀝青組合物 |
EP3105288B1 (en) | 2014-02-11 | 2020-04-08 | INEOS Styrolution Group GmbH | Blends of thermoplastic elastomers based on styrene (s-tpe) and polyolefins |
US9758970B2 (en) | 2014-02-25 | 2017-09-12 | Owens Corning Intellectual Capital, Llc | Laminated hip and ridge shingle |
USD755997S1 (en) | 2014-02-27 | 2016-05-10 | Owens Corning Intellectual Capital, Llc | Shingle |
WO2015129653A1 (ja) * | 2014-02-28 | 2015-09-03 | 日本ゼオン株式会社 | 透明粘着シート |
US10047477B2 (en) | 2014-04-02 | 2018-08-14 | Kraton Polymers U.S. Llc | Textile coating composition |
RU2016142917A (ru) | 2014-04-02 | 2018-05-08 | КРЭЙТОН ПОЛИМЕРС Ю.Эс. ЭлЭлСи | Способ получения водной эмульсии блоксополимера с сульфированным серединным блоком |
US10053603B2 (en) | 2014-04-02 | 2018-08-21 | Kraton Polymers U.S. Llc | Block copolymers containing a copolymer myrcene block |
WO2015157065A1 (en) | 2014-04-02 | 2015-10-15 | Kraton Polymers U.S. Llc | Process for the preparation of an aqueous emulsion of a midblock sulfonated block copolymer |
TWI616491B (zh) | 2014-05-08 | 2018-03-01 | Asahi Kasei Chemicals Corp | Asphalt composition |
EP3143057B1 (en) | 2014-05-16 | 2020-05-13 | Kraton Polymers U.S. LLC | Branched broad mwd conjugated diene polymer |
US9156978B1 (en) * | 2014-06-06 | 2015-10-13 | Teknor Apex Company | Low softener halogen free flame retardant styrenic block copolymer-based thermoplastic elastomer compositions |
US9216405B1 (en) | 2014-06-26 | 2015-12-22 | Kraton Polymers U.S. Llc | Rotary enthalpy exchange wheel having sulfonated block copolymer |
CN105273204B (zh) | 2014-07-16 | 2020-10-16 | 科腾聚合物美国有限责任公司 | 嵌段共聚物、其制备及其用途 |
MX2017007709A (es) | 2014-12-17 | 2017-10-27 | Fuller H B Co | Composicion adhesiva fusionada por calor para unir empaques de envases de plastico. |
CA2967861C (en) | 2014-12-17 | 2021-11-30 | H.B. Fuller Company | Hot melt adhesive composition for bonding packs of metal containers |
US9441090B1 (en) | 2015-03-12 | 2016-09-13 | Chevron Phillips Chemical Company Lp | Methods for controlling hardness of styrene-butadiene block copolymers |
US9598524B1 (en) | 2015-09-18 | 2017-03-21 | Chevron Phillips Chemical Company Lp | Styrene-butadiene block copolymers with a terminal butadiene block for tubing applications |
US9540475B2 (en) | 2015-03-12 | 2017-01-10 | Chevron Phillips Chemical Company Lp | Styrene-butadiene block copolymers for tubing applications |
BR112017022689B1 (pt) * | 2015-04-24 | 2021-06-15 | Pirelli Tyre S.P.A. | Pneu para rodas de veículo, copolímero, e processo de copolimerização de estireno e butadieno com um ou mais monômeros diênicos |
EP3307509B1 (en) | 2015-06-12 | 2020-08-05 | Kraton Polymers U.S. LLC | A composition for soft skins and uses thereof |
EP3323838B1 (en) | 2015-07-16 | 2019-04-17 | Asahi Kasei Kabushiki Kaisha | Partially hydrogenated block copolymer, viscous adhesive composition, viscous adhesive tape, label, modified asphalt composition, modified asphalt mixture, and paving binder composition |
US9738781B2 (en) | 2015-09-03 | 2017-08-22 | Ineos Styrolution Group Gmbh | Blends of styrene-butadiene block copolymer with styrenic thermoplastic elastomers for tubing applications |
US10066100B2 (en) * | 2015-09-08 | 2018-09-04 | Kraton Polymers U.S. Llc | Copolyester/controlled distribution styrenic block copolymer blends and methods of making and using same |
EP3408325B1 (en) | 2016-01-26 | 2023-03-15 | Dynasol Elastómeros, S.A.de C.V. | Counter tapered thermoplastic elastomers |
US10023676B2 (en) | 2016-02-24 | 2018-07-17 | Ineos Styrolution Group Gmbh | Styrene-butadiene block copolymers with an internal butadiene block for tubing applications |
US9828455B2 (en) | 2016-02-24 | 2017-11-28 | Ineos Styrolution Group Gmbh | Styrene-butadiene block copolymers with an internal butadiene block for tubing applications |
CN108779221B (zh) | 2016-03-24 | 2022-07-05 | 科腾聚合物美国有限责任公司 | 半结晶嵌段共聚物和得自其的组合物 |
US10539649B2 (en) | 2016-03-28 | 2020-01-21 | Michael L. Howard | System and methods for detecting a position using differential attenuation |
EP3445833B8 (en) | 2016-05-09 | 2021-05-26 | Kraton Polymers U.S. LLC | Foam adhesion promotion |
US10839979B2 (en) | 2016-07-08 | 2020-11-17 | Teknor Apex Company | Cable with flame retardant multi-layer covering |
CN106398618A (zh) * | 2016-08-27 | 2017-02-15 | 安徽天瞳智能科技有限公司 | 一种高密度树脂胶粘剂 |
US11124644B2 (en) * | 2016-09-01 | 2021-09-21 | University Of Florida Research Foundation, Inc. | Organic microgel system for 3D printing of silicone structures |
FR3059672B1 (fr) * | 2016-12-07 | 2020-10-30 | Total Marketing Services | Compositions huileuses solides |
WO2019009836A2 (en) * | 2016-12-30 | 2019-01-10 | Turkiye Petrol Rafinerileri Anonim Sirketi Tupras | BITUMINOUS MIXTURE COMPRISING POLYURETHANE OBTAINED BY A POLYMERIZATION REACTION AND PROCESS FOR PREPARING THE MIXTURE |
US20220411637A1 (en) | 2017-01-26 | 2022-12-29 | Dynasol Elastómeros, S.A. De C.V. | Counter Tapered Thermoplastic Elastomers |
KR102462740B1 (ko) * | 2017-03-16 | 2022-11-03 | 이네오스 스티롤루션 그룹 게엠베하 | 비점착성, 연질 및 투명한 스티렌계 열가소성 엘라스토머 |
JP2020523442A (ja) * | 2017-06-09 | 2020-08-06 | クレイトン・ポリマーズ・エル・エル・シー | 高度に非対称なトリブロックポリマー組成物及びその製造方法 |
EP3642280B1 (en) | 2017-06-19 | 2021-06-09 | INEOS Styrolution Group GmbH | Method for processing vinyl aromatic/diene-block copolymers having good organoleptic properties |
JP2020536139A (ja) | 2017-09-29 | 2020-12-10 | クレイトン・ポリマーズ・エル・エル・シー | 湿潤状態での握り心地が改善されたエラストマー組成物 |
CN111655786B (zh) | 2018-01-31 | 2023-12-29 | 积水富乐株式会社 | 伸缩性热熔组合物 |
DE102018109269A1 (de) | 2018-04-18 | 2019-10-24 | Clariant Plastics & Coatings Ltd | Dauerklebrige Haftklebstoffe mit verbesserter Umweltverträglichkeit |
US11759758B2 (en) | 2018-04-30 | 2023-09-19 | Kraton Corporation | Block copolymers for gel compositions with improved efficiency |
JP2020041141A (ja) | 2018-09-10 | 2020-03-19 | クレイトン・ポリマーズ・リサーチ・ベー・フェー | ゴム組成物及びその製造方法 |
EP3620477B1 (en) | 2018-09-10 | 2021-07-14 | Kraton Polymers Research B.V. | Medical tubing and compositions and methods for making therefor |
US11454623B2 (en) | 2018-10-11 | 2022-09-27 | Baker Hughes Holdings Llc | Method for quantitatively assessing stability additive performance at field dosages |
US11760826B2 (en) | 2018-12-14 | 2023-09-19 | Kraton Corporation | Block copolymers and uses thereof |
US11629215B2 (en) * | 2019-04-02 | 2023-04-18 | Kraton Corporation | Sulfonated block copolymers and uses thereof |
US11613619B2 (en) | 2019-05-29 | 2023-03-28 | Kraton Corporation | Molding compositions and foam molded articles made thereof |
FR3099766B1 (fr) * | 2019-08-07 | 2021-07-30 | Michelin & Cie | Polymère bloc diénique riche en éthylène ayant un bloc statistique et un bloc polyéthylène. |
WO2021090068A2 (en) * | 2019-11-07 | 2021-05-14 | Dynasol Elastomeros, S.A. De C.V. | Modified diene copolymers and their use |
US11739208B2 (en) | 2020-08-14 | 2023-08-29 | Kraton Corporation | Block copolymers and uses thereof |
JP2024504161A (ja) | 2021-01-24 | 2024-01-30 | クレイトン・コーポレイション | バッテリーのための電極バインダー |
KR20240024253A (ko) | 2021-06-24 | 2024-02-23 | 보레알리스 아게 | 폴리에틸렌 중합체의 제조 방법 |
KR20240023174A (ko) | 2021-06-24 | 2024-02-20 | 보레알리스 아게 | 올레핀 중합 촉매의 압축 특성을 결정하는 방법 |
CN115948121B (zh) * | 2023-01-05 | 2023-10-20 | 江苏凯伦建材股份有限公司 | 一种基于单环氧封端二嵌段共聚物的改性沥青涂料及其制备方法和应用 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4530652A (en) * | 1984-01-12 | 1985-07-23 | Buck Ollie G | Asphalt composition |
CN86102712A (zh) * | 1985-06-15 | 1986-12-10 | 吕特格尔斯末克有限公司 | 沥青材料及其应用 |
US5854335A (en) * | 1995-02-20 | 1998-12-29 | Shell Oil Company | Bituminous composition with diene/monovinyl aromatic block copolymer |
CN1305513A (zh) * | 1999-02-16 | 2001-07-25 | 戴纳索尔埃拉斯托默罗斯有限公司 | 改善用于筑路材料的含沥青混合物性能的改性剂 |
CN1324895A (zh) * | 2001-07-05 | 2001-12-05 | 上海交通大学 | 用于道路的改性沥青材料的生产工艺 |
Family Cites Families (108)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA716645A (en) | 1965-08-24 | Shell Oil Company | Block polymers and process for preparing them | |
US3149182A (en) | 1957-10-28 | 1964-09-15 | Shell Oil Co | Process for preparing block copolymers utilizing organolithium catalysts |
BE637376A (zh) | 1958-05-23 | |||
NL254508A (zh) * | 1960-08-03 | |||
US3239478A (en) * | 1963-06-26 | 1966-03-08 | Shell Oil Co | Block copolymer adhesive compositions and articles prepared therefrom |
US3600250A (en) | 1968-09-12 | 1971-08-17 | Shell Oil Co | Stretching and laminating thermoplastic elastomers |
US3595942A (en) | 1968-12-24 | 1971-07-27 | Shell Oil Co | Partially hydrogenated block copolymers |
USRE27145E (en) * | 1969-05-20 | 1971-06-22 | Side-chain | |
US3634549A (en) * | 1969-08-04 | 1972-01-11 | Shell Oil Co | Conjugated diene block copolymers having a random copolymer elastomeric block and their hydrogenated counterparts |
US3670054A (en) | 1969-10-29 | 1972-06-13 | Shell Oil Co | Block copolymers having reduced solvent sensitivity |
US3700633A (en) | 1971-05-05 | 1972-10-24 | Shell Oil Co | Selectively hydrogenated block copolymers |
US4039593A (en) | 1973-05-18 | 1977-08-02 | Lithium Corporation Of America | Preparation of hydroxy-terminated conjugated diene polymers |
US3821149A (en) * | 1973-09-28 | 1974-06-28 | Exxon Research Engineering Co | Plasticized thermoplastic semicrystalline block copolymers |
US3821148A (en) * | 1973-09-28 | 1974-06-28 | Exxon Research Engineering Co | Plasticized thermoplastic block copolymers |
US4089913A (en) * | 1974-01-10 | 1978-05-16 | Sumitomo Chemical Company, Limited | Process for producing transparent block copolymer resin |
JPS5232774B2 (zh) | 1974-02-02 | 1977-08-24 | ||
US4122134A (en) | 1974-02-13 | 1978-10-24 | Sumitomo Chemical Company, Limited | Method for producing transparent block copolymer resin |
US3985830B1 (en) | 1974-07-15 | 1998-03-03 | Univ Akron | Star polymers and process for the preparation thereof |
DE2550546A1 (de) * | 1975-11-11 | 1977-05-18 | Basf Ag | Schmelzhaftkleber auf der basis von blockcopolymerisaten |
US4107131A (en) | 1976-06-07 | 1978-08-15 | Shell Oil Company | Multicomponent polyurethane-block copolymer-polymer blends |
FR2376188A1 (fr) | 1976-12-28 | 1978-07-28 | Elf Union | Procede de preparation de compositions de bitumes polymeres |
US4267284A (en) | 1977-01-07 | 1981-05-12 | Phillips Petroleum Company | Tough, transparent articles from styrene polymers blended with certain block-random copolymers |
US4122434A (en) * | 1977-09-26 | 1978-10-24 | O.E.M. Technical Sales, Inc. | Test system for trailer brake mechanism |
US4129541A (en) | 1977-10-26 | 1978-12-12 | Phillips Petroleum Company | Asphaltic compositions containing conjugated diene-monovinyl-substituted aromatic hydrocarbon copolymers of particular structures |
US4248981A (en) * | 1979-04-30 | 1981-02-03 | Arco Polymers, Inc. | Clear impact resistant thermoplastic star-block copolymers |
JPS56149413A (en) | 1980-04-22 | 1981-11-19 | Japan Synthetic Rubber Co Ltd | Production of styrene/butadiene copolymer |
JPS57100112A (en) | 1980-12-16 | 1982-06-22 | Asahi Chem Ind Co Ltd | Perfectly random styrene-butadiene copolymer rubber |
US4444953A (en) | 1981-11-12 | 1984-04-24 | Shell Oil Company | Assymetric block copolymers and corresponding adhesive formulations |
US4391949A (en) | 1981-11-12 | 1983-07-05 | Shell Oil Company | Asymmetric block copolymers and corresponding adhesive formulations |
US4412087A (en) | 1981-12-16 | 1983-10-25 | Phillips Petroleum Company | Viscosity index improver with high thickening power |
US4603155A (en) | 1983-03-10 | 1986-07-29 | Japan Synthetic Rubber Co., Ltd. | Alkenyl aromatic compound-conjugated diene block copolymer and process for the production thereof |
JPH0615595B2 (ja) | 1984-02-07 | 1994-03-02 | シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー | ブロツク共重合体 |
JPS6129162A (ja) | 1984-07-20 | 1986-02-10 | Hitachi Ltd | 半導体装置 |
US4578429A (en) | 1984-08-31 | 1986-03-25 | Shell Oil Company | Selectively hydrogenated block copolymers modified with acid compounds or derivatives |
JPS61291610A (ja) | 1985-06-18 | 1986-12-22 | Japan Synthetic Rubber Co Ltd | ブロツク共重合体およびその組成物 |
US5371141A (en) | 1985-07-31 | 1994-12-06 | Shell Oil Company | High impact resistant blends of thermoplastic polyamides and modified block copolymers |
JPS6241213A (ja) | 1985-08-16 | 1987-02-23 | シエル・インタ−ナシヨネイル・リサ−チ・マ−チヤツピイ・ベ−・ウイ | 変性ブロツクコポリマ−、該コポリマ−を含有する耐衝撃性組成物、及び該コポリマ−の製造法 |
GB8714817D0 (en) * | 1987-06-24 | 1987-07-29 | Flymo Ltd | Grass trimmer |
US4788361A (en) | 1987-10-30 | 1988-11-29 | Shell Oil Company | Polymeric viscosity index improver and oil composition comprising the same |
US4882384A (en) | 1988-02-01 | 1989-11-21 | Shell Oil Company | Modified block copolymers |
US5239010A (en) | 1988-05-24 | 1993-08-24 | Shell Oil Company | Sulfonated block copolymers |
US4970265A (en) * | 1989-03-27 | 1990-11-13 | Shell Oil Company | Functionalized polymers and process for modifying unsaturated polymers |
DE69032963T2 (de) * | 1989-05-19 | 1999-08-19 | Japan Synthetic Rubber Co Ltd | (Modifiziertes) hydriertes Dien-Blockcopolymer und dieses enthaltende Zusammensetzung |
JPH0798890B2 (ja) * | 1989-06-23 | 1995-10-25 | 日本ゼオン株式会社 | 粘着剤用ブロック共重合体組成物及び粘着剤組成物 |
GB8918702D0 (en) * | 1989-08-16 | 1989-09-27 | Shell Int Research | Process for the preparation of random solution copolymers of conjugated dienes and vinyl aromatic compounds |
US5206300A (en) | 1990-03-30 | 1993-04-27 | Shell Oil Company | Functionalized elastomeric polymers |
KR0185671B1 (ko) | 1990-08-23 | 1999-05-15 | 요하네스 아르트 반 주트펜 | 블록 공중합체의 용융 금속화 방법 |
US5227419A (en) | 1990-12-20 | 1993-07-13 | Phillips Petroleum Company | Tapered block styrene/butadiene copolymers |
US5516831A (en) | 1991-01-30 | 1996-05-14 | Shell Oil Company | Selectively sulfonated block copolymers/extender oils |
CA2068154C (en) * | 1992-05-07 | 1997-01-14 | Janice C. Halligan | Programmable call progress tones for a switching system |
US5290875A (en) * | 1992-11-30 | 1994-03-01 | Phillips Petroleum Company | Conjugated diene/monovinylarene block copolymers with multiple tapered blocks |
US5905097A (en) * | 1993-01-08 | 1999-05-18 | The Dow Chemical Company | High-strength breathable films of block copolymer lattices |
JP3367136B2 (ja) | 1993-03-22 | 2003-01-14 | ジェイエスアール株式会社 | 熱可塑性樹脂組成物 |
GB9306517D0 (en) | 1993-03-29 | 1993-05-19 | Polyphalt Inc | Stabilized bitumen compositions |
JP3203399B2 (ja) * | 1993-05-13 | 2001-08-27 | 松下電器産業株式会社 | 経路探索装置 |
US5331028A (en) | 1993-06-30 | 1994-07-19 | Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. | Polymer-modified asphalt composition and process for the preparation thereof |
JPH07123696A (ja) | 1993-10-22 | 1995-05-12 | Oriental Motor Co Ltd | 多相リニアモータの鉄心製造方法 |
US6265484B1 (en) | 1993-11-15 | 2001-07-24 | Phillips Petroleum Company | Tapered block copolymers of monovinylarenes and conjugated dienes |
CA2134026C (en) | 1993-11-15 | 1998-06-09 | William J. Trepka | Tapered block copolymers of monovinylarenes and conjugated dienes |
JPH07149952A (ja) | 1993-11-30 | 1995-06-13 | Toray Ind Inc | 熱硬化性樹脂組成物、樹脂硬化物、プリプレグおよび繊維強化プラスチック |
US7290367B2 (en) * | 1994-04-19 | 2007-11-06 | Applied Elastomerics, Inc. | Tear resistant gel articles for various uses |
US7234560B2 (en) * | 1994-04-19 | 2007-06-26 | Applied Elastomerics, Inc. | Inflatable restraint cushions and other uses |
US7226484B2 (en) * | 1994-04-19 | 2007-06-05 | Applied Elastomerics, Inc. | Tear resistant gels and articles for every uses |
US5468574A (en) | 1994-05-23 | 1995-11-21 | Dais Corporation | Fuel cell incorporating novel ion-conducting membrane |
DE4420952A1 (de) * | 1994-06-17 | 1995-12-21 | Basf Ag | Thermoplastisches Elastomer |
US5451619A (en) | 1994-08-19 | 1995-09-19 | Shell Oil Company | Asphalt composition containing epoxidized polymers |
DE19503944A1 (de) | 1995-02-07 | 1996-08-08 | Basf Ag | Medizintechnisches Formteil, insbesondere Bauteil für ein Übertragungssystem für Infusions- oder Transfusionszwecke |
DE19523585A1 (de) * | 1995-06-29 | 1997-01-02 | Basf Ag | Schlagzähe Formmasse aus Styrolpolymeren |
DE871692T1 (de) * | 1995-08-29 | 2000-08-31 | Pennzoil Quaker State Co | Transparente gel-kerzen |
GB2305667A (en) * | 1995-09-27 | 1997-04-16 | Lawrence Lester | Bitumen-polymer compositions |
US6865759B2 (en) * | 1996-02-14 | 2005-03-15 | Edizone, Inc. | Cushions with non-intersecting-columnar elastomeric members exhibiting compression instability |
US6797765B2 (en) * | 1996-02-14 | 2004-09-28 | Edizone, Lc | Gelatinous elastomer |
US5749111A (en) * | 1996-02-14 | 1998-05-12 | Teksource, Lc | Gelatinous cushions with buckling columns |
US5994450A (en) * | 1996-07-01 | 1999-11-30 | Teksource, Lc | Gelatinous elastomer and methods of making and using the same and articles made therefrom |
US5795944A (en) | 1996-03-18 | 1998-08-18 | Shell Oil Company | Programmed addition of heavy ethers for microstructure control of diene polymers |
ZA972383B (en) * | 1996-03-22 | 1997-09-25 | Shell Int Research | High temperature, low viscosity thermoplastic elastomer block copolymer compositions. |
DE19615533A1 (de) | 1996-04-19 | 1997-10-23 | Basf Ag | Thermoplastische Formmasse |
DE19621688A1 (de) | 1996-05-30 | 1997-12-04 | Basf Ag | Transparente, nicht-blockende Folie |
US5773496A (en) | 1996-05-31 | 1998-06-30 | Koch Industries, Inc. | Polymer enhanced asphalt |
TW416971B (en) | 1996-07-31 | 2001-01-01 | Shell Internattonale Res Mij B | Oil gel formulations containing high vinyl content hydrogenated styrene-butadiene-styrene block copolymers |
US5776234A (en) | 1996-08-12 | 1998-07-07 | Westvaco Corporation | Anionic bituminous emulsions with improved adhesion |
DE19638254A1 (de) | 1996-09-19 | 1998-03-26 | Basf Ag | Thermoplastische Elastomere |
DE19638256A1 (de) * | 1996-09-19 | 1998-03-26 | Basf Ag | Thermoplastische Formmassen |
DE19645732A1 (de) | 1996-11-06 | 1998-05-07 | Basf Ag | Pulverförmige Polymerzusammensetzungen |
US5973037A (en) | 1996-11-27 | 1999-10-26 | Fields; John R. | Styrene ethylene butylene styrene (SEBS) copolymer rubber modified asphalt mixture |
SG55445A1 (en) | 1997-01-07 | 1998-12-21 | Denki Kagaku Kogyo Kabushili K | Block copolymer block copolymer compostion and heat shrinkable films made thereof |
EP0853103A1 (en) | 1997-01-08 | 1998-07-15 | Fina Research S.A. | Bituminous compositions containing linear copolymers |
JP3187848B2 (ja) | 1997-04-04 | 2001-07-16 | ポリファルト インコーポレイテッド | エラストマー改質ビチューメン組成物 |
US5886113A (en) | 1997-04-28 | 1999-03-23 | Taiwan Synthetic Rubber Corporation | Process for preparing an elastomeric copolymer composition of mono-vinyl aromatic hydrocarbons and conjugated dienes |
US6143832A (en) | 1997-05-22 | 2000-11-07 | Nippon Zeon Co., Ltd. | Aromatic vinyl-conjugated diene block copolymer and production process thereof |
US6423420B1 (en) * | 1997-08-11 | 2002-07-23 | Exxonmobil Chemical Patents Inc. | Oriented coextruded films |
US6110616A (en) | 1998-01-30 | 2000-08-29 | Dais-Analytic Corporation | Ion-conducting membrane for fuel cell |
KR100375782B1 (ko) * | 1998-08-03 | 2003-04-03 | 아사히 가세이 가부시키가이샤 | 선형 블록 공중합체 및 그를 함유하는 수지 조성물 |
US5998514A (en) | 1998-12-17 | 1999-12-07 | Basf Corporation | Random vinyl substituted aromatic/C4 -C6 conjugated diolefin polymer modified asphalt mixtures |
CN1172999C (zh) * | 1999-03-16 | 2004-10-27 | 国际壳牌研究有限公司 | 管材涂料 |
US6593430B1 (en) * | 1999-03-27 | 2003-07-15 | Basf Aktiengesellschaft | Transparent, impact-resistant polystyrene on a styrene-butadiene block copolymer basis |
DE19914075A1 (de) | 1999-03-27 | 2000-09-28 | Basf Ag | Glasklares, schlagzähes Polystyrol auf Basis von Styrol-Butadien-Blockcopolymeren |
US6391981B1 (en) | 1999-04-23 | 2002-05-21 | Kraton Polymers Us Llc | Increased throughput in the manufacture of anionic polymers by reduction in polymer cement viscosity through the addition of metal alkyls |
US6465557B1 (en) * | 1999-06-25 | 2002-10-15 | Kraton Polymers U.S. Llc | Hot melt pressure sensitive positioning adhesive |
US6310122B1 (en) | 1999-09-03 | 2001-10-30 | Fina Technology, Inc. | Stable bitumen polymer compositions |
US6395841B1 (en) * | 2000-09-06 | 2002-05-28 | The Dow Chemical Company | Process for hydrogenating unsaturated polymers |
US20040138371A1 (en) | 2002-02-07 | 2004-07-15 | St. Clair David John | Gels from controlled distribution block copolymers |
US20030181584A1 (en) | 2002-02-07 | 2003-09-25 | Kraton Polymers U.S. Llc | Elastomeric articles prepared from controlled distribution block copolymers |
US7012118B2 (en) | 2002-02-07 | 2006-03-14 | Kraton Polymers U.S. Llc | Photopolymerizable compositions and flexographic plates prepared from controlled distribution block copolymers |
US6759454B2 (en) * | 2002-02-07 | 2004-07-06 | Kraton Polymers U.S. Llc | Polymer modified bitumen compositions |
US7001956B2 (en) * | 2002-06-04 | 2006-02-21 | Kraton Polymers U.S. Llc | Articles prepared from hydrogenated block copolymers |
EP1384768A1 (en) | 2002-07-26 | 2004-01-28 | KRATON Polymers Research B.V. | Solvent-free hot melt adhesive, its use in bonding a polar leather layer to a non-polar substrate, and leather articles so produced |
US20060205904A1 (en) | 2005-03-11 | 2006-09-14 | St Clair David J | Oil gels of controlled distribution block copolymers and ester oils |
-
2003
- 2003-02-06 US US10/359,906 patent/US6759454B2/en not_active Expired - Lifetime
- 2003-02-06 US US10/359,927 patent/US6987142B2/en not_active Expired - Lifetime
- 2003-02-06 US US10/359,981 patent/US7169848B2/en not_active Expired - Lifetime
- 2003-02-06 US US10/359,462 patent/US7141621B2/en not_active Expired - Lifetime
- 2003-02-07 CN CNB03807477XA patent/CN1288209C/zh not_active Expired - Lifetime
- 2003-02-07 AU AU2003208666A patent/AU2003208666A1/en not_active Abandoned
- 2003-02-07 WO PCT/NL2003/000097 patent/WO2003066739A1/en not_active Application Discontinuation
- 2003-02-07 EP EP03705499A patent/EP1474481B1/en not_active Expired - Lifetime
- 2003-02-07 TW TW092102540A patent/TWI248962B/zh active
- 2003-02-07 EA EA200500184A patent/EA007542B1/ru not_active IP Right Cessation
- 2003-02-07 AU AU2003207422A patent/AU2003207422A1/en not_active Abandoned
- 2003-02-07 ES ES03705498T patent/ES2291615T3/es not_active Expired - Lifetime
- 2003-02-07 WO PCT/NL2003/000093 patent/WO2003066696A1/en active IP Right Grant
- 2003-02-07 AT AT03705498T patent/ATE376563T1/de not_active IP Right Cessation
- 2003-02-07 AU AU2003207423A patent/AU2003207423A1/en not_active Abandoned
- 2003-02-07 CN CN038074842A patent/CN1643016B/zh not_active Expired - Lifetime
- 2003-02-07 AU AU2003208665A patent/AU2003208665A1/en not_active Abandoned
- 2003-02-07 CN CNB038075040A patent/CN1315948C/zh not_active Expired - Fee Related
- 2003-02-07 DE DE60327051T patent/DE60327051D1/de not_active Expired - Lifetime
- 2003-02-07 AT AT03707248T patent/ATE427988T1/de not_active IP Right Cessation
- 2003-02-07 DE DE60314843T patent/DE60314843T2/de not_active Expired - Lifetime
- 2003-02-07 EP EP03705498A patent/EP1474458B1/en not_active Expired - Lifetime
- 2003-02-07 DE DE60317044T patent/DE60317044T2/de not_active Expired - Lifetime
- 2003-02-07 EP EP03707248A patent/EP1474496B1/en not_active Expired - Lifetime
- 2003-02-07 TW TW092102538A patent/TWI248447B/zh not_active IP Right Cessation
- 2003-02-07 US US10/511,992 patent/US7223816B2/en not_active Expired - Lifetime
- 2003-02-07 TW TW092102542A patent/TWI248964B/zh active
- 2003-02-07 TW TW092102529A patent/TWI301845B/zh not_active IP Right Cessation
- 2003-02-07 EP EP03707249A patent/EP1474482A1/en not_active Withdrawn
- 2003-02-07 WO PCT/NL2003/000095 patent/WO2003066770A1/en not_active Application Discontinuation
- 2003-02-07 CN CNB038074834A patent/CN1280323C/zh not_active Expired - Lifetime
- 2003-02-07 WO PCT/NL2003/000099 patent/WO2003066738A1/en active IP Right Grant
-
2005
- 2005-02-10 US US11/055,317 patent/US7138456B2/en not_active Expired - Lifetime
- 2005-02-10 US US11/055,357 patent/US7244785B2/en not_active Expired - Lifetime
- 2005-02-10 US US11/055,316 patent/US7067589B2/en not_active Expired - Lifetime
- 2005-02-10 US US11/055,367 patent/US7332542B2/en not_active Expired - Lifetime
- 2005-02-10 US US11/055,318 patent/US7169850B2/en not_active Expired - Lifetime
- 2005-02-10 US US11/055,349 patent/US7282536B2/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4530652A (en) * | 1984-01-12 | 1985-07-23 | Buck Ollie G | Asphalt composition |
CN86102712A (zh) * | 1985-06-15 | 1986-12-10 | 吕特格尔斯末克有限公司 | 沥青材料及其应用 |
US5854335A (en) * | 1995-02-20 | 1998-12-29 | Shell Oil Company | Bituminous composition with diene/monovinyl aromatic block copolymer |
CN1305513A (zh) * | 1999-02-16 | 2001-07-25 | 戴纳索尔埃拉斯托默罗斯有限公司 | 改善用于筑路材料的含沥青混合物性能的改性剂 |
CN1324895A (zh) * | 2001-07-05 | 2001-12-05 | 上海交通大学 | 用于道路的改性沥青材料的生产工艺 |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1315948C (zh) | 聚合物改性沥青组合物 | |
KR100470395B1 (ko) | 역청조성물 | |
WO2008137394A1 (en) | Bituminous binder composition and process for preparing the same | |
JP3641053B2 (ja) | アスファルト組成物 | |
CN1313540C (zh) | 沥青组合物 | |
US5854335A (en) | Bituminous composition with diene/monovinyl aromatic block copolymer | |
EP1358270B1 (en) | Bituminous composition with reduced gelation tendency | |
CN1232583C (zh) | 具有改进“可行走性”的沥青组合物和其在盖屋顶应用中的用途 | |
JP4602770B2 (ja) | ビチューメン組成物 | |
AU2002229602A1 (en) | Bituminous composition with reduced gelation tendency | |
JP2021183691A (ja) | ブロックコポリマー及びこれに由来するポリマー改質ビチューメン | |
RU2767536C1 (ru) | Полимерно-битумная композиция для кровельных материалов и блок-сополимер, входящий в её состав | |
KR102241925B1 (ko) | 블록 공중합체 조성물, 이의 제조방법 및 이를 포함하는 아스팔트 조성물 | |
KR20210090369A (ko) | 블록 공중합체 조성물, 이의 제조방법 및 이를 포함하는 아스팔트 조성물 | |
ZA200304245B (en) | Bituminous composition with reduced gelation tendency. |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070516 Termination date: 20160207 |