CN116874696A - Butyl benzene resin composition and preparation method and application thereof - Google Patents
Butyl benzene resin composition and preparation method and application thereof Download PDFInfo
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- CN116874696A CN116874696A CN202310893308.2A CN202310893308A CN116874696A CN 116874696 A CN116874696 A CN 116874696A CN 202310893308 A CN202310893308 A CN 202310893308A CN 116874696 A CN116874696 A CN 116874696A
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- styrene
- butadiene
- block copolymer
- butylbenzene
- resin composition
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- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 239000011342 resin composition Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 152
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 146
- 239000002174 Styrene-butadiene Substances 0.000 claims abstract description 80
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000011115 styrene butadiene Substances 0.000 claims abstract description 80
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229920001577 copolymer Polymers 0.000 claims abstract description 47
- 238000006116 polymerization reaction Methods 0.000 claims description 78
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 64
- 238000006243 chemical reaction Methods 0.000 claims description 42
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 39
- 229920001400 block copolymer Polymers 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 239000004793 Polystyrene Substances 0.000 claims description 30
- 229920002223 polystyrene Polymers 0.000 claims description 25
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 19
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 18
- 239000005049 silicon tetrachloride Substances 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 239000005062 Polybutadiene Substances 0.000 claims description 9
- 229920002857 polybutadiene Polymers 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 239000007822 coupling agent Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 4
- 239000004200 microcrystalline wax Substances 0.000 claims description 4
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 230000006353 environmental stress Effects 0.000 abstract description 7
- 239000011259 mixed solution Substances 0.000 description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 229920005989 resin Polymers 0.000 description 23
- 239000011347 resin Substances 0.000 description 23
- 239000003292 glue Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 15
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000000155 melt Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011885 synergistic combination Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000011787 zinc oxide 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/044—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- 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)
- Inorganic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to a butylbenzene resin composition, a preparation method and application thereof, wherein the butylbenzene resin composition comprises a first butylbenzene segmented copolymer and a second butylbenzene segmented copolymer; the first butylbenzene segmented copolymer has a star-shaped structure; the second butylbenzene segmented copolymer is of a linear structure; the mass percentage of the styrene structural unit is 70-90% and the mass percentage of the butadiene structural unit is 10-30% based on the total mass of the first butylbenzene segmented copolymer and the second butylbenzene segmented copolymer being 100%. The styrene-butadiene resin composition disclosed by the invention has the advantages of excellent hardness, high impact resistance, higher elongation and higher flexural modulus, and has environmental stress resistance and processability.
Description
Technical Field
The invention relates to the technical field of styrene-butadiene resin, in particular to a styrene-butadiene resin composition and a preparation method and application thereof.
Background
The styrene-butadiene resin is prepared by copolymerization of butadiene and styrene serving as monomers, and has a rigid benzene ring structure and a flexible butadiene chain segment in a polymer chain, so that the styrene-butadiene resin is widely applied to various fields such as packaging, medical devices, household appliances, high-grade daily use and office supplies, and the hardness, impact resistance, environmental stress resistance and processability of the styrene-butadiene resin are important to the application of the styrene-butadiene resin.
CN104119617a discloses an impact-resistant polystyrene material and a preparation method thereof, wherein the impact-resistant polystyrene material disclosed by the invention consists of polystyrene, styrene-butadiene rubber, sulfur, zinc oxide, stearic acid, a rubber accelerator and accelerator diphenyl guanidine. The impact-resistant polystyrene material disclosed by the method not only increases the impact resistance of polystyrene and improves the conversion rate, but also has the characteristics of easy processing, good performance and low cost. However, the composition is complicated, and a plurality of additives are required to be blended.
CN105331035a discloses a butylbenzene resin composition and a preparation method thereof, the disclosed butylbenzene resin composition contains a block copolymer (PS 1 )SBS(PS 1 ) And linear polystyrene PS 2 Wherein SBS is a styrene-butadiene-styrene block copolymer chain segment with a number average molecular weight of 10-40 ten thousand, PS 1 PS as polystyrene segment 2 The number average molecular weight of (2) is 10 ten thousand to 80 ten thousand. However, the disclosed styrene-butadiene resin composition cannot have both impact resistance and processability.
In summary, it is important to develop a styrene-butadiene resin composition having excellent hardness and high impact resistance, as well as environmental stress resistance and processability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a butylbenzene resin composition, a preparation method and application thereof, wherein the butylbenzene resin composition has excellent hardness and notch cantilever impact strength, and has environmental stress resistance and processability.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a styrene-butadiene resin composition comprising a first styrene-butadiene block copolymer and a second styrene-butadiene block copolymer;
the first butylbenzene segmented copolymer has a star-shaped structure;
the second butylbenzene segmented copolymer is of a linear structure;
the mass percent of the styrene structural unit is 70% -90% (e.g., 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88%, 90%, etc.), and the mass percent of the butadiene structural unit is 10% -30% (e.g., 10%, 12%, 15%, 20%, 22%, 25%, 28%, 30%, etc.), based on the total mass of the first and second styrene-butadiene block copolymers being 100%.
In the invention, the first butylbenzene segmented copolymer with a star structure and the second butylbenzene segmented copolymer with a linear structure are compounded and cooperatively matched, the mass percentage of the styrene structural units is regulated and controlled within a specific percentage range, and the formed butylbenzene resin composition has excellent hardness, high shock resistance, higher elongation and higher bending modulus, and has environmental stress resistance and processability, wherein the first butylbenzene segmented copolymer with the star structure provides hardness and rigidity, and the second butylbenzene segmented copolymer with the linear structure provides high elongation and shock resistance.
Preferably, in the first butylbenzene block copolymer and the second butylbenzene block copolymer, the mass percentage of the styrene structural units is 70% -90% (e.g., 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88%, 90%, etc.), and the mass percentage of the butadiene structural units is 10% -30% (e.g., 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, etc.), respectively.
Preferably, the mass percent of the first butylbenzene block copolymer is 80% -95%, such as 80%, 82%, 84%, 86%, 88%, 90%, 92% or 94%, etc., based on 100% of the total mass of the first butylbenzene block copolymer and the second butylbenzene block copolymer.
Preferably, the mass percent of the second styrene-butadiene block copolymer is 5% -20%, such as 5%, 7%, 10%, 12%, 13%, 15%, 17%, 18% or 20%, etc., based on 100% of the total mass of the first and second styrene-butadiene block copolymers.
Preferably, the first butylbenzene block copolymer has a molecular formula comprising (St 1 -St 2 -Bd) m -X-(Bd-St 2 ) n 。
Wherein St 1 And St 2 Is a polystyrene segment, bd is a polybutadiene segment, X is a coupling agent, the functionality of the coupling agent is equal to or greater than 3 (e.g., 4, 5, 6, 7, 8, 9, or 10, etc.), m, n is an integer, m is equal to or greater than 0 (e.g., 0, 1, 2, 3, 4, 5, 6, or 7, etc.), and n is equal to or greater than 0 (e.g., 0, 1, 2, 3, 4, 5, 6, or 7, etc.).
Preferably, the first butylbenzene block copolymer has a number average molecular weight of 100000-300000g/mol, for example 150000g/mol, 180000g/mol, 200000g/mol, 220000g/mol, 250000g/mol or 300000g/mol, etc.
In the present invention, the number average molecular weight of the first butylbenzene block copolymer is controlled to 100000 to 300000g/mol because: the first butylbenzene segmented copolymer in the butylbenzene resin composition has a large proportion, and the number average molecular weight of the first butylbenzene segmented copolymer influences the overall hardness and impact resistance of the butylbenzene resin composition; if the number average molecular weight is higher, the styrene-butadiene resin composition is difficult to process, has too high hardness and too high rigidity, and is unfavorable for production and processing; the lower number average molecular weight of the styrene-butadiene resin composition can lead to lower hardness, lower impact resistance and lower rigidity of the styrene-butadiene resin composition.
Preferably, the coupling agent comprises any one or a combination of at least two of tetramethoxysilane, silicon tetrachloride, tin tetrachloride or epoxidized soybean oil, wherein typical but non-limiting combinations include: a combination of silicon tetrachloride and tin tetrachloride, a combination of tin tetrachloride and epoxidized soybean oil, a combination of silicon tetrachloride, tin tetrachloride and epoxidized soybean oil, and the like.
Preferably, the number average molecular weight of the second styrene-butadiene block copolymer is 10000-100000g/mol, such as 20000g/mol, 30000g/mol, 40000g/mol, 50000g/mol, 60000g/mol, 70000g/mol, 80000g/mol, 90000g/mol, or the like.
In the present invention, the number average molecular weight of the second styrene-butadiene block copolymer is controlled to 10000-100000g/mol because: the second butylbenzene segmented copolymer mainly plays a role in improving the impact resistance of the butylbenzene resin composition, and the number average molecular weight of the second butylbenzene segmented copolymer can influence the hardness and the impact resistance of the butylbenzene resin composition; if the number average molecular weight is too high, the hardness of the styrene-butadiene resin composition is lowered, and the rigidity is too low; if the number average molecular weight is too low, the impact resistance of the styrene-butadiene resin composition is lowered.
Preferably, the styrene-butadiene resin composition further comprises an auxiliary agent.
Preferably, the auxiliary agent includes an antioxidant and a lubricant.
Preferably, the antioxidants include phenolic antioxidants and/or phosphite antioxidants, illustratively including but not limited to any one or a combination of at least two of antioxidant 1076, antioxidant 1010 or antioxidant 168, wherein typical but non-limiting combinations include: a combination of antioxidant 1076 and antioxidant 168, a combination of antioxidant 1010, antioxidant 1076 and antioxidant 168, and the like.
Preferably, the lubricant comprises microcrystalline wax and/or zinc stearate.
In a second aspect, the present invention provides a method for preparing the styrene-butadiene resin composition of the first aspect, the method comprising the steps of:
and mixing the first butylbenzene segmented copolymer and the second butylbenzene segmented copolymer to obtain the butylbenzene resin composition.
Preferably, the preparation method of the first butylbenzene segmented copolymer comprises the following steps:
(1) Mixing solvent, regulator and part of styrene, adding part of initiator to make polymerization reaction so as to obtain the product A containing polystyrene chain segment.
(2) And (3) mixing the product A obtained in the step (1), the rest of the initiator and the rest of the styrene, and carrying out polymerization reaction to generate a product B containing a polystyrene chain segment and a product C containing the polystyrene chain segment.
(3) And (3) mixing the product B and the product C obtained in the step (2) with butadiene, and carrying out polymerization reaction to generate a product D containing a polystyrene chain segment and a polybutadiene chain segment and a product E containing the polystyrene chain segment and the polybutadiene chain segment.
(4) And (3) mixing the product D obtained in the step (2), the product E obtained in the step (2) and a coupling agent, reacting, and adding a terminator to obtain the first butylbenzene segmented copolymer.
In the preparation method of the first butylbenzene segmented copolymer, the step (1) generates a product A with the molecular formula St 1 Li, step (2) yields products B and C, of formula St, respectively 1 -St 2 -Li and St 2 Li, step (3) yields the products D and E, of the formula St, respectively 1 -St 2 -Bd-Li and St 2 -Bd-Li, step (4) obtaining said first butylbenzene block copolymer having the formula (St 1 -St 2 -Bd) m -X-(Bd-St 2 ) n . Wherein St is 1 、St 2 Bd is a polybutadiene block, which is a polystyrene block having the same or different degrees of polymerization.
Preferably, in step (1), the portion of styrene is 30% to 70% by mass, such as 35%, 38%, 40%, 45%, 50%, 55%, 60%, 65% or 70% by mass, of the total styrene employed in the preparation of the first butylbenzene block copolymer.
Preferably, in step (1), the fraction of initiator is 50% to 70% by mass, such as 50%, 52%, 55%, 57%, 60%, 62%, 65%, 67% or 70% by mass, of the total initiator employed in the preparation of the first butylbenzene block copolymer.
Preferably, the solvent comprises any one or a combination of at least two of cyclohexane, n-hexane or toluene.
Preferably, the modifier comprises any one or a combination of at least two of Tetrahydrofuran (THF), tetramethyl ethylenediamine or diethanol dimethyl ether.
Preferably, the initiator used in the polymerization reaction comprises n-butyllithium.
Preferably, in steps (1) and (2), the polymerization reactions are each independently to a conversion of 99% or more, for example 99.1%, 99.2%, 99.4%, 99.5%, 99.6%, 99.7% or 99.8% etc.
Preferably, in step (4), the terminator comprises any one or a combination of at least two of methanol, carbonic acid or water.
Preferably, in step (4), the reaction further comprises adding an auxiliary agent for mixing.
Preferably, the polymerization reaction temperatures in steps (1) - (3) are each independently 50-55 ℃, e.g., 51 ℃, 51.5 ℃, 52 ℃, 52.5 ℃, 53 ℃, 53.5 ℃, 54 ℃, etc.
Preferably, the polymerization times are each independently 20-30min, e.g., 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, 29min, etc.
Preferably, the preparation method of the second styrene-butadiene block copolymer comprises the following steps:
(1 ') mixing the solvent, the regulator and part of the styrene, adding the initiator to carry out polymerization reaction, and generating a product A' containing polystyrene chain segments.
(2 ') mixing the product A' obtained in (1 ') with a part of butadiene and a part of styrene, and carrying out polymerization reaction to obtain a product B' containing a polystyrene segment and a polybutadiene segment.
(3 ') mixing the product B' obtained in (2 '), the rest butadiene and part of styrene, and carrying out polymerization reaction to obtain a product C'.
And (4 ') mixing the product C ' obtained in the step (3 ') and the rest of styrene, carrying out polymerization reaction, and adding a terminator to obtain the second styrene-butadiene block copolymer.
In the preparation method of the second butylbenzene segmented copolymer, the step (1 ') generates a product A' with the molecular formula St 1 ' -Li, step (2 ') yielding a product B ' of formula St 1 '-Bd 1 '/St 2 ' -Li, where Bd 1 '/St 2 ' represents a segment of a random block of butadiene and styrene, step (3 ') yielding a product C ' of formula St 1 '-Bd 1 '/St 2 '-Bd 2 '/St 3 ' -Li, where Bd 2 '/St 3 'represents a segment of a random block of butadiene and styrene, and step (4') gives the second styrene-butadiene block copolymer having the formula St 1 '-Bd 1 '/St 2 '-Bd 2 '/St 3 '-St 4 ', st 1 '、St 4 ' being polystyrene segments of the same or different degrees of polymerization, bd 1 '/St 2 ' and Bd 2 '/St 3 ' are segments of identical or different butadiene and styrene random blocks.
Preferably, the solvent comprises any one or a combination of at least two of cyclohexane, n-hexane or toluene.
Preferably, the modifier comprises any one or a combination of at least two of Tetrahydrofuran (THF), tetramethyl ethylenediamine or diethanol dimethyl ether.
Preferably, the initiator used in the polymerization reaction comprises n-butyllithium.
Preferably, in step (1'), the polymerization reactions are each independently carried out to a conversion of ≡99%, for example 99.1%, 99.2%, 99.4%, 99.5%, 99.6%, 99.7% or 99.8% etc.
Preferably, in step (1'), the portion of styrene has a mass percentage of 65% to 80%, such as 65%, 67%, 69%, 70%, 72%, 74%, 76%, 78%, 79% or 80%, etc., of the total styrene used in the preparation of the second styrene-butadiene block copolymer.
Preferably, in step (2'), the portion of styrene has a mass percent of 10% to 25%, such as 10%, 12%, 14%, 16%, 18%, 19%, 20%, 22%, 24% or 25%, etc., of the total styrene used in the preparation of the second styrene-butadiene block copolymer.
Preferably, in step (2'), the portion of butadiene is 40% -55%, such as 40%, 42%, 45%, 48%, 50%, 51%, 52%, 53%, 54% or 55% by mass of the total butadiene used in the preparation of the second styrene-butadiene block copolymer.
Preferably, in step (3'), the portion of styrene is 5% to 20% by mass, such as 5%, 8%, 9%, 10%, 12%, 14%, 16%, 17%, 18%, 19% or 20% by mass, of the total styrene used in the preparation of the second styrene-butadiene block copolymer.
Preferably, in step (4'), the reaction further comprises adding an auxiliary agent for mixing.
Preferably, in step (4'), the terminator comprises any one or a combination of at least two of methanol, carbonic acid or water.
Preferably, the polymerization reaction temperatures in steps (1 ') - (4') are each independently 50-55 ℃, e.g., 51 ℃, 51.5 ℃, 52 ℃, 52.5 ℃, 53 ℃, 53.5 ℃, 54 ℃, etc.
Preferably, the polymerization times are each independently 20-30min, e.g., 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, 29min, 30min, etc.
In a third aspect, the present invention provides the use of the styrene-butadiene resin composition as defined in the first aspect in impact-resistant articles.
Compared with the prior art, the invention has the following beneficial effects:
(1) The styrene-butadiene resin composition disclosed by the invention has the advantages of excellent hardness, high impact resistance, higher elongation and higher flexural modulus, and has environmental stress resistance and processability.
(2) In the invention, the hardness of the styrene-butadiene resin composition is between 76 and 87A, the flexural modulus is more than or equal to 1085MPa, and the notched Izod impact strength is 3.2kJ/m 2 Above, at 200deg.CThe melt index of the styrene-butadiene resin composition is 2.4-18.6g/10min under the test condition of 5kg, preferably, the hardness of the styrene-butadiene resin composition is 76-84A, the notched Izod impact strength is above 5.1kJ/m < 2 >, the flexural modulus is above 1430MPa, and the melt index of the styrene-butadiene resin composition is 6.2-9.3g/10min under the test condition of 200 ℃/5 kg.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The present embodiment provides a styrene-butadiene resin composition including a first styrene-butadiene block copolymer and a second styrene-butadiene block copolymer, and a method of preparing the same;
the first butylbenzene segmented copolymer has a star-shaped structure, and the number average molecular weight is 200000g/mol;
the second butylbenzene segmented copolymer is of a linear structure, and the number average molecular weight is 50000g/mol.
The styrene-butadiene resin composition is prepared by a preparation method which comprises the following steps:
(S1) preparation of a first butylbenzene block copolymer:
replacing a 10L stainless steel polymerization kettle with refined nitrogen for multiple times, adding 4500g of solvent (cyclohexane), 0.35g of regulator (diethanol dimethyl ether) and 800g of styrene into the kettle in a nitrogen atmosphere, mixing, adding 13.1mL of mixed solution of n-butyllithium and cyclohexane, carrying out polymerization reaction at 53 ℃ for 25 minutes, completing the reaction, adding 9.4mL of mixed solution of n-butyllithium and cyclohexane, adding 400g of styrene, carrying out polymerization reaction, completing the reaction after 20 minutes, adding 300g of butadiene, carrying out polymerization reaction, completing the reaction after 30 minutes, adding 10mL of mixed solution of silicon tetrachloride and cyclohexane, adding 20% of silicon tetrachloride in the mixed solution, carrying out the reaction, adding 0.6g of terminator (methanol), and then adding 6g of styrene-butadiene resin glue solution containing first butylbenzene segmented copolymer, wherein the mass ratio of antioxidant 1076 and antioxidant 168 is 1:1.
(S2) preparation of a second styrene-butadiene block copolymer:
the method comprises the steps of replacing a 5L stainless steel polymerization kettle with refined nitrogen for a plurality of times, adding 2000g of solvent (cyclohexane), 0.15g of regulator (diethanol dimethyl ether) and 85.0g of styrene into the kettle in a nitrogen atmosphere, mixing, adding 2.5mL of mixed solution of n-butyllithium and cyclohexane, carrying out polymerization reaction at 53 ℃ for 25 minutes, adding 16.5g of butadiene and 20.0g of styrene, carrying out polymerization reaction, carrying out reaction after 30 minutes, adding 16.5g of butadiene and 12.8g of styrene, carrying out polymerization reaction, carrying out reaction after 30 minutes, adding 14.3g of styrene, carrying out polymerization reaction, carrying out reaction after 25 minutes, adding 0.2g of terminator (methanol), and then adding 0.8g of antioxidant (antioxidant 1076 and antioxidant with the mass ratio of 1:1), and styrene-butadiene resin glue solution containing a second styrene-butadiene block copolymer.
(S3) mixing the styrene-butadiene resin glue solution containing the first butylbenzene segmented copolymer obtained in the step (S1) with the styrene-butadiene resin glue solution containing the second butylbenzene segmented copolymer obtained in the step (S2), devolatilizing and granulating to obtain the styrene-butadiene resin composition.
Example 2
The present embodiment provides a styrene-butadiene resin composition including a first styrene-butadiene block copolymer and a second styrene-butadiene block copolymer, and a method of preparing the same;
the first butylbenzene segmented copolymer is of a linear structure, and the number average molecular weight is 100000g/mol;
the second butylbenzene segmented copolymer has a star-shaped structure, and the number average molecular weight is 100000g/mol.
The styrene-butadiene resin composition is prepared by a preparation method which comprises the following steps:
(S1) preparation of a first butylbenzene block copolymer:
10L of stainless steel polymerization kettle is replaced by refined nitrogen for many times, 4500g of solvent (cyclohexane), 0.35g of regulator (tetramethyl ethylenediamine) and 552g of styrene are added into the kettle in a nitrogen atmosphere to be mixed, 20.6mL of mixed solution of n-butyllithium and cyclohexane is added, the mass percent of n-butyllithium in the mixed solution is 20 percent, the polymerization reaction is carried out at 53 ℃, the reaction is completed after 25 minutes, 11.8mL of mixed solution of n-butyllithium and cyclohexane is added, the mass percent of n-butyllithium in the mixed solution is 20 percent, 498g of styrene is added to be mixed, the polymerization reaction is carried out after 20 minutes, 450g of butadiene is added to be mixed, the polymerization reaction is carried out after 30 minutes, 15mL of mixed solution of silicon tetrachloride and cyclohexane are added, the mass percent of silicon tetrachloride in the mixed solution is 20 percent, the reaction is carried out, 0.6g of terminator (water) is added, and then 6g of antioxidant 1076 and antioxidant 168 are added, and 1.5g of microcrystalline wax are added, so that styrene-butadiene resin containing first butylbenzene glue solution is obtained.
(S2) preparation of a second styrene-butadiene block copolymer:
the method comprises the steps of replacing a 5L stainless steel polymerization kettle with refined nitrogen for a plurality of times, adding 2000g of solvent (cyclohexane), 0.15g of regulator (tetramethyl ethylenediamine) and 196g of styrene into the kettle in a nitrogen atmosphere, mixing, adding 2.7mL of mixed solution of n-butyllithium and cyclohexane, carrying out polymerization reaction at 53 ℃ for 25 minutes, completing the reaction, adding 60g of butadiene and 28g of styrene, carrying out polymerization reaction, completing the reaction after 30 minutes, adding 52.5g of butadiene and 18g of styrene, carrying out polymerization reaction, completing the reaction after 30 minutes, adding 20.5g of styrene, carrying out polymerization reaction, completing the reaction after 25 minutes, adding 0.2g of terminator (water), and then adding 0.8g of antioxidant (the mass ratio of antioxidant 1076 to antioxidant 168 is 1:1) and 0.2g of microcrystalline wax, and containing styrene-butadiene resin glue solution of a second styrene-butadiene block copolymer.
(S3) mixing the styrene-butadiene resin glue solution containing the first butylbenzene segmented copolymer obtained in the step (S1) with the styrene-butadiene resin glue solution containing the second butylbenzene segmented copolymer obtained in the step (S2), devolatilizing and granulating to obtain the styrene-butadiene resin composition.
Example 3
The present embodiment provides a styrene-butadiene resin composition including a first styrene-butadiene block copolymer and a second styrene-butadiene block copolymer, and a method of preparing the same;
the first butylbenzene segmented copolymer is of a linear structure, and the number average molecular weight is 300000g/mol;
the second butylbenzene segmented copolymer is of a star-shaped structure, and the number average molecular weight is 10000g/mol.
The styrene-butadiene resin composition is prepared by a preparation method which comprises the following steps:
(S1) preparation of a first butylbenzene block copolymer:
10L of stainless steel polymerization kettle is replaced by refined nitrogen for many times, 4500g of solvent (toluene), 0.35g of regulator (tetrahydrofuran) and 810g of styrene are added into the kettle in a nitrogen atmosphere to be mixed, 7.8mL of mixed solution of n-butyllithium and cyclohexane is added, the mass percent of n-butyllithium in the mixed solution is 20 percent, the polymerization reaction is carried out at 53 ℃ for 25 minutes, the reaction is completed, 7mL of mixed solution of n-butyllithium and cyclohexane is added, the mass percent of n-butyllithium in the mixed solution is 20 percent, 540g of styrene is added to be mixed, the polymerization reaction is carried out, the reaction is completed after 20 minutes, 150g of butadiene is added to be mixed, the polymerization reaction is carried out after 30 minutes, 12.5mL of mixed solution of silicon tetrachloride and cyclohexane are added, the mass percent of silicon tetrachloride in the mixed solution is 20 percent, the reaction is carried out, 0.5g of terminator (carbonic acid) is added, and then 6g of antioxidant (the mass ratio of antioxidant 1076 and antioxidant 168 is 1:1) and 1.5g of zinc stearate are added, so that the styrene-butadiene resin glue solution containing the first butylbenzene segmented copolymer is obtained.
(S2) preparation of a second styrene-butadiene block copolymer:
the method comprises the steps of replacing a 5L stainless steel polymerization kettle with refined nitrogen for a plurality of times, adding 2000g of solvent (toluene), 0.15g of regulator (tetrahydrofuran) and 44.2g of styrene into the kettle in a nitrogen atmosphere to be mixed, adding 4.5mL of mixed solution of n-butyllithium and cyclohexane, carrying out polymerization reaction at 50 ℃ for 25 minutes to complete the reaction, adding 4g of butadiene and 10.8g of styrene to be mixed, carrying out polymerization reaction for 30 minutes to complete the reaction, adding 6.2g of styrene to be mixed, carrying out polymerization reaction for 25 minutes to complete the reaction, adding 0.2g of terminator (carbonic acid), and then adding 0.7g of antioxidant 1076 and antioxidant 168 with 0.1g of zinc stearate in a mass ratio of 1:1, and styrene-butadiene resin glue solution containing a second styrene-butadiene block copolymer.
(S3) mixing the styrene-butadiene resin glue solution containing the first butylbenzene segmented copolymer obtained in the step (S1) with the styrene-butadiene resin glue solution containing the second butylbenzene segmented copolymer obtained in the step (S2), devolatilizing and granulating to obtain the styrene-butadiene resin composition.
Example 4
This example provides a styrene-butadiene resin composition and a method for preparing the same, which are different from example 1 in that the number average molecular weight of the first styrene-butadiene block copolymer is 50000g/mol, and the method for preparing the same is adjusted as follows:
(S1) preparation of a first butylbenzene block copolymer: 10L of stainless steel polymerization kettle is replaced by refined nitrogen for many times, 4500g of solvent (cyclohexane), 0.35g of regulator (diethanol dimethyl ether) and 800g of styrene are added into the kettle in a nitrogen atmosphere to be mixed, 22.3mL of mixed solution of n-butyllithium and cyclohexane is added, the mass percent of n-butyllithium in the mixed solution is 20 percent, the polymerization reaction is carried out at 53 ℃, the reaction is completed after 25 minutes, 24.6mL of mixed solution of n-butyllithium and cyclohexane is added, the mass percent of n-butyllithium in the mixed solution is 20 percent and 400g of styrene are added to be mixed, the polymerization reaction is carried out after 20 minutes, 300g of butadiene is added to be mixed, the polymerization reaction is carried out after 30 minutes, 17.2mL of mixed solution of silicon tetrachloride and cyclohexane are added, the mass percent of silicon tetrachloride in the mixed solution is 20 percent, the reaction is carried out, 0.6g of terminator (methanol) is added, and then 6g of antioxidant 1076 and antioxidant 168 (the mass ratio is 1:1) is added, so that the styrene-butadiene resin glue solution containing the first butylbenzene copolymer is obtained.
The remainder was the same as in example 1.
Example 5
This example provides a styrene-butadiene resin composition and a method of preparing the same, which are different from example 1 in that the number average molecular weight of the first styrene-butadiene block copolymer is 350000g/mol, and the method of preparing the first styrene-butadiene block copolymer is adjusted as follows:
(S1) preparation of a first butylbenzene block copolymer: 10L of stainless steel polymerization kettle is replaced by refined nitrogen for many times, 4500g of solvent (cyclohexane), 0.35g of regulator (diethanol dimethyl ether) and 800g of styrene are added into the kettle in a nitrogen atmosphere to be mixed, 4.3mL of mixed solution of n-butyllithium and cyclohexane is added, the mass percent of n-butyllithium in the mixed solution is 20 percent, the polymerization reaction is carried out at 53 ℃, the reaction is completed after 25 minutes, 7.6mL of mixed solution of n-butyllithium and cyclohexane is added, the mass percent of n-butyllithium in the mixed solution is 20 percent, 400g of styrene is added to be mixed, the polymerization reaction is carried out after 20 minutes, 300g of butadiene is added to be mixed, the polymerization reaction is carried out after 30 minutes, 7.2mL of mixed solution of silicon tetrachloride and cyclohexane are added, the mass percent of silicon tetrachloride in the mixed solution is 20 percent, the reaction is carried out, 0.5g of terminator (methanol) is added, and then 6g of antioxidant (the mass ratio is 1:1) of antioxidant 1076 and antioxidant 168) are added, so as to obtain styrene-butadiene resin glue solution containing the first butylbenzene segmented copolymer.
The remainder was the same as in example 1.
Example 6
This example provides a styrene-butadiene resin composition and a method of preparing the same, which are different from example 1 in that the number average molecular weight of the second styrene-butadiene block copolymer is 5000g/mol, and in order to prepare the styrene-butadiene resin composition, the method of preparing the second styrene-butadiene block copolymer is adjusted as follows:
(S2) preparation of a second styrene-butadiene block copolymer: the method comprises the steps of replacing a 5L stainless steel polymerization kettle with refined nitrogen for a plurality of times, adding 2000g of solvent (cyclohexane), 0.15g of regulator (diethanol dimethyl ether) and 85.0g of styrene into the kettle in a nitrogen atmosphere, mixing, adding 22.5mL of mixed solution of n-butyllithium and cyclohexane, carrying out polymerization reaction at 53 ℃ for 25 minutes, adding 16.5g of butadiene and 20.0g of styrene, carrying out polymerization reaction, carrying out reaction after 30 minutes, adding 16.5g of butadiene and 12.8g of styrene, carrying out polymerization reaction, carrying out reaction after 30 minutes, adding 14.3g of styrene, carrying out polymerization reaction, carrying out reaction after 25 minutes, adding 0.2g of terminator (methanol), and then adding 0.8g of antioxidant (antioxidant 1076 and antioxidant with the mass ratio of 1:1), and styrene-butadiene resin glue solution containing a second styrene-butadiene block copolymer.
The remainder was the same as in example 1.
Example 7
This example provides a styrene-butadiene resin composition and a method of preparing the same, which are different from example 1 in that the number average molecular weight of the second styrene-butadiene block copolymer is 120000g/mol, and the method of preparing the second styrene-butadiene block copolymer is adjusted as follows:
(S2) preparation of a second styrene-butadiene block copolymer: the method comprises the steps of replacing a 5L stainless steel polymerization kettle with refined nitrogen for a plurality of times, adding 2000g of solvent (cyclohexane), 0.15g of regulator (diethanol dimethyl ether) and 85.0g of styrene into the kettle in a nitrogen atmosphere, mixing, adding 1.2mL of mixed solution of n-butyllithium and cyclohexane, carrying out polymerization reaction at 53 ℃ for 25 minutes, adding 16.5g of butadiene and 20.0g of styrene, carrying out polymerization reaction, carrying out reaction after 30 minutes, adding 16.5g of butadiene and 12.8g of styrene, carrying out polymerization reaction, carrying out reaction after 30 minutes, adding 14.3g of styrene, carrying out polymerization reaction, carrying out reaction after 25 minutes, adding 0.2g of terminator (methanol), and then adding 0.8g of antioxidant (antioxidant 1076 and antioxidant with the mass ratio of 1:1), and styrene-butadiene resin glue solution containing a second styrene-butadiene block copolymer.
The remainder was the same as in example 1.
Example 8
The present example provides a styrene-butadiene resin composition and a method for preparing the same, which are different from the first styrene-butadiene block copolymer in that the mass percentage of the styrene structural unit is 55% in the first styrene-butadiene block copolymer, and the method for preparing the first styrene-butadiene block copolymer is adjusted as follows:
(S1) preparation of a first butylbenzene block copolymer: replacing a 10L stainless steel polymerization kettle with refined nitrogen for multiple times, adding 4500g of solvent (cyclohexane), 0.35g of regulator (diethanol dimethyl ether) and 700g of styrene into the kettle in a nitrogen atmosphere, mixing, adding 13.1mL of mixed solution of n-butyllithium and cyclohexane, carrying out polymerization reaction at 53 ℃ for 25 minutes, completing the reaction, adding 9.4mL of mixed solution of n-butyllithium and cyclohexane, adding 125g of styrene, carrying out polymerization reaction, completing the reaction after 20 minutes, adding 675g of butadiene, carrying out polymerization reaction, completing the reaction after 30 minutes, adding 10mL of mixed solution of silicon tetrachloride and cyclohexane, adding 20% of silicon tetrachloride in the mixed solution, carrying out the reaction, adding 0.6g of terminator (methanol), and then adding 6g of antioxidant (antioxidant 1076 and antioxidant 168 in a mass ratio of 1:1), thus obtaining styrene-butadiene resin glue solution containing the first butylbenzene segmented copolymer.
The remainder was the same as in example 1.
Example 9
The present example provides a styrene-butadiene resin composition and a method for preparing the same, which are different from the first styrene-butadiene block copolymer in that the mass percentage of the styrene structural units in the first styrene-butadiene block copolymer is 95%, and the method for preparing the first styrene-butadiene block copolymer is adjusted as follows:
(S1) preparation of a first butylbenzene block copolymer: 10L of stainless steel polymerization kettle is replaced by refined nitrogen for many times, 4500g of solvent (cyclohexane), 0.35g of regulator (diethanol dimethyl ether) and 800g of styrene are added into the kettle in a nitrogen atmosphere to be mixed, 13.1mL of mixed solution of n-butyllithium and cyclohexane is added, the mass percent of n-butyllithium in the mixed solution is 20 percent, the polymerization reaction is carried out at 53 ℃ for 25 minutes, the reaction is completed, 9.4mL of mixed solution of n-butyllithium and cyclohexane, the mass percent of n-butyllithium in the mixed solution is 20 percent, 625g of styrene is added to be mixed, the polymerization reaction is carried out for 20 minutes, 75g of butadiene is added to be mixed, the polymerization reaction is carried out for 30 minutes, 10mL of mixed solution of silicon tetrachloride and cyclohexane are added to be mixed, the mass percent of silicon tetrachloride in the mixed solution is 20 percent, 0.6g of terminator (methanol) is added, and then 6g of antioxidant 1076 and antioxidant 168 (the mass ratio is 1:1) is added, so that styrene-butadiene resin glue solution containing first butylbenzene segmented copolymer is obtained.
The remainder was the same as in example 1.
Comparative example 1
This comparative example provides a styrene-butadiene resin composition and a method of preparing the same, which are different from example 1 in that the styrene-butadiene resin composition does not include a first styrene-butadiene block copolymer, and the rest is the same as example 1.
Comparative example 2
This comparative example provides a styrene-butadiene resin composition and a method of preparing the same, which are different from example 1 in that the styrene-butadiene resin composition does not include a second styrene-butadiene block copolymer, and the rest is the same as example 1.
Performance testing
The styrene-butadiene resin compositions described in examples 1 to 9 and comparative examples 1 to 2 were subjected to the following test:
(1) Hardness: indentation hardness (Shore hardness) was measured using a durometer in accordance with GB/T2411-2008 for plastics and hard rubber.
(2) Notched Izod impact Strength: the impact strength of the plastic cantilever beam is measured according to GB/T1843-2008.
(3) Flexural modulus: the flexural properties of the plastics were determined according to GB/T9341-2008.
(4) Melt index (200 ℃/5 kg): the melt Mass Flow Rate (MFR) and melt volume flow rate (MVR) of the plastics thermoplastic were determined in accordance with GB/T3682.1-2018.
The test results are summarized in table 1.
TABLE 1
As can be seen from an analysis of the data in Table 1, in the present invention, the styrene-butadiene resin composition had a hardness of 76 to 87A and a notched Izod impact strength of 3.2kJ/m 2 The flexural modulus is more than 1085MPa, and the melt index is between 2.4 and 18.6g/10min under the test condition of 200 ℃/5 kg; the styrene-butadiene resin compositions provided in examples 1 to 3 had a hardness of 76 to 84A and a notched Izod impact strength of 5.1kJ/m 2 The flexural modulus is above 1430MPa, and the melt index is between 6.2 and 9.3g/10min under the test condition of 200 ℃/5kg, so that the styrene-butadiene resin composition has excellent hardness and notch cantilever impact strength, and has environmental stress resistance and processability.
As is clear from the analysis of comparative examples 1 to 2 and example 1, the hardness and flexural modulus were decreased when the first styrene-butadiene block copolymer was not added to the styrene-butadiene resin composition (comparative example 1), and the notched Izod impact strength was decreased when the second styrene-butadiene block copolymer was not added to the styrene-butadiene resin composition (comparative example 2), which proves that the styrene-butadiene resin composition formed by the synergistic combination of the first styrene-butadiene block copolymer and the second styrene-butadiene block copolymer of the present invention was better in performance.
Analysis of examples 4-5 and example 1 shows that if the number average molecular weight of the first butylbenzene block copolymer is low (example 4), notched Izod impact strength and flexural modulus are reduced, and if the number average molecular weight of the first butylbenzene block copolymer is high (example 5), the styrene-butadiene resin composition has high hardness and low melt index, which is disadvantageous for production and processing, and the number average molecular weight of the first butylbenzene block copolymer is 100000-300000g/mol, resulting in a styrene-butadiene resin composition having better properties.
As is evident from the analysis of examples 6 to 7 and example 1, if the number average molecular weight of the second styrene-butadiene block copolymer is low (example 6), the notched Izod impact strength is low, and if the number average molecular weight of the second styrene-butadiene block copolymer is high (example 7), the flexural modulus is low, and it is confirmed that the number average molecular weight of the second styrene-butadiene block copolymer is 10000 to 100000g/mol, and the resulting styrene-butadiene resin composition has better properties.
Analysis of examples 8-9 and example 1 shows that if the mass percent of styrene structural units in the first butylbenzene block copolymer is low (example 8), the hardness is low, and if the mass percent of styrene structural units in the first butylbenzene block copolymer is high (example 9), the notched Izod impact strength is low, which proves that the styrene structural units form a first butylbenzene block copolymer and a second butylbenzene block copolymer in a specific ratio which cooperate with each other, and the formed butylbenzene resin composition has better performance.
The present invention is described in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be practiced depending on the above detailed methods. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A styrene-butadiene resin composition, characterized in that the styrene-butadiene resin composition comprises a first styrene-butadiene block copolymer and a second styrene-butadiene block copolymer;
the first butylbenzene segmented copolymer has a star-shaped structure;
the second butylbenzene segmented copolymer is of a linear structure;
the mass percentage of the styrene structural unit is 70-90% and the mass percentage of the butadiene structural unit is 10-30% based on the total mass of the first butylbenzene segmented copolymer and the second butylbenzene segmented copolymer being 100%.
2. The styrene-butadiene resin composition according to claim 1, wherein the mass percentage of the styrene structural units in the first and second styrene-butadiene block copolymers is each independently 70 to 90%, and the mass percentage of the butadiene structural units is each independently 10 to 30%.
3. The styrene-butadiene resin composition according to claim 1 or 2, wherein the mass percentage of the first butyl benzene block copolymer is 80% to 95% based on 100% of the total mass of the first butyl benzene block copolymer and the second butyl benzene block copolymer;
preferably, the mass percentage of the second styrene-butadiene block copolymer is 5% -20% based on 100% of the total mass of the first styrene-butadiene block copolymer and the second styrene-butadiene block copolymer.
4. The styrene-butadiene resin composition of any one of claims 1-3, wherein the molecular formula of the first butyl benzene block copolymer comprises (St 1 -St 2 -Bd) m -X-(Bd-St 2 ) n ，
Wherein St 1 And St 2 Is a polystyrene chain segment, bd is a polybutadiene chain segment, X is a coupling agent, the functionality of the coupling agent is more than or equal to 3, m and n are integers, m is more than or equal to 0, and n is more than or equal to 0;
preferably, the first butylbenzene block copolymer has a number average molecular weight of 100000-300000g/mol;
preferably, the coupling agent comprises any one or a combination of at least two of tetramethoxysilane, silicon tetrachloride, tin tetrachloride or epoxidized soybean oil;
preferably, the number average molecular weight of the second styrene-butadiene block copolymer is 10000-100000g/mol.
5. The styrene-butadiene resin composition of any one of claims 1-4, wherein the styrene-butadiene resin composition further comprises an auxiliary agent;
preferably, the auxiliary agent comprises an antioxidant and a lubricant;
preferably, the lubricant comprises microcrystalline wax and/or zinc stearate.
6. A method for preparing the styrene-butadiene resin composition of any one of claims 1 to 5, comprising the steps of:
and mixing the first butylbenzene segmented copolymer and the second butylbenzene segmented copolymer to obtain the butylbenzene resin composition.
7. The method of preparing according to claim 6, wherein the method of preparing the first butylbenzene block copolymer comprises the steps of:
(1) Mixing a solvent, a regulator and part of styrene, and adding part of initiator to perform polymerization reaction to generate a product A containing polystyrene chain segments;
(2) Mixing the product A obtained in the step (1), the rest of the initiator and the rest of the styrene, and carrying out polymerization reaction to generate a product B containing a polystyrene chain segment and a product C containing the polystyrene chain segment;
(3) Mixing the product B and the product C obtained in the step (2) with butadiene, and performing polymerization reaction to generate a product D containing a polystyrene chain segment and a polybutadiene chain segment and a product E containing the polystyrene chain segment and the polybutadiene chain segment;
(4) And (3) mixing the product D obtained in the step (2), the product E obtained in the step (2) and a coupling agent, reacting, and adding a terminator to obtain the first butylbenzene segmented copolymer.
8. The method according to claim 6 or 7, wherein in the step (1), the mass percentage of the part of styrene in the total styrene used for the preparation of the first butylbenzene block copolymer is 30% to 70%;
preferably, in step (1), the portion of initiator is 50% to 70% by mass of the total initiator used to prepare the first butylbenzene block copolymer;
preferably, the solvent comprises any one or a combination of at least two of cyclohexane, n-hexane or toluene;
preferably, the regulator comprises any one or a combination of at least two of tetrahydrofuran, tetramethyl ethylenediamine or diethanol dimethyl ether;
preferably, the initiator used in the polymerization reaction comprises n-butyllithium;
preferably, in steps (1) and (2), the polymerization reactions are each independently carried out to a conversion of > 99%;
preferably, in step (4), the terminator comprises any one or a combination of at least two of methanol, carbonic acid or water;
preferably, in step (4), the reaction further comprises adding an auxiliary agent for mixing.
9. The method according to any one of claims 6 to 8, wherein the method for preparing the second styrene-butadiene block copolymer comprises the steps of:
(1 ') mixing a solvent, a regulator and part of styrene, and adding an initiator to perform polymerization reaction to generate a product A' containing a polystyrene chain segment;
(2 ') mixing the product A' obtained in the step (1 ') with part of butadiene and part of styrene, and carrying out polymerization reaction to generate a product B' containing a polystyrene chain segment and a polybutadiene chain segment;
(3 ') mixing the product B' obtained in the step (2 ') with the rest butadiene and part of styrene, and carrying out polymerization reaction to obtain a product C';
(4 ') mixing the product C ' obtained in the step (3 ') and the rest of styrene, carrying out polymerization reaction, and adding a terminator to obtain the second styrene-butadiene block copolymer;
preferably, in the step (1'), the mass percentage of the part of styrene in the total styrene used for preparing the second styrene-butadiene block copolymer is 60% -80%;
preferably, in the step (2'), the mass percentage of the part of styrene in the total styrene used for preparing the second styrene-butadiene block copolymer is 10% -20%;
preferably, in the step (2'), the mass percentage of the part of butadiene in the whole butadiene used for preparing the second styrene-butadiene block copolymer is 40% -55%;
preferably, in the step (3'), the mass percentage of the part of styrene in the total styrene used for preparing the second styrene-butadiene block copolymer is 5% to 20%;
preferably, in step (4'), the reaction further comprises adding an auxiliary agent for mixing.
10. Use of the styrene-butadiene resin composition of any one of claims 1 to 5 in impact-resistant articles.
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