CN117304373A - Modified styrene-butadiene-styrene block copolymer, preparation method thereof, modified asphalt and application thereof - Google Patents
Modified styrene-butadiene-styrene block copolymer, preparation method thereof, modified asphalt and application thereof Download PDFInfo
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- CN117304373A CN117304373A CN202311349794.8A CN202311349794A CN117304373A CN 117304373 A CN117304373 A CN 117304373A CN 202311349794 A CN202311349794 A CN 202311349794A CN 117304373 A CN117304373 A CN 117304373A
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- styrene
- butadiene
- modified
- block copolymer
- sbs
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- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 title claims abstract description 76
- 239000010426 asphalt Substances 0.000 title claims abstract description 38
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical class C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical group C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 2
- 238000005917 acylation reaction Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 229960003638 dopamine Drugs 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 238000010382 chemical cross-linking Methods 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 230000001172 regenerating effect Effects 0.000 abstract description 2
- 125000003368 amide group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 238000004448 titration Methods 0.000 description 12
- 239000012086 standard solution Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 6
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- AKPUJVVHYUHGKY-UHFFFAOYSA-N hydron;propan-2-ol;chloride Chemical compound Cl.CC(C)O AKPUJVVHYUHGKY-UHFFFAOYSA-N 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- -1 mercapto compound Chemical class 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012075 bio-oil Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004643 material aging Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007248 oxidative elimination reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/10—Acylation
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N5/00—Roofing materials comprising a fibrous web coated with bitumen or another polymer, e.g. pitch
- D06N5/003—Roofing materials comprising a fibrous web coated with bitumen or another polymer, e.g. pitch coated with bitumen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Textile Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a modified styrene-butadiene-styrene block copolymer, which can perform chemical crosslinking and hydrogen bonding with carboxyl and hydroxyl at the double bond of an oxidized butadiene unit by grafting an amide structure and a hydroxyl structure to the para position of a PS segment benzene ring of SBS, thereby playing the roles of self-repairing and regenerating. Meanwhile, the single bond in the butadiene unit is reserved, so that the low-temperature performance of the modified SBS is not obviously reduced. Therefore, the modified styrene-butadiene-styrene block copolymer is suitable for modifying asphalt, can not only improve the service time, but also not affect the low-temperature performance of coiled materials, and can be used for asphalt modification and recycling of asphalt recovery.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a modified styrene-butadiene-styrene block copolymer, a preparation method thereof and modified asphalt.
Background
Styrene-butadiene-styrene block copolymers (SBS) can be used to modify asphalt to improve its high/low temperature properties. Therefore, the SBS modified asphalt is widely applied to expressway construction. However, the SBS modified asphalt gradually deteriorates in performance due to the aging of the binder and the influence of ultraviolet rays, heat and oxygen.
The aging of base asphalt is that the asphalt is hardened as the asphalt volatilizes light components and the asphalt condenses during stirring, paving and use, which breaks the balance of asphalt colloid structure. Therefore, the regenerant containing high proportions of saturation and aromatic hydrocarbons can effectively restore its properties, for example, 15% of bio-oil extracted from waste wood can rebalance the aged asphalt compounds and improve its fatigue and crack resistance. However, common reclaimed oil can only rebalance the colloidal structure of the aged binder, but degraded SBS cannot be effectively utilized. This is because the crosslinked structure of the modifier SBS dominates the properties of the binder, however the crosslinked structure of the aged SBS modifier is not recovered by the usual physical blending regeneration process of adding the light component.
Therefore, the idea for solving the technical problems is as follows: 1. develop a modified SBS with good ageing resistance, which can prolong the service life of asphalt, 2. Reactivate the oxidative degradation SBS (or modified SBS).
However, the prior art modified SBS cannot fully solve the above technical problems, and chinese patent CN102391424a discloses a modification method of SBS block copolymers, in which by grafting a mercapto compound containing a functional group to the double bond of SBS, the risk of oxidative cleavage of the double bond is avoided, but the low temperature performance of these modified SBS is severely reduced due to reduction or even disappearance of the double bond. At the same time, these modified SBS also cannot be applied to recycling asphalt to reactivate the oxidatively broken SBS.
The researchers of the invention find that the regeneration of the aged SBS modified asphalt not only needs the recovery of the components of the aged binder, but also the repair of the crosslinked structure of the aged SBS modifier in the aged SBS modified asphalt is important. This is due to the fact that the unsaturated double bonds present in SBS (at the polybutadiene block) are easily oxidized during aging, which results in some broken fragments with reactive end groups (including carboxyl and hydroxyl groups). Thus, it is critical to be able to utilize these oxidative degradation groups.
Disclosure of Invention
The invention aims to overcome the technical defects and provide the modified SBS which can effectively prolong the service life of the SBS and does not obviously reduce the low-temperature performance. The modified SBS of the invention can also be applied to recycled asphalt.
The invention is realized by the following technical scheme:
a modified styrene-butadiene-styrene block copolymer, wherein the modified styrene-butadiene-styrene block copolymer is prepared by grafting groups shown in a formula 1 on para positions of benzene rings of polystyrene chain segments, and the weight content of the grafting groups accounts for 5-25wt% of the total weight of the modified styrene-butadiene-styrene block copolymer;
formula 1.
Preferably, the weight content of the grafting groups (i.e., the grafting ratio) is 15 to 20wt% based on the total weight of the modified styrene-butadiene-styrene block copolymer.
The molecular weight range of the modified styrene-butadiene-styrene block copolymer is not particularly limited in the present invention, and the weight average molecular weight range of the modified SBS of the present invention, which is generally applied to modified asphalt, is 3 to 18 ten thousand, depending on practical application requirements.
The preparation method of the modified styrene-butadiene-styrene block copolymer comprises the following steps:
step A: carrying out acylation reaction on the styrene-butadiene-styrene block copolymer and maleic anhydride to obtain a copolymer A (taking Lewis acid aluminum trichloride (or at least one of boron trichloride, zinc dichloride and aluminum trichloride) as a catalyst, and carrying out Friedel-crafts acylation reaction to carry out ring-opening grafting on the maleic anhydride to PS segment para-benzene ring of SBS);
；
and (B) step (B): carrying out dehydration condensation reaction on the copolymer A and 4- (2-aminoethyl) benzene-1, 2-diol to obtain a modified styrene-butadiene-styrene block copolymer;
。
wherein a, b, c, d, m, n is a natural number; the value of n can be 0~a; the value of m may be 0~d. In the polymerization of SBS, which may contain, in addition to the 1, 4-added polybutadiene repeating unit b, a part of the 1, 2-added polybutadiene repeating unit c, the content of which is related to the preparation process of SBS, without affecting the technical effect of the present invention. In the reaction formula, since maleic anhydride grafting has a certain randomness, grafted styrene and ungrafted styrene in the structural formula are randomly arranged, and are not meant to be two block structures, which have the same meaning as butadiene blocks comprising two different addition polymerization structures.
SBS which can be used in the present invention is block copolymerized and commercially available or homemade SBS can be modified in the above formulae using the above methods.
Specifically, step A: adding solvent and SBS into a reaction container, stirring until the SBS is completely dissolved in a solvent system, then adding maleic anhydride, after the SBS is completely dissolved in the solvent system, slowly adding aluminum trichloride, reacting for 3-4 hours at the temperature of 18-23 ℃, after the reaction is completed, pouring the reaction system into ice water, adding hydrochloric acid at the temperature of-10 ℃ to wash out precipitate, filtering to obtain maleic anhydride grafted SBS, and filtering to obtain maleic anhydride grafted SBS (copolymer A);
and (B) step (B): dispersing the maleic anhydride grafted SBS (copolymer A) in a solvent, adding a dopamine solution, reacting for 8-20 hours at 10-35 ℃ under the catalysis of a catalyst, filtering to obtain a solid, washing the solid with at least one solution of ethyl acetate/water solution, butyl acetate/water solution and dimethyl carbonate/water solution for several times (removing a byproduct DCU), and drying to obtain the modified styrene-butadiene-styrene block copolymer.
In the step A, the reaction solvent is at least one selected from dichloromethane and toluene; the catalyst is aluminum trichloride (or at least one of boron trichloride, zinc dichloride and aluminum trichloride); the reaction temperature is controlled to be 0-30 ℃. In the step B, the reaction solvent is at least one selected from dichloromethane and toluene; the catalyst is dicyclohexylcarbodiimide.
The modified SBS can be applied to modified asphalt, and comprises the following components in parts by weight:
85-99 parts of asphalt and 1-15 parts of modified styrene-butadiene-styrene block copolymer;
wherein, the modified styrene-butadiene-styrene segmented copolymer is characterized in that the para position of the benzene ring of the polystyrene chain segment is grafted with a grafting group with the following structural formula, and the weight content of the grafting group accounts for 5-25wt%, preferably 15-20wt% of the total weight of the modified styrene-butadiene-styrene segmented copolymer;
。
the weight average molecular weight of the modified styrene-butadiene-styrene block copolymer ranges from 3 to 18 ten thousand.
The modified asphalt can be applied to preparing waterproof coiled materials.
The invention has the following beneficial effects:
the invention grafts the amide structure and the hydroxyl structure on the para position of the benzene ring of the PS chain segment of SBS, and has the following advantages: 1. can carry out chemical crosslinking and hydrogen bonding with carboxyl and hydroxyl at the oxidized PB double bond to play a role in self-repairing and regenerating, can prolong the service time when being applied to asphalt, and can repair SBS degraded by oxidation; 2. the double bond of the polybutadiene chain segment is reserved, so that the modified SBS does not obviously reduce the low-temperature performance compared with the original SBS.
Drawings
Fig. 1: the IR spectrum of copolymer A shows that copolymer A is present at 1690cm -1 There is a strong c=o absorption peak affected by benzene ring near 1709cm -1 C=O fusion absorption peak after maleic anhydride hydrolysis appears nearby, 3450cm -1 NearbyThe absorption peak of O-H after maleic anhydride hydrolysis appears, and MAH can be successfully grafted to benzene rings of SBS.
Fig. 2: the final product of the invention is a modified styrene-butadiene-styrene block copolymer 1 An HMNR profile is provided, 1 the HMNR pattern showed that the final product exhibited a carbonyl-affected N-H characteristic peak around 9.21 and no-NH 2 structural characteristic peak, indicating that 4- (2-aminoethyl) benzene-1, 2-diol had been grafted onto the copolymer by dehydration condensation reaction with copolymer A to form the final product.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The experimental raw materials used in the invention are as follows:
SBS-1: brand LG501, weight average molecular weight 5 ten thousand, LG chemistry;
SBS-2: trade name LG473, weight average molecular weight 8 ten thousand, LG chemistry;
SBS-3: trade name LG411, weight average molecular weight 10 ten thousand, LG chemistry;
SBS-4: brand LG813, 12 thousands of weight average molecular weight, LG chemistry;
asphalt: high rich, trademark AH-90.
4- (2-aminoethyl) benzene-1, 2-diol: purchased from ala Ding Shiji Shanghai limited.
Maleic anhydride: purchased from alaa Ding Shiji Shanghai limited;
dichloromethane: purchased from alaa Ding Shiji Shanghai limited;
aluminum trichloride: purchased from alaa Ding Shiji Shanghai limited;
dilute hydrochloric acid: the concentration is 0.5mol/L;
dicyclohexylcarbodiimide: allatin Agents Shanghai Co., ltd;
modified SBS parameters and methods:
preparation of modified SBS the grafting ratio and weight average molecular weight parameters are shown in table 1 below, prepared according to the summary of the invention:
| grafting ratio, wt% | Weight average molecular weight (ten thousand) | SBS source | |
| Modified SBS-A | 10.14 | 5.5 | SBS-1 |
| Modified SBS-B | 10.33 | 8.7 | SBS-2 |
| Modified SBS-C | 10.08 | 10.9 | SBS-3 |
| Modified SBS-D | 10.20 | 13.2 | SBS-4 |
| Modified SBS-E | 5.09 | 8.3 | SBS-2 |
| Modified SBS-F | 15.21 | 9.0 | SBS-2 |
| Modified SBS-G | 20.00 | 9.5 | SBS-2 |
| Modified SBS-H | 25.00 | 9.8 | SBS-2 |
The testing method comprises the following steps:
1. method for measuring grafting rate of modified SBS (titration method):
(1) Dissolution/neutralization
Accurately weighing 0.5g of refined graft, placing into a 500mL three-port distillation flask, adding 80mL of dimethylbenzene, heating and refluxing for 10min until the graft is completely dissolved, cooling to 90 ℃, adding 1 drop of distilled water and one drop of pyridine by using a rubber head dropper, adding 1.5 mL of KOH-ethanol standard solution by using a pipette, heating and refluxing for 30min, cooling to 100 ℃, opening a glass plug at one side of the three-port flask, rapidly adding 6mL of isopropanol solution, adding two drops of phenolphthalein indicator, adding a rotor, covering the glass plug, and keeping the color of the solution dark red. In the process, flocculent precipitate cannot be separated out from the solution, and if the flocculent precipitate is separated out, the solution is heated until the flocculent precipitate is dissolved.
(2) Titration
Placing the three-port distillation flask into a water bath of a constant temperature magnetic stirrer, wherein the water bath temperature is 75 ℃, and starting a rotor to stirPerforming constant temperature titration at 75+ -2deg.C with HCl-isopropanol standard solution, stopping titration when the solution turns pink, and recording volume V of consumed HCl-isopropanol standard solution 2 . And (3) injection: in the titration process, stopping titration when the color of the solution becomes pink, adding one drop of phenolphthalein indicator, and if the color of the solution becomes red, continuing to add two drops of phenolphthalein indicator, and continuing to perform titration; if the solution does not darken, no further phenolphthalein indicator is added. After the titration is completed, a back-drop test is performed with KOH-ethanol standard solution to see if the drop is excessive. If one drop of KOH-ethanol standard solution is added, if the solution turns red, the excess is proved to be untrimmed; otherwise, re-titration is performed.
(3) Blank titration experiment
Accurately weighing 0.5g of ungrafted polymer raw material, placing the mixture in a 500mL three-necked flask, operating according to the steps (1) and (2) above, and recording the volume Vx of HCl-isopropanol standard solution consumed by a blank test. The volume of KOH-ethanol standard covered by the system was calculated according to formula 1 and recorded as A V The titration was performed three times to average.
A V = (1.5×C 1 - Vx×C 2 )/C 1 ----------------（1）
(4) Calculation of grafting ratio
The calculation is performed according to formula 2:
C MAH % =9.806×[C 1 (V 1 -A V )-V 2 C 2 ]/2m------------------(2)
wherein: c (C) MAH Is the grafting rate; m is the mass of the refined maleic anhydride graft; v (V) 1 Is the volume of KOH-ethanol standard solution; c (C) 1 Is the concentration of KOH-ethanol standard solution; v (V) 2 Is the volume of HCl-isopropanol standard solution; c (C) 2 Is the concentration of HCl-isopropanol standard solution.
Repeating the titration test for two to three times to calculate C MAH Average value of (2).
2. Weight average molecular weight of modified SBS: by GPC testing.
SBS modified asphalt coiled material parameters and methods:
preparation of SBS modified asphalt coiled material: 41% of AH-90 asphalt, 10% of 61#, 4% of SBS (modified SBS or unmodified SBS), 15% of 158 rubber powder and 30% of C100 stone powder in percentage by weight; adding asphalt and No. 61, heating to 175 deg.C, adding SBS, swelling, adding rubber powder, and maintaining at 175 deg.C for 3 hr. Then adding stone powder for reaction for 0.5h, and then discharging. The corresponding asphalt coating material can be obtained. Then coating the base cloth on two sides of the base cloth, controlling the thickness, cooling, laminating, bending, packaging and warehousing. The thickness was 4mm.
(2.1) testing the low-temperature flexibility of SBS modified asphalt coiled materials: the low temperature flexibility before aging was tested according to the GB-T328.14-2007 test method.
(2.2) Low temperature flexibility test after SBS modified asphalt coiled material aging: low temperature flexibility test after aging for 10d, 20d, 30d at 80 ℃.
AH-90 bitumen is derived from: medium oil is high in oil content.
61# is derived from: princess kaolin 61# base oil.
158 rubber powder is derived from: chinese 158 rubber powder (tyre rubber).
C100 stone dust is derived from: clear peak powder limited (talcum powder).
Table 2: examples SBS modified asphalt coiled Material type of SBS added and test results
From the above examples and comparative examples, the present invention not only realizes the improvement of low temperature flexibility but also significantly improves the temperature resistance by modifying SBS. Specifically, as is clear from examples 1 to 8, the grafting ratio is preferably 15 to 20wt%, and the aging resistance is better.
Claims (9)
1. The modified styrene-butadiene-styrene block copolymer is characterized in that a grafting group with a structural formula shown in a formula 1 is grafted on the para position of a benzene ring of a polystyrene chain segment, wherein the weight content of the grafting group accounts for 5-25wt% of the total weight of the modified styrene-butadiene-styrene block copolymer;
formula 1.
2. The modified styrene-butadiene-styrene block copolymer of claim 1, wherein the weight content of the grafting group is 15 to 20% wt% of the total weight of the modified styrene-butadiene-styrene block copolymer.
3. The modified styrene-butadiene-styrene block copolymer of claim 1, wherein the modified styrene-butadiene-styrene block copolymer has a weight average molecular weight in the range of 3 to 18 ten thousand.
4. A process for the preparation of a modified styrene-butadiene-styrene block copolymer according to any one of claims 1 to 3, characterized by comprising the steps of:
step A: carrying out acylation reaction on the styrene-butadiene-styrene block copolymer and maleic anhydride to obtain a copolymer A;
and (B) step (B): the copolymer A and 4- (2-amino ethyl) benzene-1, 2-diol are subjected to dehydration condensation reaction to obtain the modified styrene-butadiene-styrene segmented copolymer.
5. The method for producing a modified styrene-butadiene-styrene block copolymer according to claim 4, wherein step A: adding a solvent and SBS into a reaction container, stirring until the SBS is completely dissolved in a solvent system, then adding maleic anhydride, slowly adding at least one of aluminum trichloride, boron trichloride, zinc dichloride and aluminum trichloride after the SBS is completely dissolved in the solvent system, reacting for 3-4 hours at the temperature of 18-23 ℃, pouring the reaction system into ice water after the reaction is completed, adding hydrochloric acid at the temperature of-10 ℃ to wash out precipitate, and filtering to prepare the maleic anhydride grafted SBS;
and (B) step (B): dispersing the maleic anhydride grafted SBS in a solvent, adding a dopamine solution, reacting for 8-20 hours at the temperature of 10-35 ℃ under the catalysis of a catalyst, filtering to obtain a solid, washing the solid for several times by at least one solution of ethyl acetate/water solution, butyl acetate/water solution and dimethyl carbonate/water solution, and drying to obtain the modified styrene-butadiene-styrene segmented copolymer.
6. The method for producing a modified styrene-butadiene-styrene block copolymer according to claim 5, wherein in the step A, the reaction solvent is at least one selected from the group consisting of methylene chloride and toluene; the catalyst is at least one of aluminum trichloride; the reaction temperature is 0-30 ℃.
7. The method for producing a modified styrene-butadiene-styrene block copolymer according to claim 5, wherein in the step B, the reaction solvent is at least one selected from the group consisting of methylene chloride and toluene; the catalyst is dicyclohexylcarbodiimide.
8. The modified asphalt is characterized by comprising the following components in parts by weight: 85-99 parts of asphalt and 1-15 parts of the modified styrene-butadiene-styrene block copolymer according to any one of claims 1-3.
9. Use of the modified asphalt according to claim 8 for the preparation of a waterproof roll.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050101702A1 (en) * | 2003-11-12 | 2005-05-12 | Stuart Richard K.Jr. | Modified asphalt compositions |
| KR20110038245A (en) * | 2009-10-08 | 2011-04-14 | 주식회사 엘지화학 | Vinyl aromatic hydrocarbon-conjugated diene block copolymer composition for improving low temperature property of asphalt, method of manufacturing the same, and asphalt composition comprising the same |
| CN106700578A (en) * | 2017-01-13 | 2017-05-24 | 上海化工研究院有限公司 | High-content and high-elasticity special modifier for asphalt, and preparation method thereof |
| CN114752310A (en) * | 2022-04-11 | 2022-07-15 | 安徽省奥佳建材有限公司 | SBS modified asphalt waterproof coiled material with self-adhesive layer |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050101702A1 (en) * | 2003-11-12 | 2005-05-12 | Stuart Richard K.Jr. | Modified asphalt compositions |
| KR20110038245A (en) * | 2009-10-08 | 2011-04-14 | 주식회사 엘지화학 | Vinyl aromatic hydrocarbon-conjugated diene block copolymer composition for improving low temperature property of asphalt, method of manufacturing the same, and asphalt composition comprising the same |
| CN106700578A (en) * | 2017-01-13 | 2017-05-24 | 上海化工研究院有限公司 | High-content and high-elasticity special modifier for asphalt, and preparation method thereof |
| CN114752310A (en) * | 2022-04-11 | 2022-07-15 | 安徽省奥佳建材有限公司 | SBS modified asphalt waterproof coiled material with self-adhesive layer |
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