CN116375957A - Transparent impact-resistant styrene-butadiene resin and preparation method and application thereof - Google Patents
Transparent impact-resistant styrene-butadiene resin and preparation method and application thereof Download PDFInfo
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- CN116375957A CN116375957A CN202310578889.0A CN202310578889A CN116375957A CN 116375957 A CN116375957 A CN 116375957A CN 202310578889 A CN202310578889 A CN 202310578889A CN 116375957 A CN116375957 A CN 116375957A
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- 229920005989 resin Polymers 0.000 title claims abstract description 56
- 239000011347 resin Substances 0.000 title claims abstract description 56
- 239000002174 Styrene-butadiene Substances 0.000 title claims abstract description 48
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000011115 styrene butadiene Substances 0.000 title claims abstract description 48
- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 116
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims description 104
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 32
- 239000003999 initiator Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 22
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- 239000012046 mixed solvent Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000007334 copolymerization reaction Methods 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- -1 ether compound Chemical class 0.000 claims description 10
- 239000007822 coupling agent Substances 0.000 claims description 7
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003607 modifier Substances 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 235000012343 cottonseed oil Nutrition 0.000 claims description 2
- 239000002385 cottonseed oil Substances 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 2
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000005049 silicon tetrachloride Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 description 17
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 238000010998 test method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000002087 whitening effect Effects 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
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
Abstract
The invention provides a transparent impact-resistant styrene-butadiene resin and a preparation method and application thereof, wherein the preparation method comprises the steps of preparing a styrene active chain segment, preparing a styrene butadiene random chain segment and preparing a butadiene block chain segment.
Description
Technical Field
The invention belongs to the technical field of styrene-butadiene resin, and particularly relates to a transparent impact-resistant styrene-butadiene resin, and a preparation method and application thereof.
Background
The styrene-butadiene transparent impact resin is synthesized by adopting lithium anions, does not add any substances such as plasticizer, anti-reflection agent, coloring agent and the like in the process, has environmental protection and sanitation, and is widely used in the fields of medical treatment, toys, food packaging, electronic packaging and the like. However, the conventional styrene-butadiene resin has two extreme ends, namely, the hardness is high, the brittleness of the product is too high, or the toughness is enough, but the hardness cannot meet the requirements, so that the styrene-butadiene resin is not suitable in the fields of high rigidity, high anti-falling property and the like, and the application range of the styrene-butadiene resin is greatly influenced.
The styrene-butadiene transparent impact resin is obtained by modifying polystyrene resin in most of the market. CN110041477a discloses an amino multifunctional styrene-butadiene transparent impact resin and a preparation method thereof, wherein the styrene-butadiene transparent impact resin is a terpolymer of butadiene, styrene and amino functional diphenylethylene derivatives. Is prepared from alkyl lithium initiated butadiene, styrene and amino functionalized diphenyl ethylene derivative through copolymerization, and has number average molecular weight of 1X 10 4 ～100×10 4 g/mol, wherein the copolymer chain contains not less than 2 amino functionalized diphenylethylene derivative units; based on 100% of the total terpolymer, the mass percentage of styrene is 45-90%, the mass percentage of butadiene is 5-50%, and the balance is amine functionalized diphenylethylene derivative. The amino functionalized diphenylethylene derivative contains one or two amino substituent groups, and the substituent groups are directly connected to the para position of the double bond of the diphenylethylene derivative. The invention improves the thermal performance of the styrene-butadiene transparent impact resin, and the compatibility with other polar polymers, and finally realizes the preparation of the high-performance styrene-butadiene transparent impact resin and the composite material thereof. CN101191004a discloses a MBS resin composition with high transparency and stress whitening resistance, which is obtained according to the following method: (1) synthesis of styrene-butadiene latex: butadiene, styrene, an emulsifier, a molecular weight regulator and an initiator are polymerized into 80-100 nm styrene-butadiene latex by adopting seed emulsion at 75 ℃; (2) graft polymerization: the polymerization monomers are methyl methacrylate and styrene, styrene-butadiene latex is firstly subjected to emulsion polymerization with styrene, then is subjected to emulsion polymerization with methyl methacrylate, and is introduced with an ester cross-linking agent (ethylene glycol dimethacrylate) with double bonds; (3) Adding a dispersing agent and sulfuric acid into the MBS resin emulsion for flocculation, and then drying by an airflow boiling dryer; the invention provides MBS resin withExcellent transparency and anti-whitening performance, and can improve the impact resistance and fluidity of MBS resin.
However, in the fields of materials such AS transparent ABS, MS, AS and PC, the polarity problem is that the materials are incompatible or poor in compatibility with a plurality of polar materials and weak polar materials, for example, when styrene-butadiene resin is added into the materials such AS MS, AS, PC and the like for modification, the materials are easily layered, fogged or milky white and the like, the quality of the products is seriously affected, and the application limitation of the products is stronger.
Therefore, development of a method for preparing a transparent impact resistant resin having excellent impact resistance and high hardness is an urgent technical problem to be solved in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the transparent impact-resistant styrene-butadiene resin, and the preparation method and application thereof, wherein the preparation method effectively optimizes the molecular chain composition and the block structure in the molecular chain of the styrene-butadiene resin, and further obtains the transparent impact-resistant styrene-butadiene resin with high hardness and excellent impact resistance.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a transparent impact-resistant styrene-butadiene resin, the method comprising the steps of:
(1) Mixing a structure regulator with a mixed solvent to obtain a mixed solution;
(2) Mixing a first styrene monomer with the mixed solution obtained in the step (1), adding a first initiator to react, adding a first butadiene monomer to react, and adding a second initiator to react with a second styrene monomer to obtain a styrene active polymer chain segment;
(3) Carrying out random copolymerization on the styrene active polymer chain segment obtained in the step (2), a random regulator, third styrene and a second butadiene monomer to obtain a random polymer chain segment;
(4) And (3) performing a block reaction on the random polymer chain segment obtained in the step (3) and a third butadiene monomer, and adding a fourth styrene monomer to perform an end-capping reaction to obtain the transparent impact-resistant styrene-butadiene resin.
Firstly, mixing a structure regulator with a mixed solvent to obtain a mixed solution containing the structure regulator, then mixing a first styrene monomer with the mixed solution, adding a first initiator to initiate polymerization to form a first segment styrene block, and then adding a first butadiene monomer to react to form a butadiene transition section; continuing to add a second initiator and a second styrene monomer to carry out polymerization again to form a new styrene active chain segment; and then adding a random regulator, a third styrene monomer and a second butadiene monomer for random copolymerization to obtain a random polymer chain segment, finally adding the third butadiene monomer for block polymerization, and adding a fourth styrene monomer for end-capping reaction after polymerization is completed to obtain the transparent impact-resistant styrene-butadiene resin. According to the preparation method provided by the invention, the composition of the molecular chain segments of the styrene-butadiene resin and the block structure in the molecular chain segments are optimized, so that the molecular weight distribution coefficient of the product is effectively improved, the processability of the product is improved, the mechanical anisotropy of the product is weakened, the rigidity of the product is further improved, the impact resistance (namely the anti-falling performance) of the product is effectively improved, the defect of single performance of the traditional styrene-butadiene resin is overcome, and the application range of the product is enlarged.
Preferably, the structure modifier of step (1) comprises an ether compound.
Preferably, the ether compound comprises a monoether and/or a polyether.
Preferably, the structure modifier comprises any one or a combination of at least two of tetrahydrofuran, diethylene glycol dimethyl ether or ethylene glycol dimethyl ether, and further preferably tetrahydrofuran.
Preferably, the mass of the structure-modifying agent in the step (1) is 0.01 to 0.1%, for example 0.02%, 0.04%, 0.06% or 0.08%, more preferably 0.02 to 0.03%, based on 100% of the mass of the mixed solvent in the step (1).
Preferably, the mixed solvent of step (1) includes cyclohexane and n-hexane.
Preferably, the mass ratio of cyclohexane to n-hexane is (1.5-20): 1, for example, 2:1, 4:1, 6:1, 8:1, 10:1, 12:1, 14:1, 16:1, 18:1, etc., and further preferably (4-9): 1.
Preferably, the mass of the first styrene monomer in the step (2) is 15 to 45%, for example, 20%, 25%, 30%, 35% or 40%, etc., and more preferably 15 to 20%, based on 100% of the mass of all the reaction materials.
In the present invention, the term "all reaction materials" refers to all materials involved in the reaction, including an initiator and a result modifier, and the following references to the same concept have the same meaning.
Preferably, the first initiator and the second initiator in step (2) each independently comprise any one or a combination of at least two of n-butyllithium, tert-butyllithium, sec-butyllithium or sodium naphthalene, and further preferably n-butyllithium.
Preferably, the mass of the first initiator in step (2) is 0.01 to 0.07%, for example 0.02%, 0.03%, 0.04%, 0.05% or 0.06%, etc., more preferably 0.035 to 0.055% based on 100% of the mass of all the reaction materials.
Preferably, the reaction temperature at which the reaction is carried out by adding the first initiator in the step (2) is 37 to 55 ℃, for example, 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, etc., and more preferably 43 to 46 ℃.
Preferably, the mass of the first butadiene monomer in the step (2) is 0 to 10% and not equal to 0, for example, 2%, 4%, 6% or 8%, etc., and more preferably 0 to 5% and not equal to 0, based on 100% of the mass of all the reaction materials.
Preferably, the reaction temperature at which the reaction is carried out by adding the first butadiene monomer in step (2) is 50 to 70 ℃, for example, 52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃, etc., and more preferably 55 to 65 ℃.
Preferably, the mass of the second initiator in the step (2) is 0.01 to 0.1%, for example 0.02%, 0.04%, 0.06%, 0.08%, etc., based on 100% of the mass of all the reaction materials, and more preferably 0.045 to 0.1%.
Preferably, the mass of the second styrene monomer in the step (2) is 10 to 35%,12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 30%, 32% or 34% based on 100% of the mass of all the reaction materials, and more preferably 10 to 20%.
Preferably, the reaction temperature at which the second initiator and the second styrene monomer are further added in the step (2) to perform the reaction is 70 to 95 ℃, for example 73 ℃, 76 ℃, 79 ℃, 82 ℃, 85 ℃, 88 ℃, 91 ℃, 94 ℃, etc., and more preferably 85 to 90 ℃.
Preferably, the random regulator of step (3) comprises potassium tert-butoxide;
preferably, the mass of the random regulator of step (3) is 0.005 to 0.015%, for example 0.007%, 0.009%, 0.011% or 0.013%, based on 100% of the mass of all reaction materials.
Preferably, the mass of the third styrene monomer in step (3) is 3 to 10%, for example 4%, 5%, 6%, 7%, 8% or 9%, etc., based on 100% of the mass of all the reaction materials.
Preferably, the mass of the second butadiene monomer of step (3) is 3 to 10%, for example 4%, 5%, 6%, 7%, 8% or 9%, etc., based on 100% mass of all reaction materials.
Preferably, the temperature of the random copolymerization in step (3) is 60 to 90 ℃, for example 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, or the like.
Preferably, the mass of the third butadiene monomer in step (4) is 5 to 40%, e.g., 10%, 15%, 20%, 25%, 30%, 35%, etc., based on 100% of the mass of all reaction materials.
Preferably, the peak temperature of the block reaction in step (4) is 80 to 105 ℃, more preferably 85 to 90 ℃, such as 86 ℃, 87 ℃, 88 ℃, 89 ℃ or the like.
Preferably, the mass of the fourth styrene monomer in the step (4) is 1 to 45%, for example, 5%, 10%, 15%, 20%, 25%, 30%, 35% or 40%, etc., and more preferably 15 to 20%, based on 100% of the mass of all the reaction materials.
Preferably, a coupling agent is further added in the end capping reaction in the step (4).
The end-capping reaction of step (4) may be followed by adding a certain amount of a coupling agent to produce a polymer having a multi-molecular weight distribution, for example, a branched or star-structured polymer product.
Preferably, the mass of the coupling agent is 20 to 60%, for example 25%, 30%, 35%, 40%, 45%, 50% or 55%, etc., more preferably 40 to 50%, based on 100% of the total mass of the first initiator and the second initiator.
Preferably, the coupling agent comprises any one or a combination of at least two of an epoxy compound, a methoxy compound or a halide.
Preferably, the epoxy-based compound includes any one or a combination of at least two of ethylene glycol triglycidyl ether, glycerol triglycidyl ether, epoxidized soybean oil or epoxidized cottonseed oil.
Preferably, the methoxy compound comprises trimethoxysilane and/or tetramethoxysilane.
Preferably, the halide comprises any one or at least two of epichlorohydrin, silicon tetrachloride, tin tetrachloride or methyltrichlorosilane.
Preferably, the end capping reaction of step (4) further comprises the steps of solvent removal and granulation.
In a second aspect, the present invention provides a transparent impact resistant resin prepared by the preparation method according to the first aspect.
In a third aspect, the present invention provides the use of a transparent impact resin according to the second aspect in medical device products, toy products or packaging products.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method of the transparent impact-resistant styrene-butadiene resin provided by the invention effectively improves the molecular weight distribution coefficient of the product, improves the processability of the product, weakens the mechanical anisotropy of the product, further improves the rigidity of the product, effectively improves the impact resistance (namely the anti-falling performance) of the product, solves the defect of single performance of the traditional styrene-butadiene resin, and expands the application range of the product by optimizing the composition of the molecular chain segment of the styrene-butadiene resin and the block structure in the molecular chain segment.
(2) Specifically, the styrene-butadiene resin obtained by the preparation method provided by the invention has the hardness of 74-77D and the impact strength of 4.5-4.9 KJ/m 2 The haze is 1.5-2.0, and the paint has excellent impact resistance and high transparency.
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
A preparation method of transparent impact-resistant styrene-butadiene resin specifically comprises the following steps:
(1) Adding 4.5L of a mixed solvent of n-hexane and cyclohexane (the mass ratio of cyclohexane to n-hexane is 5:1) into a 10L stainless steel reaction kettle with stirring paddles, adding 0.9g of Tetrahydrofuran (THF), fully stirring, and heating to 45 ℃ to obtain a mixed solution;
(2) Adding 2.75g of n-butyllithium (with the concentration of 20%), adding 450g of styrene for reaction, wherein the reaction temperature is 45 ℃, cooling is not needed in the step, adding 45g of butadiene when the styrene is completely reacted, preserving heat in the step, preserving heat to 55 ℃, reacting, adding 4.5g of n-butyllithium (with the concentration of 20%) and 450g of styrene for reaction, and controlling the reaction temperature at 90 ℃ to obtain a styrene active polymer chain segment;
(3) Adding 0.16g of potassium tert-butoxide, stirring uniformly, adding 50g of butadiene and 50g of styrene which are blended in advance into the mixture, carrying out random copolymerization reaction, controlling the reaction temperature at 85 ℃, and obtaining a random polymer chain segment after the reaction is completed;
(4) Adding 300g of butadiene for block reaction, adding 255g of styrene monomer for end-capping reaction after the reaction peak temperature reaches 85 ℃, and finally devolatilizing, extruding and granulating the glue solution to obtain the transparent impact-resistant styrene-butadiene resin.
Example 2
A preparation method of transparent impact-resistant styrene-butadiene resin specifically comprises the following steps:
(1) Adding 4.5L of a mixed solvent of n-hexane and cyclohexane (the mass ratio of cyclohexane to n-hexane is 4:1) into a 10L stainless steel reaction kettle with stirring paddles, adding 0.9g of Tetrahydrofuran (THF), fully stirring, and heating to 45 ℃ to obtain a mixed solution;
(2) Adding 2.75g of n-butyllithium (with the concentration of 20%), adding 450g of styrene for reaction, wherein the reaction temperature is 45 ℃, cooling is not needed in the step, adding 45g of butadiene when the styrene is completely reacted, preserving heat in the step, preserving heat to 55 ℃, reacting, adding 4.5g of n-butyllithium (with the concentration of 20%) and 450g of styrene for reaction, and controlling the reaction temperature at 90 ℃ to obtain a styrene active polymer chain segment;
(3) Adding 0.16g of potassium tert-butoxide, stirring uniformly, adding 50g of butadiene and 50g of styrene which are blended in advance into the mixture, carrying out random copolymerization reaction, controlling the reaction temperature at 85 ℃, and obtaining a random polymer chain segment after the reaction is completed;
(4) Adding 300g of butadiene for block reaction, after the reaction peak temperature reaches 85 ℃, adding 255g of styrene monomer and 2.75g of ethylene glycol triglycidyl ether for end-capping reaction, and finally devolatilizing, extruding and granulating the glue solution to obtain the transparent impact-resistant styrene-butadiene resin.
Example 3
A preparation method of transparent impact-resistant styrene-butadiene resin is different from example 1 only in that tert-butyl lithium is adopted to replace n-butyl lithium, and other components, amounts and preparation methods are the same as those of example 1.
Example 4
A preparation method of transparent impact-resistant styrene-butadiene resin is different from example 1 only in that sec-butyllithium is used for replacing n-butyllithium, and other components, amounts and preparation methods are the same as those of example 1.
Comparative example 1
The preparation method of the butyl benzene resin specifically comprises the following steps:
(1) Adding 4.5L of a mixed solvent of n-hexane and cyclohexane (the mass ratio of cyclohexane to n-hexane is 5:1) into a 10L stainless steel reaction kettle with stirring paddles, adding 0.9g of Tetrahydrofuran (THF), fully stirring, and heating to 45 ℃ to obtain a mixed solution;
(2) Adding 2.75g of n-butyllithium (with the concentration of 20%), adding 450g of styrene for reaction, wherein the reaction temperature is 45 ℃, cooling is not needed in the step, adding 45g of butadiene when the styrene is completely reacted, preserving heat in the step, preserving heat to 55 ℃, reacting, adding 4.5g of n-butyllithium (with the concentration of 20%) and 450g of styrene for reaction, and controlling the reaction temperature at 90 ℃ to obtain a styrene active polymer chain segment;
(3) Adding 50g of butadiene and 50g of styrene into the mixture to carry out random copolymerization reaction, controlling the reaction temperature at 85 ℃, and obtaining a random polymer chain segment after the reaction is completed;
(4) Adding 300g of butadiene for block reaction, adding 255g of styrene monomer for end-capping reaction after the reaction peak temperature reaches 85 ℃, and finally devolatilizing, extruding and granulating the glue solution to obtain the transparent impact-resistant styrene-butadiene resin.
Comparative example 2
The preparation method of the butyl benzene resin specifically comprises the following steps:
(1) Adding 4.5L of a mixed solvent of n-hexane and cyclohexane (the mass ratio of cyclohexane to n-hexane is 5:1) into a 10L stainless steel reaction kettle with stirring paddles, adding 0.9g of Tetrahydrofuran (THF), fully stirring, and heating to 45 ℃ to obtain a mixed solution;
(2) Adding 2.75g of n-butyllithium (with the concentration of 20%), adding 450g of styrene for reaction, wherein the reaction temperature is 45 ℃, cooling is not needed in the step, after the styrene is completely reacted, preserving the temperature to 55 ℃, adding 4.5g of n-butyllithium (with the concentration of 20%) and 450g of styrene for reaction, and controlling the reaction temperature at 90 ℃ to obtain a styrene active polymer chain segment;
(3) Adding 0.16g of potassium tert-butoxide, stirring uniformly, adding 50g of butadiene and 50g of styrene which are blended in advance into the mixture, carrying out random copolymerization reaction, controlling the reaction temperature at 85 ℃, and obtaining a random polymer chain segment after the reaction is completed;
(4) Adding 345g of butadiene for block reaction, adding 255g of styrene monomer for end-capping reaction after the reaction peak temperature reaches 85 ℃, and finally devolatilizing, extruding and granulating the glue solution to obtain the transparent impact-resistant styrene-butadiene resin.
Comparative example 3
The preparation method of the butyl benzene resin specifically comprises the following steps:
(1) Adding 4.5L of a mixed solvent of n-hexane and cyclohexane (the mass ratio of cyclohexane to n-hexane is 5:1) into a 10L stainless steel reaction kettle with stirring paddles, adding 0.9g of Tetrahydrofuran (THF), fully stirring, and heating to 45 ℃ to obtain a mixed solution;
(2) Adding 2.75g of n-butyllithium (with the concentration of 20%), adding 450g of styrene for reaction at the temperature of 45 ℃, keeping the temperature at the step without cooling until the styrene is completely reacted, keeping the temperature to 55 ℃, and adding 4.5g of n-butyllithium (with the concentration of 20%) and 330g of styrene for reaction, wherein the reaction temperature is controlled at 90 ℃ to obtain a styrene active polymer chain segment;
(3) Adding 0.16g of potassium tert-butoxide, stirring uniformly, adding 176g of butadiene and 176g of styrene which are blended in advance, carrying out random copolymerization reaction, controlling the reaction temperature at 85 ℃, and obtaining a random polymer chain segment after the reaction is completed;
(4) Adding 225g of butadiene for block reaction, adding 255g of styrene monomer for end-capping reaction after the reaction peak temperature reaches 85 ℃, and finally devolatilizing, extruding and granulating the glue solution to obtain the transparent impact-resistant styrene-butadiene resin.
Comparative example 4
The preparation method of the butyl benzene resin specifically comprises the following steps:
(1) Adding 4.5L of a mixed solvent of n-hexane and cyclohexane (the mass ratio of cyclohexane to n-hexane is 4:1) into a 10L stainless steel reaction kettle with stirring paddles, adding 0.9g of Tetrahydrofuran (THF), fully stirring, and heating to 45 ℃ to obtain a mixed solution;
(2) Adding 2.75g of n-butyllithium (with the concentration of 20%), adding 480g of styrene for reaction at the temperature of 45 ℃, keeping the temperature at the step without cooling until the styrene is completely reacted, keeping the temperature to 55 ℃, and adding 4.5g of n-butyllithium (with the concentration of 20%) and 420g of styrene for reaction, wherein the reaction temperature is controlled at 90 ℃ to obtain a styrene active polymer chain segment;
(3) Adding 0.16g of potassium tert-butoxide, stirring uniformly, adding 50g of butadiene and 50g of styrene which are blended in advance into the mixture, carrying out random copolymerization reaction, controlling the reaction temperature at 85 ℃, and obtaining a random polymer chain segment after the reaction is completed;
(4) Adding 345g of butadiene for block reaction, after the reaction peak temperature reaches 85 ℃, adding 255g of styrene monomer and 2.75g of ethylene glycol triglycidyl ether for end-capping reaction, and finally devolatilizing, extruding and granulating the glue solution to obtain the transparent impact-resistant styrene-butadiene resin.
Performance test:
(1) Hardness: the test is carried out by referring to the test method provided by GB/T2411;
(2) Impact strength: the test is carried out by referring to the test method provided by GB/T1843;
(3) Haze: the test is performed by referring to the test method provided in GB/T2410.
The styrene-butadiene resins provided in examples 1 to 4 and comparative examples 1 to 4 were tested according to the above test methods, and the test results are shown in table 1:
TABLE 1
From the data in table 1, it can be seen that: the styrene-butadiene resins obtained in examples 1 to 4 had a hardness of 74 to 77D and an impact strength of 4.5 to 4.9KJ/m 2 The haze is 1.5-2.0, and the glass has excellent mechanical properties and high transparency.
As can be seen from comparing the data of example 1 and comparative example 1, the styrene-butadiene resin obtained in the step (3) without adding the random regulator has higher haze and lower impact resistance.
As can also be seen from comparing the data of example 2 with the data of comparative examples 2 to 4, the absence of the addition of butadiene monomer in step (2) also results in the final styrene-butadiene resin having lower impact resistance and lower haze.
The applicant states that the present invention is described by way of the above examples as a transparent impact-resistant styrene-butadiene resin, and a method for preparing the same and applications thereof, but the present invention is not limited to the above examples, i.e., it is not meant that the present invention must be practiced by relying on the above examples. 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. The preparation method of the transparent impact-resistant styrene-butadiene resin is characterized by comprising the following steps of:
(1) Mixing a structure regulator with a mixed solvent to obtain a mixed solution;
(2) Mixing a first styrene monomer with the mixed solution obtained in the step (1), adding a first initiator to react, adding a first butadiene monomer to react, and adding a second initiator to react with a second styrene monomer to obtain a styrene active chain segment;
(3) Carrying out random copolymerization on the styrene active polymer chain segment obtained in the step (2), a random regulator, third styrene and a second butadiene monomer to obtain a random polymer;
(4) And (3) performing a block reaction on the random polymer obtained in the step (3) and a third butadiene monomer, and adding a fourth styrene monomer for performing an end-capping reaction to obtain the transparent impact-resistant styrene-butadiene resin.
2. The method of claim 1, wherein the structure modifier of step (1) comprises an ether compound;
preferably, the ether compound comprises a monoether and/or a polyether;
preferably, the structure modifier comprises any one or a combination of at least two of tetrahydrofuran, diethylene glycol dimethyl ether or ethylene glycol dimethyl ether, and further preferably tetrahydrofuran;
preferably, the mass of the structure-adjusting agent in the step (1) is 0.01 to 0.1%, more preferably 0.02 to 0.03%, based on 100% of the mass of the mixed solvent in the step (1);
preferably, the mixed solvent of step (1) comprises cyclohexane and n-hexane;
preferably, the mass ratio of cyclohexane to n-hexane is (1.5 to 20): 1, more preferably (4 to 9): 1.
3. The production method according to claim 1 or 2, wherein the mass of the first styrene monomer in the step (2) is 15 to 45%, further preferably 15 to 20%, based on 100% of the mass of all the reaction raw materials;
preferably, the first initiator and the second initiator of step (2) each independently comprise any one or a combination of at least two of n-butyllithium, tert-butyllithium, sec-butyllithium or sodium naphthalene, further preferably n-butyllithium;
preferably, the mass of the first initiator in the step (2) is 0.01 to 0.07%, more preferably 0.035 to 0.055% based on 100% of the mass of all reaction materials;
preferably, the reaction temperature of the reaction carried out by adding the first initiator in the step (2) is 37-55 ℃, and more preferably 43-46 ℃;
preferably, the mass of the first butadiene monomer in the step (2) is 0 to 10% and not equal to 0, more preferably 0 to 5% and not equal to 0, based on 100% of the mass of all the reaction materials;
preferably, the reaction temperature of the reaction carried out by adding the first butadiene monomer in the step (2) is 50-70 ℃, and more preferably 55-65 ℃.
4. A process according to any one of claims 1 to 3, wherein the mass of the second initiator in step (2) is 0.01 to 0.1%, more preferably 0.045 to 0.1%, based on 100% of the mass of all reaction materials;
preferably, the mass of the second styrene monomer in the step (2) is 10 to 35%, more preferably 10 to 20%, based on 100% of the mass of all the reaction raw materials;
preferably, the reaction temperature of the reaction of the step (2) with the second initiator and the second styrene monomer is 70 to 95 ℃, and more preferably 85 to 90 ℃.
5. The process according to any one of claims 1 to 4, wherein the random regulator of step (3) comprises potassium t-butoxide;
preferably, the mass of the random regulator in the step (3) is 0.005-0.015% based on 100% of the mass of all reaction raw materials;
preferably, the mass of the third styrene monomer in the step (3) is 3-10% based on 100% of the mass of all the reaction raw materials;
preferably, the mass of the second butadiene monomer in the step (3) is 3 to 10 percent based on 100 percent of the mass of all reaction raw materials;
preferably, the temperature of the random copolymerization in the step (3) is 60-90 ℃.
6. The process according to any one of claims 1 to 5, wherein the mass of the third butadiene monomer in the step (4) is 5 to 40% based on 100% of the mass of all the reaction raw materials;
preferably, the peak temperature of the block reaction in the step (4) is 80-105 ℃, and more preferably 85-90 ℃;
preferably, the mass of the fourth styrene monomer in the step (4) is 1 to 45%, preferably 15 to 20%, based on 100% of the mass of all the reaction materials.
7. The method according to any one of claims 1 to 6, wherein a coupling agent is further added to the end-capping reaction in step (4);
preferably, the mass of the coupling agent is 20 to 60%, further preferably 40 to 50%, based on 100% of the total mass of the first initiator and the second initiator;
preferably, the coupling agent comprises any one or a combination of at least two of an epoxy compound, a methoxy compound or a halide;
preferably, the epoxy-based compound comprises any one or a combination of at least two of ethylene glycol triglycidyl ether, glycerol triglycidyl ether, epoxidized soybean oil or epoxidized cottonseed oil;
preferably, the methoxy compound comprises trimethoxysilane and/or tetramethoxysilane;
preferably, the halide comprises any one or at least two of epichlorohydrin, silicon tetrachloride, tin tetrachloride or methyltrichlorosilane.
8. The process according to any one of claims 1 to 7, wherein the end-capping reaction of step (4) is followed by a solvent removal and granulation step.
9. A transparent impact resin prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the transparent impact resin according to claim 9 in medical device products, toy products or packaging products.
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