LU504304B1 - Modified styrene-butadiene rubber and the process for preparing the same and bitumen waterproofing membrane - Google Patents
Modified styrene-butadiene rubber and the process for preparing the same and bitumen waterproofing membrane Download PDFInfo
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- LU504304B1 LU504304B1 LU504304A LU504304A LU504304B1 LU 504304 B1 LU504304 B1 LU 504304B1 LU 504304 A LU504304 A LU 504304A LU 504304 A LU504304 A LU 504304A LU 504304 B1 LU504304 B1 LU 504304B1
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- butadiene rubber
- monomer
- styrene
- modified styrene
- modified
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- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 142
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000010426 asphalt Substances 0.000 title claims abstract description 50
- 239000012528 membrane Substances 0.000 title claims abstract description 48
- 238000004078 waterproofing Methods 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 89
- 229920000642 polymer Polymers 0.000 claims abstract description 51
- 239000003999 initiator Substances 0.000 claims abstract description 39
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 229920000098 polyolefin Polymers 0.000 claims abstract description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 81
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 45
- 239000012986 chain transfer agent Substances 0.000 claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 19
- -1 acrylamide compound Chemical class 0.000 claims description 18
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 238000012546 transfer Methods 0.000 claims description 11
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims description 10
- 238000010526 radical polymerization reaction Methods 0.000 claims description 10
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 8
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 5
- DZFGVGDQHQHOKZ-UHFFFAOYSA-N 2-dodecylsulfanylcarbothioylsulfanyl-2-methylpropanoic acid Chemical compound CCCCCCCCCCCCSC(=S)SC(C)(C)C(O)=O DZFGVGDQHQHOKZ-UHFFFAOYSA-N 0.000 claims description 5
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 5
- NNAHKQUHXJHBIV-UHFFFAOYSA-N 2-methyl-1-(4-methylthiophen-2-yl)-2-morpholin-4-ylpropan-1-one Chemical compound CC1=CSC(C(=O)C(C)(C)N2CCOCC2)=C1 NNAHKQUHXJHBIV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 238000013467 fragmentation Methods 0.000 claims description 5
- 238000006062 fragmentation reaction Methods 0.000 claims description 5
- 230000002441 reversible effect Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 4
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 4
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 claims description 4
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 claims description 4
- 239000012989 trithiocarbonate Substances 0.000 claims description 4
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 claims description 3
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012934 organic peroxide initiator Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- JTRQFTBOUAVPHA-UHFFFAOYSA-N 4-dodecylsulfanylcarbothioylsulfanylpentanoic acid Chemical compound C(CCCCCCCCCCC)SC(=S)SC(CCC(=O)O)C JTRQFTBOUAVPHA-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 35
- 230000032683 aging Effects 0.000 abstract description 15
- 238000004132 cross linking Methods 0.000 abstract description 9
- 125000000524 functional group Chemical group 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000003607 modifier Substances 0.000 abstract description 4
- 239000002174 Styrene-butadiene Substances 0.000 description 53
- 238000005406 washing Methods 0.000 description 21
- 150000003254 radicals Chemical class 0.000 description 17
- 239000007788 liquid Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000005062 Polybutadiene Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 229920002857 polybutadiene Polymers 0.000 description 10
- 239000005457 ice water Substances 0.000 description 9
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 9
- 239000000543 intermediate Substances 0.000 description 7
- 229940095095 2-hydroxyethyl acrylate Drugs 0.000 description 6
- RNTXYZIABJIFKQ-UHFFFAOYSA-N 4-cyano-4-dodecylsulfanylcarbothioylsulfanylpentanoic acid Chemical compound CCCCCCCCCCCCSC(=S)SC(C)(C#N)CCC(O)=O RNTXYZIABJIFKQ-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000005591 trimellitate group Chemical group 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- NFPBWZOKGZKYRE-UHFFFAOYSA-N 2-propan-2-ylperoxypropane Chemical compound CC(C)OOC(C)C NFPBWZOKGZKYRE-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003412 degenerative effect Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft 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
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present application discloses a modified styrene-butadiene rubber, a process for preparing the same and a bitumen waterproofing membrane. The modified styrene-butadiene rubber provided by the present application includes a styrene-butadiene rubber matrix and a modified polymer bound to at least part of the surface of the styrene-butadiene rubber matrix, wherein the modified polymer includes a polymeric chain segment of a first monomer and a polymeric chain segment of a second monomer; wherein the first monomer is selected from acrylamide compounds, (meth)acrylate compounds, polyolefin compounds and any combinations thereof; and wherein the second monomer is selected from an azo initiator containing an ethylenically unsaturated group. The modified styrene-butadiene rubber of the present application has a high grafting rate, and during the preparation of the bitumen waterproofing membrane, the polymeric chain segment of the second monomer in the modified styrene-butadiene rubber can continue to promote the cross-linking reaction between the functional groups on the polymeric chain segment of the first monomer and other modifiers containing ethylenically unsaturated groups, thus resulting in good ageing resistance.
Description
MODIFIED STYRENE-BUTADIENE RUBBER AND THE PROCESS FOR
PREPARING THE SAME AND BITUMEN WATERPROOFING MEMBRANE
[0001] The present application belongs to the field of SBR modification technology and specifically relates to a modified SBR, the process for preparing the same and a bitumen waterproofing membrane.
[0002] Styrene-butadiene rubber (SBR) consists of a hard segment (a polystyrene segment having high Tg) and a soft segment (a polybutadiene segment having low Tg) with a high softening point and low-temperature flexibility, and is commonly used in bitumen waterproofing membranes, tyres, wires and cables, hoses, medical appliances and other applications.
[0003] However, in the field of bitumen waterproofing membranes, although SBR has a good effect in the early stage, due to the polarity difference between SBR and asphalt, it is easy to separate from asphalt in the later ageing process, making the effect of SBR reduced or lost, which in turn leads to the poor ageing resistance of bitumen waterproofing membranes. The existing methods to improve the performance of bitumen waterproofing membrane through SBR include the following two aspects: on the one hand, physical methods such as adding compatibilizers, plasticizers or other stabilizers to enhance the compatibility of SBR and asphalt, but the above methods are short-lived and do not have the effect of ageing resistance; on the other hand, methods such as hydrogenation of SBR or chemical grafting of functional groups can be used to improve the compatibility of SBR and asphalt, however, the grafting rate of the above-mentioned chemical methods is low, the residual content of double bonds is high, and the functional groups cannot effectively play their roles, which limits the application of SBR. 1
[0004] In view of the above problems, the present application provides a modified styrene- butadiene rubber and a process for preparing the same and bitumen waterproofing membrane, aiming to solve the problems of low grafting rate of polar groups of the modified styrene-butadiene rubber and the poor ageing resistance of the bitumen waterproofing membrane.
[0005] In a first aspect, the present application provide a modified styrene-butadiene rubber comprising: a styrene-butadiene rubber matrix; and a modified polymer bound to at least part of the surface of the styrene-butadiene rubber matrix, wherein the modified polymer comprises a polymeric chain segment of a first monomer and a polymeric chain segment of a second monomer; wherein the first monomer is selected from acrylamide compounds, (methacrylate compounds, polyolefin compounds and any combinations thereof; and wherein the second monomer is selected from an azo initiator containing an ethylenically unsaturated group.
[0006] In the embodiments according to the first aspect of the present application, the modified polymer further comprises a structural unit of chain transfer agent.
[0007] In the embodiments according to the first aspect of the present application, the acrylamide compound is selected from one or more of diacetone acrylamide, N-(2- hydroxyethyl)acrylamide, N-hydroxymethylacrylamide, N,N-methylenebisacrylamide and methacrylamide.
[0008] In the embodiments according to the first aspect of the present application, the (meth)acrylate compound is selected from one or more of 2-hydroxyethyl acrylate, 2- hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and hydroxypropyl acrylate.
[0009] In the embodiments according to the first aspect of the present application, the polyolefin compound is selected from divinylbenzene and/or trivinylbenzene.
[0010] In the embodiments according to the first aspect of the present application, the azo initiator containing an ethylenically unsaturated group is an azo initiator containing a (meth)acrylate functional group; preferably, the azo initiator containing a (meth)acrylate 2 functional group is selected from esterification product of 4,4'-azobis(4-cyanovaleric acid) with 2-hydroxyethyl acrylate, and/or esterification product of 4,4'-azobis(4-cyanovaleric acid) with 2-hydroxypropyl acrylate.
[0011] In the embodiments according to the first aspect of the present application, the chain transfer agent is a chain transfer agent for reversible addition-fragmentation chain transfer radical polymerization.
[0012] In the embodiments according to the first aspect of the present application, the chain transfer agent is selected from one or more of 2-(dodecylsulfanylthiocarbonyl)sulfanyl-2- methylpropanoic acid, s,s'-bis(a-hydroxyethyl dimethylacetate) trithiocarbonate, 4-cyano- 4-(dodecylsulfanylthiocarbonyl)sulfanyl pentanoic acid and (4-cyanopentanoic acid) trithioacetate.
[0013] In a second aspect, the present application provide a process for preparing the modified styrene-butadiene rubber, comprising: adding the chain transfer agent, the first monomer and a thermal initiator to the styrene- butadiene rubber dissolved in a good solvent under inert atmosphere, stirring well and heating to reflux to obtain a first product; and adding the second monomer and photoinitiator to the first product dissolved in a good solvent under inert atmosphere to perform photoinitiated polymerization grafting to obtain the modified styrene-butadiene rubber.
[0014] In the embodiments according to the second aspect of the present application, the good solvent is selected from one or more of dichloromethane, cyclohexane, hexane, xylene and petroleum ether.
[0015] In the embodiments according to the first aspect of the present application, the thermal initiator is selected from azo initiators and/or organic peroxide initiators.
[0016] In the embodiments according to the first aspect of the present application, the thermal initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile and benzoyl peroxide.
[0017] In the embodiments according to the first aspect of the present application, the photoinitiator is selected from one or more of 2-hydroxy-2-methylpropiophenone, 1- hydroxycyclohexyl phenyl ketone, methyl 2-benzoylbenzoate and 2-methyl-1-(4- methylthiophenyl)-2-morpholinyl-1-propanone. 3
[0018] In a third aspect, the present application further provides a bitumen waterproofing membrane comprising the modified styrene-butadiene rubber according to the first aspect or modified styrene-butadiene rubber prepared by the process according to the second aspect.
[0019] Compared to the prior art, the present application has at least the following beneficial effects: (1) The modified SBR provided in the present application has a high grafting rate, and during the preparation of the bitumen waterproofing membrane, the polymeric chain segment of the second monomer in the modified SBR can continue to promote the cross- linking reaction between the functional groups on the polymeric chain segment of the first monomer and other modifiers containing ethylenically unsaturated groups, and the cross- linked network formed can wrap the other components, thereby delaying the ageing process of the waterproofing membrane.
[0020] The modified styrene-butadiene rubber of the present application is based on styrene-butadiene rubber as the main body and is obtained by "living" controlled free radical polymerization, such as reversible addition-fragmentation chain transfer polymerization (RAFT), by introducing a polymeric chain segment of a first monomer and a polymeric chain segment of a second monomer into the styrene-butadiene rubber chain segment. In the above "living" controlled polymerization process, the first monomer undergoes free radical polymerization in the presence of the SBR and the chain transfer agent, initiated by a thermal initiator, and forms with the chain transfer a polymerized chain segment capped by the chain transfer agent (SBR-polymeric chain segment of first monomer-chain transfer agent). Due to that the chain transfer agent attached to the end of such polymeric chain segment, the radical as a chain growth center is less likely to undergo irreversible bimolecular termination and instead forms a dormant intermediate. The dormant intermediate, even if deactivated after washing, can still be activated under certain conditions (e.g. by the action of a photoinitiator) to form a radical active center, which continues the chain growth reaction with the subsequent addition of a second monomer, forming a polymeric chain segment of the second monomer on the basis of the polymeric chain segment of the first monomer.
[0021] By the above process, a modified styrene-butadiene rubber having a higher grafting rate can be obtained, and the modified styrene-butadiene rubber can continue to trigger 4 cross-linking during the preparation process of bitumen waterproofing membrane, with other components to form a more compact cross-linked network structure, improving the anti-ageing performance of bitumen waterproofing membrane. (2) The application provides a simple, time-consuming and low-equipment requirement for the preparation of modified styrene-butadiene rubber, which is compatible with existing processes and has great potential for large-scale application.
[0022] In order to make the purpose, technical solutions and advantages of the present application clearer, the application will be described in further detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application, but not to limit the present application.
[0023] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
Additionally, within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.
[0024] In the description herein, it should be noted that, unless otherwise stated, the recitation of numerical ranges by "no less than" and "no more than" include all numbers within that range including the endpoints, and the recitation of “more” in the phrase “one or more” includes two or more.
[0025] The above summary of the present application is not intended to describe each and every disclosed embodiment implementation in this application. The following description illustrates exemplary embodiments more specifically. In many places throughout the application, guidance is provided through a series of examples, which can be used in various combinations. In each instance, the enumeration is only a representative group and should not be interpreted as exhaustive. 5
[0026] Existing modified SBRs suffer from the following disadvantages: low monomer utilization, high double bond residues in graft-modified SBRs and low grafting efficiency of modified SBRs. Based on this, the inventors have conducted extensive research and found that the grafting rate of modified SBR can be improved by introducing block-type polymeric chain segments into conventional SBR chain segments by means of "living" controlled radical polymerization, such as RAFT.
[0027] Modified styrene-butadiene rubber
[0028] In a first aspect, the present application provides a modified styrene-butadiene rubber comprising a styrene-butadiene rubber matrix; and a modified polymer bound to at least part of the surface of the styrene-butadiene rubber matrix, wherein the modified polymer comprises a polymeric chain segment of a first monomer and a polymeric chain segment of a second monomer; wherein the first monomer is selected from acrylamide compounds, (meth)acrylate compounds, polyolefin compounds and any combinations thereof; and wherein the second monomer is selected from an azo initiator containing an ethylenically unsaturated group.
[0029] According to the embodiments of the present application, the modified styrene- butadiene rubber is obtained by introducing the polymeric chain segment of the first monomer and the polymeric chain segment of the second monomer into the chain segments of a conventional styrene-butadiene rubber matrix by means of a "living" controlled radical polymerization, such as RAFT, into the main body of the styrene-butadiene rubber matrix.
[0030] According to the embodiments of the present application, the above-mentioned styrene-butadiene rubber matrix has a volatile fraction of < 0.8%, a combined styrene content of 20-25%, a tensile strength of 26-30 MPa and an elongation at break of 400-500%.
[0031] According to embodiments of the present application, the free radicals in the above
RAFT process can continuously participate in the reaction and initiate the polymerization of SBR and monomer, so that modified SBR having a high grafting rate can be obtained, which can be widely used in products such as waterproofing rolls, tyres, wires and cables, hoses, medical appliances, etc.
[0032] According to the embodiments of the present application, during the synthesis of the above products, the functional group on the polymeric chain segment of the second 6 monomer in the modified styrene-butadiene rubber can continue to trigger cross-linking with other components in the products, forming a more compact cross-linked network structure, further enhancing the ageing resistance of the products. In addition, the modified styrene-butadiene rubber produces no significant irritating odor during both preparation and application, in line with the concept of green environmental protection.
[0033] In some embodiments, the modified polymer may further comprise a structural unit of chain transfer agent.
[0034] According to the embodiments of the present application, the chain transfer agent enables a degenerative transfer between the growth radical and the chain transfer agent, thereby reducing the concentration of radicals and lowering the probability of bimolecular termination, and the chain transfer radical can continue to initiate the polymerization of the
SBR chain segments and monomers without continuing the polymerization on the same polymeric chain segment, resulting in a controllable molecular mass of the polymer and improved grafting efficiency.
[0035] In some embodiments, the acrylamide compound may be selected from one or more of diacetone acrylamide, N-(2-hydroxyethyl)acrylamide, N-hydroxymethyl acrylamide,
N,N-methylenebisacrylamide and methacrylamide. For example, the acrylamide compound may be diacetone acrylamide, or N-hydroxymethyl acrylamide, or a mixture consisting of
N-(2-hydroxyethyl)acrylamide and N-hydroxymethyl acrylamide. The acrylamide compound may also be any one or any combination of the above compounds.
[0036] In some embodiments, the (meth)acrylate compound may be selected from one or more of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and hydroxypropyl acrylate. For example, the (meth)acrylate compound may be 2-hydroxyethyl acrylate, or 2-hydroxypropyl methacrylate, or a mixture consisting of 2- hydroxypropyl methacrylate and hydroxypropyl acrylate. The (meth)acrylate compound may be any one or any combination of the above (meth)acrylate compounds.
[0037] In some embodiments, the polyolefin compound may be selected from divinylbenzene and/or trivinylbenzene.
[0038] According to embodiments of the present application, the acrylamide compound, the (meth)acrylate compound and the polyolefin compound all contain unsaturated double bonds. In the presence of a thermal initiator, the double bonds in the molecules of the above 7 compound monomers are opened and grafted to the chain segments of butadiene rubber, bound to at least part of the surface of the butadiene rubber matrix.
[0039] In some embodiments, the azo initiator containing an ethylenically unsaturated group may be an azo initiator containing a (meth)acrylate functional group. 10040] According to the embodiments of the present application, the azo initiator containing a (meth)acrylate functional group contains an unsaturated double bond that can be grafted and a functional group that can initiate a cross-linking reaction, so that the azo initiator with a (meth)acrylate functional group can be grafted onto the first monomer-modified styrene- butadiene rubber in the presence of a photoinitiator and provides a good basis for initiating the cross-linking reaction between the components in subsequent modified SBR products.
[0041] In some embodiments, the azo initiator containing a (meth)acrylate functional group may be selected from the esterification product of 4,4'-azobis(4-cyanovaleric acid) with 2- hydroxyethyl acrylate (ACVA-HEA), and/or the esterification product of 4,4'-azobis(4- cyanovaleric acid) with 2-hydroxypropyl acrylate (ACVA-HPA).
[0042] In some embodiments, the chain transfer agent is a chain transfer agent for the reversible addition-fragmentation chain transfer radical polymerization.
[0043] According to the embodiments of the present application, the chain transfer agent for reversible addition-fragmentation chain transfer radical polymerization may form a dormant intermediate by a chain transfer reaction of chain growth radicals, first bound to the end of the polymeric chain segment of the SBR-first monomer. Such dormant intermediate, even if deactivated after washing, can still be activated under certain conditions (e.g. in the presence of a photoinitiator) to form a radical active center to initiate a chain growth reaction with the subsequent addition of a second monomer to form a polymeric chain segment of the second monomer on the basis of the polymeric chain segment of the first monomer. As a result, the SBR can be grafted with the polymeric chain segment of the first monomer and the polymeric chain segment of the second monomer, resulting in a SBR modified by a block polymer. In addition, the presence of a chain transfer agent at the end of the block polymer segment of the modified SBR allows the chain growth reaction of other monomers to continue under certain conditions. Thus, one or more other monomers can be added in turn to form the corresponding polymeric chain segments, as required, resulting in a versatile modified SBR. 8
[0044] In some embodiments, the chain transfer agent is selected from one or more of 2- (dodecylsulfanylthiocarbonyl)sulfanyl-2-methylpropanoic acid, s,s'-bis(a-hydroxyethyl dimethylacetate) trithiocarbonate, 4-cyano-4-(dodecylsulfanylthiocarbonyl)sulfanyl pentanoic acid and (4-cyanopentanoic acid) trithioacetate. For example, the chain transfer agent may be 2-(dodecylsulfanylthiocarbonyl)sulfanyl-2-methylpropanoic acid and may be a mixture of 4-cyano-4-(dodecylsulfanylthiocarbonyl)sulfanyl pentanoic acid and (4- cyanopentanoic acid) trithioacetate. The chain transfer agent may be any one or any combination of the above chain transfer agents.
[0045] According to the embodiments of the present application, the above chain transfer agents can be used in reversible addition-fragmentation chain transfer radical polymerization, forming dormant intermediates with the chain growth radicals and limiting irreversible bimolecular termination side reactions between the growth chain radicals, allowing the polymerization reaction to be effectively controlled.
[0046] Process for preparing modified styrene-butadiene rubber
[0047] In a second aspect, the present application proposes a process for preparing the modified styrene-butadiene rubber, comprising:
S10, adding the chain transfer agent, the first monomer and a thermal initiator to the styrene-butadiene rubber dissolved in a good solvent under inert atmosphere, stirring well and heating to reflux to obtain a first product;
S20, adding the second monomer and photoinitiator to the first product dissolved in a good solvent under inert atmosphere to perform photoinitiated polymerization grafting to obtain the modified styrene-butadiene rubber.
[0048] In some embodiments, the above step S10 further comprises:
S100, continuously injecting an inert gas into the reactor, adding the styrene- butadiene rubber to the reactor and dissolving it in a good solvent, adding the chain transfer agent, the first monomer and the thermal initiator and stirring at room temperature for 20- min until uniformly dispersed;
S110, placing the reactor in an oil bath at 80°C and heating to reflux for 2-4 h; at the end of the reaction, placing the reactor in ice water to stop the thermal reaction; 30 S120, adding hexane and good solvent for washing, repeating 2-3 times and drying the product in an oven at 8°C for 3-4 h to obtain the first product.
[0049] In some embodiments, the above step S20 further comprises: 9
S200, continuously injecting an inert gas into the reactor, adding the first product to the reactor and dissolving it in a good solvent, adding the second monomer and the photoinitiator and stirring at room temperature for 0.5-1 h until well dispersed;
S210, initiating the polymerization reaction with UV light at a wavelength of 360- 400 nm for 2-3 h;
S220, adding hexane and good solvent for washing, repeating 2-3 times and drying the product in an oven at 40°C for 3-4 h to obtain modified styrene-butadiene rubber.
[0050] According to the embodiments of the present application, in step S10, under high temperature conditions, the thermal initiator decomposes to produce free radicals, which initiate the polymerization of SBR and the first monomer to realize the grafting of the first monomer polymerization chain segment to SBR, and at the same time to produce SBR-first monomer chain segment free radicals, which react with the chain transfer agent to form dormant intermediates. The dormant intermediate is less stable and can be cleaved by itself, releasing new reactive radicals from the corresponding sulphur atoms, which will re-initiate the polymerization of the SBR and the first monomer, thus repeating the above grafting process and finally obtaining the first product.
[0051] The chain transfer agent reduces the concentration of free radicals and chain transfers the active free radicals instead of continuing the polymerization on the same polymeric chain segment, thereby reducing the probability of bimolecular termination and increasing the grafting efficiency.
[0052] In step S20, under the irradiation of UV light, the photoinitiator decomposes to produce a free radical which activates the chain transfer agent dormant at the end of the chain segment of the first product and produces a new active radical which initiates the polymerization of the first product and the second monomer to produce a polymeric chain segment of the second monomer on the basis of the polymeric chain segment of the first monomer, completing the grafting of the second monomer. In step S20, it is not necessary to add an additional chain transfer agent, since the chain transfer agent attached to the end of the chain segment of the first monomer in the S10 reaction can still be activated and continue to participate in the reaction in step S20.
[0053] According to the embodiments of the present application, oxygen needs to be removed from the reactor prior to the reaction in order to prevent oxygen from creating an
Inhibition and affecting the grafting rate of the monomers. 10
[0054] According to the embodiments of the present application, refluxing for 2-4 h in step
S110 allows sufficient grafting of the SBR and the first monomer. If the reflux time 1s less than 2 h, it will result in a lower grafting rate of the first monomer; a shorter polymerization time in step S210 will result in a lower grafting rate of the second monomer.
[0055] According to the embodiments of the present application, the washing in step S120 removes the unsuccessfully grafted styrene-butadiene rubber, the residual first monomer, and the washing in step S220 removes the unsuccessfully grafted first product, the residual second monomer.
[0056] In some embodiments, the S20 step should be completed under light-proof conditions prior to photoinitiated polymerization in order to prevent premature decomposition and loss of activity of the photoinitiator.
[0057] In some embodiments, the good solvent may be selected from one or more of dichloromethane, cyclohexane, hexane, xylene and petroleum ether.
[0058] According to the embodiments of the present application, the styrene-butadiene rubber and the first product have good dispersion and compatibility in the above-mentioned good solvents.
[0059] In some embodiments, the thermal initiator may be selected from azo initiators and/or organic peroxide initiators, preferably, the thermal initiator may be selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile and benzoyl peroxide.
[0060] In some embodiments, the photoinitiator may be selected from one or more of 2- hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, methyl 2- benzoylbenzoate and 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone. For example, the photoinitiator may be 2-hydroxy-2-methylpropiophenone, or 2-methyl-1-(4- (methylthiophenyl)-2-morpholinyl-1-propanone, or a mixture of 2-hydroxy-2- methylpropiophenone and 1-hydroxycyclohexyl phenyl ketone. The photoinitiator may be any one or any combination of the above photoinitiators.
[0061] The process for preparing the modified styrene-butadiene rubber provided in the present application is simple, time-consuming, requires low equipment requirements, is well compatible with existing processes and has great potential for large-scale application.
[0062] Bitumen waterproofing membrane
[0063] The present application proposes in a third aspect a bitumen waterproofing membrane comprising the modified styrene-butadiene rubber according to the first aspect 11 or the modified styrene-butadiene rubber prepared by the process according to the second aspect.
[0064] The modified styrene-butadiene rubber provided in the present application has a high grafting rate and an initiating effect, which allows the modified styrene-butadiene rubber to be cross-linked with other components during the preparation of the bitumen waterproofing membrane, resulting in a cross-linked network structure, which in turn gives the bitumen waterproofing membrane good ageing resistance. Therefore, compared with conventional
SBR, the modified SBR provided in the present application has a broader application prospect.
[0065] Examples
[0066] The following examples describe the disclosure of the present application in more detail and are provided for illustrative purposes only, as various modifications and changes within the scope of the disclosure of the present application will be apparent to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios described in the following embodiments are based on weight, all reagents used in the embodiments are commercially available or synthesized according to conventional methods and can be directly used without further treatment, and all instruments used in the embodiments are commercially available.
[0067] Example 1
[0068] Modified SBR: 100 g of SBR was dissolved in 300 mL of methylene chloride under inert atmosphere, and 2 g of 4-cyano-4-(dodecylsulfanylthiocarbonyl)sulfanyl pentanoic acid, 15 g of diacetone acrylamide and 5 g of azobisisobutyronitrile were added, and stirred for 20 min at room temperature. The reactor was placed in an oil bath at 80°C to reflux for 4 h. At the end of the reaction, the reactor was placed in ice water to stop the thermal reaction. 4-5 times (volume) of n-hexane were added and stirred for 6 h, standing for 2 h. The upper layer of clarified liquid was poured off to remove the ungrafted styrene-butadiene rubber, the residual first monomer and the thermal initiator, then dissolved with excess dichloromethane, repeating the washing three times and drying the product in an oven at 80°C for 4 h to obtain the first product;
[0069] 80 g of the first product was added to the reactor and dissolved in 300 mL of dichloromethane, stirred for 2 h. 15 g of ACVA-HPA and 3 g of 2-hydroxy-2- methylpropiophenone were added and stirred for 0.5 h at room temperature until well 12 dispersed. The polymerization reaction was initiated with UV light at 365 nm for 2 h. 4-5 times (volume) of n-hexane were added and stirred for 6 h, standing for 2 h. The upper layer of clarified liquid was poured off to remove the ungrafted first product, the residual second monomer and photoinitiator, and then dissolved with excess dichloromethane, repeating the washing 3 times, and then the product was placed in the oven at 40°C and dried for 4h to obtain modified styrene-butadiene rubber.
[0070] Bitumen waterproofing membrane: 50g 70# asphalt, 10g styrene-butadiene-styrene block copolymer, 15g modified styrene-butadiene rubber from Example 1, 20g flame retardant filler (zinc borate HT-207, from Jinan Taixing), 3.5g diisopropyl peroxide, 18g fumed silica, 2g 3-aminopropyltriethoxysilane, 3g Tiangang ® HS-200 (BASF 2020) and 1g of antioxidant 1330 were placed in a mixing tank, stirred and mixed. The above mixture was extruded, molded, cooled, to obtain bitumen waterproofing membrane.
[0071] Example 2
[0072] Modified SBR: 90 g of SBR was dissolved in 250 mL of dichloromethane under inert atmosphere, and 1.5 g of 2-(dodecylsulfanylthiocarbonyl)sulfanyl-2-methylpropanoic acid, 13 g of diacetone acrylamide and 4 g of azobisisoheptonitrile were added, and stirred for 20 min at room temperature; the reactor was placed in an oil bath at 80°C and heated to reflux for 3 h. At the end of the reaction, the reactor was placed in ice water to stop the thermal reaction. 4-5 times (volume) of n-hexane were added and stirred for 6 h, standing for 2 h. The upper layer of the clarified liquid was poured off to remove the ungrafted butadiene rubber, residual first monomer and thermal initiator, then dissolved with excess dichloromethane, repeating the washing three times and drying the product in an oven at 80°C for 4 h to obtain the first product;
[0073] 70 g of the first product was added to the reactor and dissolved in 300 mL of dichloromethane, stirred for 1.5 h. 13 g of ACVA-HPA and 2.5 g of methyl 2- benzoylbenzoate were added and stirred for 0.5 h at room temperature until well dispersed.
The polymerization reaction was initiated with UV light at 400 nm for 2 h. 4-5 times (volume) of n-hexane were added and stirred for 6 h, standing for 2 h. The upper layer of clarified liquid was poured off to remove the ungrafted first product, the residual second monomer and photoinitiator, and then dissolved with excess dichloromethane, repeating the washing 3 times, and then the product was placed in the oven at 40°C and dried for 4h to obtain modified styrene-butadiene rubber. 13
[0074] Bitumen waterproofing membrane: the bitumen waterproofing membrane was similar to that in Example 1, except that the modified styrene-butadiene rubber obtained in
Example 2 was used.
[0075] Example 3
[0076] Modified SBR: 95 g of SBR was dissolved in 250 mL of dichloromethane under inert atmosphere and 2 g of (4-cyanovaleric acid) trithioacetate, 14 g of diacetone acrylamide and 4.5 g of benzoyl peroxide were added and stirred for 20 min at room temperature; the reactor was placed in an oil bath at 80°C and heated to reflux for 3.5 h. At the end of the reaction, the reactor was placed in ice water to stop the thermal reaction. 4-5 times (volume) of n-hexane were added and stirred for 6 h, standing for 2 h. The upper layer of the clarified liquid was poured off to remove the ungrafted butadiene rubber, residual first monomer and thermal initiator, then dissolved with excess dichloromethane, repeating the washing three times and drying the product in an oven at 80°C for 4 h to obtain the first product;
[0077] 75 g of the first product was added to the reactor and dissolved in 300 mL of dichloromethane, stirred for 2 h. 14 g of ACVA-HEA and 2.6 g of 2-methyl-1-(4- methylthiophenyl)-2-morpholinyl-1-propanone were added and stirred for 0.5 h at room temperature until well dispersed. The polymerization reaction was initiated with UV light at 400 nm for 2 h. 4-5 times (volume) of n-hexane were added and stirred for 6 h, standing for 2 h. The upper layer of clarified liquid was poured off to remove the ungrafted first product, the residual second monomer and photoinitiator, and then dissolved with excess dichloromethane, repeating the washing 3 times, and then the product was placed in the oven at 40°C and dried for 4h to obtain modified styrene-butadiene rubber.
[0078] Bitumen waterproofing membrane: the bitumen waterproofing membrane was similar to that in Example 1, except that the modified styrene-butadiene rubber obtained in
Example 3 was used.
[0079] Example 4
[0080] Modified SBR: 95 g of SBR was dissolved in 250 mL of cyclohexane under inert atmosphere and 2 g of (4-cyanovaleric acid) trithioacetate, 14 g of 2-hydroxyethyl acrylate and 4.5 g of benzoyl peroxide were added and stirred for 20 min at room temperature; the reactor was placed in an oil bath at 80°C and heated to reflux for 3.5 h. At the end of the reaction, the reactor was placed in ice water to stop the thermal reaction. 4-5 times (volume) 14 of n-hexane were added and stirred for 6 h, standing for 2 h. The upper layer of the clarified liquid was poured off to remove the ungrafted butadiene rubber, residual first monomer and thermal initiator, then dissolved with excess dichloromethane, repeating the washing three times and drying the product in an oven at 80°C for 4 h to obtain the first product;
[0081] 75 g of the first product was added to the reactor and dissolved in 300 mL of cyclohexane, stirred for 2 h. 14 g of ACVA-HEA and 2.6 g of 2-methyl-1-(4- methylthiophenyl)-2-morpholinyl-1-propanone were added and stirred for 0.5 h at room temperature until well dispersed. The polymerization reaction was initiated with UV light at 380 nm for 2 h. 4-5 times (volume) of n-hexane were added and stirred for 6 h, standing for 2 h. The upper layer of clarified liquid was poured off to remove the ungrafted first product, the residual second monomer and photoinitiator, and then dissolved with excess cyclohexane, repeating the washing 3 times, and then the product was placed in the oven at 40°C and dried for 4h to obtain modified styrene-butadiene rubber.
[0082] Bitumen waterproofing membrane: the bitumen waterproofing membrane was similar to that in Example 1, except that the modified styrene-butadiene rubber obtained in
Example 4 was used.
[0083] Example 5
[0084] Modified SBR: 100 g of SBR was dissolved in 250 mL of xylene under inert atmosphere and 2 g of s,s'-bis(a-hydroxyethyl dimethylacetate)trithiocarbonate, 15 g of divinylbenzene and 5 g of azobisisobutyronitrile were added and stirred for 20 min at room temperature; the reactor was placed in an oil bath at 80°C and heated to reflux for 3.5 h. At the end of the reaction, the reactor was placed in ice water to stop the thermal reaction. 4-5 times (volume) of n-hexane were added and stirred for 6 h, standing for 2 h. The upper layer of the clarified liquid was poured off to remove the ungrafted butadiene rubber, residual first monomer and thermal initiator, then dissolved with excess dichloromethane, repeating the washing three times and drying the product in an oven at 80°C for 4 h to obtain the first product;
[0085] 80 g of the first product was added to the reactor and dissolved in 300 mL of xylene, stirred for 2 h. 15 g of ACVA-HPA and 3 g of methyl 2-benzoylbenzoate were added and stirred for 0.5 h at room temperature until well dispersed. The polymerization reaction was initiated with UV light at 360 nm for 2 h. 4-5 times (volume) of n-hexane were added and stirred for 6 h, standing for 2 h. The upper layer of clarified liquid was poured off to remove 15 the ungrafted first product, the residual second monomer and photoinitiator, and then dissolved with excess xylene, repeating the washing 3 times, and then the product was placed in the oven at 40°C and dried for 4h to obtain modified styrene-butadiene rubber.
[0086] Bitumen waterproofing membrane: the bitumen waterproofing membrane was similar to that in Example 1, except that the modified styrene-butadiene rubber obtained in
Example 5 was used.
[0087] Comparative Example
[0088] Comparative Example 1
[0089] Modified SBR: 100 g of SBR was dissolved in 300 mL of methylene chloride under inert atmosphere, and 2 g of 4-cyano-4-(dodecylsulfanylthiocarbonyl)sulfanyl pentanoic acid, 15 g of diacetone acrylamide and 5 g of azobisisobutyronitrile were added, and stirred for 20 min at room temperature. The reactor was placed in an oil bath at 80°C to reflux for 2 h. Atthe end of the reaction, the reactor was placed in ice water to stop the thermal reaction. 4-5 times (volume) of n-hexane were added and stirred for 6 h, standing for 2 h. The upper layer of clarified liquid was poured off to remove the ungrafted styrene-butadiene rubber, the residual first monomer and the thermal initiator, then dissolved with excess dichloromethane, repeating the washing three times and drying the product in an oven at 80°C for 4 h to obtain the first product;
[0090] 80 g of the first product was added to the reactor and dissolved in 300 mL of dichloromethane, stirred for 2 h. 15 g of ACVA-HPA and 3 g of 2-hydroxy-2- methylpropiophenone were added and stirred for 0.5 h at room temperature until well dispersed. The polymerization reaction was initiated with UV light at 365 nm for 1.5 h. 4-5 times (volume) of n-hexane were added and stirred for 6 h, standing for 2 h. The upper layer of clarified liquid was poured off to remove the ungrafted first product, the residual second monomer and photoinitiator, and then dissolved with excess dichloromethane, repeating the washing 3 times, and then the product was placed in the oven at 40°C and dried for 4h to obtain modified styrene-butadiene rubber.
[0091] Bitumen waterproofing membrane: the bitumen waterproofing membrane was similar to that in Example 1, except that the modified styrene-butadiene rubber obtained in
Comparative Example 1 was used.
[0092] Comparative Example 2 16
[0093] Modified SBR: 100 g of SBR was dissolved in 300 mL of dichloromethane under inert atmosphere, 15 g of diacetone acrylamide and 5 g of azobisisobutyronitrile were added, and stirred for 20 min at room temperature; the reactor was placed in an oil bath at 80°C and heated to reflux for 4 h. At the end of the reaction, the reactor was placed in ice water to stop the thermal reaction. 4-5 times (volume) of n-hexane were added and stirred for 6 h, standing for 2 h. The upper layer of the clarified liquid was poured off to remove the ungrafted butadiene rubber, residual first monomer and thermal initiator, then dissolved with excess dichloromethane, repeating the washing three times and drying the product in an oven at 80°C for 4 h to obtain the first product;
[0094] 80 g of the first product was added to the reactor and dissolved in 300 mL of dichloromethane, stirred for 2 h. 15 g of ACVA-HPA and 3 g of 2-hydroxy-2- methylpropiophenone were added and stirred for 0.5 h at room temperature until well dispersed. The polymerization reaction was initiated with UV light at 365 nm for 2 h. 4-5 times (volume) of n-hexane were added and stirred for 6 h, standing for 2 h. The upper layer of clarified liquid was poured off to remove the ungrafted first product, the residual second monomer and photoinitiator, and then dissolved with excess dichloromethane, repeating the washing 3 times, and then the product was placed in the oven at 40°C and dried for 4h to obtain modified styrene-butadiene rubber.
[0095] Bitumen waterproofing membrane: the bitumen waterproofing membrane was similar to that in Example 1, except that the modified styrene-butadiene rubber obtained in
Comparative Example 2 was used.
[0096] Comparative Example 3
[0097] Modified SBR: 100 g of SBR was dissolved in 300 mL of dichloromethane under inert atmosphere and 2 g of 4-cyano-4-(dodecylsulfanylthiocarbonyl)sulfanyl pentanoic acid, 15 g of diacetone acrylamide and 5 g of azobisisobutyronitrile were added and stirred for 20 min at room temperature; the reactor was placed in an oil bath at 80°C and heated to reflux for 4 h. At the end of the reaction, the reactor was placed in ice water to stop the thermal reaction. 4-5 times (volume) of n-hexane were added and stirred for 6 h, standing for 2 h. The upper layer of the clarified liquid was poured off to remove the ungrafted butadiene rubber, residual monomer and thermal initiator, then dissolved with excess dichloromethane, repeating the washing three times and drying the product in an oven at 80°C for 4 h to obtain modified styrene-butadiene rubber. 17
[0098] Bitumen waterproofing membrane: the bitumen waterproofing membrane was similar to that in Example 1, except that the modified styrene-butadiene rubber obtained in
Comparative Example 3 was used.
[0099] Test section 100100] Determination of grafting rate: the grafting rate of SBR can be determined by using nuclear magnetic resonance hydrogen spectroscopy (NMR), using trimellitate as an external standard reagent (not involved in the reaction in the system), taking 0.2mL of the liquids mixed well before and after the reaction, respectively, dissolving with the corresponding deuterium reagent, followed by NMR testing, using the integral area at the H position of the trimellitate structure as a benchmark, observing the change in the integrated area at the H position of the double bond in the functional monomer, and the corresponding grafting rate can be calculated by:
[00101] Grafting rate = (S1-S2)/S1 x 100% in which Si is the area of the peak at the H-position of the double bond before the reaction and S» is the area of the peak at the H-position of the double bond after the reaction.
[00102] Referring to the standard GB 23441-2009, bitumen waterproofing membrane was measured for thermal ageing test at 70°C, tracking the limit of low temperature flexibility and peel strength failure days of the membrane, with 7 days as a test cycle for determination.
[00103] The modified styrene-butadiene rubber and bitumen waterproofing membrane from the above-mentioned Examples 1-5 and Comparative Examples 1-3 were tested for relevant performance, and the results were shown in Table 1 below.
[00104] Table 1 Results of the performance tests for the modified styrene-butadiene rubber of Example 1 to 5 and Comparative Example 1 to 3
Grafting rate of moditied styrene- 93 92 91 72 58 butadiene rubber (%)
Ageing resistance of 21days | 28 days | 21 days | 21 days | 28 days | 14 days 7 days 14 days waterproofing pass pass pass pass pass pass pass pass membrane
[00105] From the above grafting rates of the modified SBR, it can be seen that the grafting rate of the modified SBR prepared in Examples 1 to 5 was higher than 89%, indicating that the grafting efficiency of the modified SBR can be sufficiently improved by the RAFT two- 18 step grafting method in the present application. In contrast, as can be seen from Comparative
Example 1, the shorter grafting time of the monomer lead to a lower grafting efficiency of the modified SBR. The modified styrene-butadiene rubber obtained by conventional radical polymerization in Comparative Example 2 had a significantly lower grafting rate compared to Examples 1-5, which further shown the advantages of such RAFT polymerization.
Compared to Example 1, the modification in Comparative Example 3 was only done by first functional monomer, resulting in a higher grafting rate as both using RAFT polymerization.
In addition, the modified styrene-butadiene rubber of Examples 1 to 5 was safe and environmentally friendly as no significant irritating odors were generated during the preparation process.
[00106] As can be seen from the ageing resistance of the bitumen waterproofing membrane, the bitumen waterproofing membrane of Examples 1 to 5 had good ageing performance, because during the later high-temperature modification process the modified styrene- butadiene rubber grafted monomer chain segment can crosslink with and polymer modifiers containing unsaturated double bond such as with styrene-butadiene-styrene block copolymer, forming a three-dimensional cross-linked network structure. The network structure can wrap around lighter components of the asphalt such as saturated and aromatic components, thus improving the performance of the waterproofing membrane. In both
Comparative Example 1 and Comparative Example 2, the modified styrene-butadiene rubber did not form a cross-linked structure with the other components or the cross-linked structure was small, resulting in poor ageing resistance of the bitumen waterproofing membrane. In contrast, in Comparative Example 3, despite the high grafting rate of the first functional monomer, there was a gap in the degree of cross-linking compared to Example 1 in the later stages of the SBR-modified bitumen waterproofing membrane due to the absence of the introduction of a second functional monomer that can trigger the cross-linking reaction, and therefore the ageing resistance was poorer.
[00107] In summary, by using RAFT the present application introduced the polymeric chain segment of the first monomer and the polymeric chain segment of the second monomer into the SBR chain segment, thus a high grafting rate of modified SBR was obtained, and during the preparation of bitumen waterproofing membrane, the polymeric chain segment of the second monomer in the modified SBR can continue to promote the cross-linking reaction between the functional groups on the polymeric chain segment of the first monomer and 19 other modifiers containing ethylenically unsaturated groups, forming a more compact cross- linked network structure, further enhancing the ageing resistance of the bitumen waterproofing membrane.
[00108] The above mentioned descriptions only show particular implementations of the present application and but are not intended to limit the protection scope of the present application. Any modification or replacement readily figured out by a person skilled in the art within the technical scope disclosed in the present application shall fall within the protection scope of the present application. Therefore, the protection scope of the present application shall be determined by the protection scope of the claims.
Claims (10)
1. A modified styrene-butadiene rubber, comprising a styrene-butadiene rubber matrix; and a modified polymer bound to at least part of the surface of the styrene-butadiene rubber matrix, wherein the modified polymer comprises a polymeric chain segment of a first monomer and a polymeric chain segment of a second monomer; wherein the first monomer is selected from acrylamide compounds, (meth)acrylate compounds, polyolefin compounds and any combinations thereof; and wherein the second monomer is selected from an azo initiator containing an ethylenically unsaturated group.
2. The modified styrene-butadiene rubber according to claim 1, wherein the modified polymer further comprises a structural unit of chain transfer agent.
3. The modified styrene-butadiene rubber according to claim 1, wherein the acrylamide compound is selected from one or more of diacetone acrylamide, N-(2- hydroxyethyl)acrylamide, N-hydroxymethyl acrylamide, N,N-methylenebisacrylamide and methacrylamide; wherein the (meth)acrylate compound is selected from one or more of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and hydroxypropyl acrylate; and wherein the polyolefin compound is selected from divinylbenzene and/or trivinylbenzene.
4. The modified styrene-butadiene rubber according to claim 1, wherein the azo initiator containing an ethylenically unsaturated group is an azo initiator containing a (meth)acrylate functional group; preferably, the azo initiator containing a (meth)acrylate functional group is selected from esterification product of 4,4'-azobis(4-cyanovaleric acid) with 2-hydroxyethyl acrylate, and/or esterification product of 4,4'-azobis(4-cyanovaleric acid) with 2-hydroxypropyl acrylate.
5. The modified styrene-butadiene rubber according to claim 2, wherein the chain transfer agent is a chain transfer agent for reversible addition-fragmentation chain transfer radical polymerization.
6. The modified styrene-butadiene rubber according to claim 5, wherein the chain transfer agent is selected from one or more of 2-(dodecylsulfanylthiocarbonyl)sulfanyl-2- methylpropanoic acid, s,s'-bis(a-hydroxyethyl dimethylacetate) trithiocarbonate, 4-cyano- 21
4-(dodecylsulfanylthiocarbonyl)sulfanyl pentanoic acid and (4-cyanopentanoic acid) trithioacetate. 7, À process for preparing the modified styrene-butadiene rubber according to any one of claims 1-6, comprising adding the chain transfer agent, the first monomer and a thermal initiator to the styrene- butadiene rubber dissolved in a good solvent under inert atmosphere, stirring well and heating to reflux to obtain a first product; and adding the second monomer and photoinitiator to the first product dissolved in a good solvent under inert atmosphere to perform photoinitiated polymerization grafting to obtain the modified styrene-butadiene rubber.
8. The process according to claim 7, wherein the good solvent is selected from one or more of dichloromethane, cyclohexane, hexane, xylene and petroleum ether; and/or wherein the thermal initiator 1s selected from an azo initiator and/or an organic peroxide initiator; preferably, the thermal initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile and benzoyl peroxide.
9. The process according to claim 7, wherein the photoinitiator 1s selected from one or more of 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, methyl 2- benzoylbenzoate and 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone.
10. A bitumen waterproofing membrane, comprising the modified styrene-butadiene rubber according to any one of claims 1-6 or the modified styrene-butadiene rubber prepared by the process according to any one of claims 7-9. 22
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210617010.4A CN115124663B (en) | 2022-06-01 | 2022-06-01 | Modified styrene-butadiene rubber, preparation method thereof and asphalt waterproof coiled material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6136899A (en) * | 1999-09-14 | 2000-10-24 | The Goodyear Tire & Rubber Company | SBR for asphalt cement modification |
| KR101345217B1 (en) * | 2012-04-27 | 2013-12-27 | 부산대학교 산학협력단 | Novel hydrophilic chain transfer agent and end-modified styrene-butadiene copolymer using them |
| WO2020068955A1 (en) * | 2018-09-27 | 2020-04-02 | Basf Se | Latex styrene butadiene powders and asphalt composition comprising said powder |
| CN109929259B (en) * | 2019-04-17 | 2021-06-04 | 山东显元化工研究院有限公司 | SBR (styrene butadiene rubber) asphalt modifier and preparation method thereof |
| CN110003672B (en) * | 2019-04-17 | 2021-05-04 | 山东显元化工研究院有限公司 | SBR (styrene butadiene rubber) modified asphalt and preparation method thereof |
| CN113528018B (en) * | 2021-09-13 | 2021-11-26 | 科顺防水科技股份有限公司 | Coating material, preparation method thereof and coiled material |
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