CN112442149A - Styrene-butadiene resin and preparation method and application thereof - Google Patents
Styrene-butadiene resin and preparation method and application thereof Download PDFInfo
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- CN112442149A CN112442149A CN202011310334.0A CN202011310334A CN112442149A CN 112442149 A CN112442149 A CN 112442149A CN 202011310334 A CN202011310334 A CN 202011310334A CN 112442149 A CN112442149 A CN 112442149A
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- styrene
- glue solution
- mass ratio
- butadiene resin
- butadiene
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- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 88
- 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 84
- 239000011347 resin Substances 0.000 title claims abstract description 84
- 229920005989 resin Polymers 0.000 title claims abstract description 84
- 239000002174 Styrene-butadiene Substances 0.000 title claims abstract description 82
- 239000011115 styrene butadiene Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000003292 glue Substances 0.000 claims abstract description 75
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000003999 initiator Substances 0.000 claims abstract description 28
- 238000009775 high-speed stirring Methods 0.000 claims abstract description 25
- 239000002535 acidifier Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 75
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 48
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 20
- 239000003963 antioxidant agent Substances 0.000 claims description 20
- 230000003078 antioxidant effect Effects 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 7
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 6
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 claims description 6
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000001630 malic acid Substances 0.000 claims description 6
- 235000011090 malic acid Nutrition 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000005639 Lauric acid Substances 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005022 packaging material Substances 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 5
- 239000000499 gel Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 239000000839 emulsion Substances 0.000 description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 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 4
- 125000003368 amide group Chemical group 0.000 description 4
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Chemical group 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/10—Copolymers of styrene with conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/02—Applications for biomedical use
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a styrene-butadiene resin and a preparation method and application thereof, wherein the preparation method comprises the following steps: reacting an initiator, a solvent, styrene and butadiene to obtain a mixed glue solution; reacting the mixed glue solution, the acidifying agent and the neutralizing agent under the condition of high-speed stirring to obtain the styrene-butadiene resin; the rotating speeds of the high-speed stirring are 1000-2500 r/min respectively and independently; according to the preparation method, the acidifying agent and the neutralizing agent react with the mixed glue solution under the condition of high-speed stirring, so that oxides generated in the reaction and storage processes of the initiator and peroxides generated in the reaction process are effectively removed, and the aim of reducing gel in the styrene-butadiene resin is fulfilled. The preparation method has simple process and convenient operation, and is suitable for mass production and use.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to styrene-butadiene resin as well as a preparation method and application thereof.
Background
The styrene-butadiene resin is a thermoplastic high polymer material with a block structure synthesized by using styrene and butadiene as monomers, alkyl lithium as an initiator and adopting an anionic solution polymerization technology. The styrene-butadiene resin has the advantages of high transparency, good impact resistance, small density, excellent processing performance, no toxicity and the like, so that the styrene-butadiene resin is widely applied to various fields of packaging, medical devices, household appliances, high-grade daily products, office supplies and the like.
In the prior art, a styrene-butadiene block copolymer and a production method thereof are reported, and CN103030756A discloses a styrene-butadiene copolymer and a preparation method and application thereof, wherein the styrene-butadiene copolymer with a polybutadiene chain segment capable of freely moving is obtained by adjusting the arrangement mode of a polystyrene chain segment and the polybutadiene chain segment, and the styrene-butadiene copolymer is mainly used for preparing high-gloss high-impact-resistance polystyrene. The styrene-butadiene copolymer solution with 5% concentration has low viscosity, and is added into polystyrene to form block in the molecular chain of polystyrene polymer and to flow freely in polystyrene. CN110041477A discloses an amido multifunctional styrene-butadiene transparent impact-resistant resin and a preparation method thereof, wherein the styrene-butadiene transparent impact-resistant resin is a terpolymer of butadiene, styrene and amido functional diphenylethylene derivatives, and is prepared by copolymerization of butadiene, styrene and amido functional diphenylethylene derivatives initiated by alkyl lithium, and a copolymer chain contains not less than 2 amido functional diphenylethylene derivative units; based on 100 percent of the total weight of the terpolymer, the mass percent of styrene is 45-90 percent, the mass percent of butadiene is 5-50 percent, and the balance is amino functionalized diphenylethylene derivatives; the method and the obtained amino multifunctional styrene-butadiene transparent impact-resistant resin can improve the thermal property of the styrene-butadiene transparent impact-resistant resin and the compatibility with other polar high polymers. However, in actual use, the prepared styrene-butadiene resin is difficult to use in time, the catalyst solution in the resin glue solution is long in standing time, a substance insoluble in cyclohexane is easy to precipitate out, the substance is strong in basicity, and if the substance is not treated in time, the strong basicity substance not only can influence the pH value of the polymer glue solution, but also influences the stability of the styrene-butadiene resin and reduces the anti-aging effect of an antioxidant in the styrene-butadiene resin; and the modified styrene-butadiene resin is easy to react with some substances with strong oxidizing property to form peroxide, so that the internal crosslinking of the molecular chain segment of the styrene-butadiene resin is accelerated, gel is generated, and the performance of the styrene-butadiene resin product is influenced.
Therefore, it is very important to avoid the generation of solvent-insoluble substances in the storage process of the styrene-butadiene resin, and to avoid the internal crosslinking of the molecular chain segments of the styrene-butadiene resin, thereby generating gel. CN102485762A discloses a butylbenzene segmented copolymer synthesized by organic lithium initiator and a preparation method thereof, organic lithium is adopted as initiator to carry out butadiene-styrene anion polymerization reaction in inert solvent; then, the termination reaction and the neutralization reaction of the hydroxy acid are respectively carried out in sequence. The styrene-butadiene block copolymer monomer unit prepared by the method has the bound styrene content of 10-60% by weight and the vinyl content of 6-18% by weight; and has the excellent properties of colorless and low gel content. However, the butylbenzene segmented copolymer prepared by the method still generates a small amount of gel in the storage process, and the gel reduction effect still needs to be improved.
Therefore, it is an urgent need to solve the problem of developing a preparation method capable of effectively removing peroxide and oxide generated during the reaction process to obtain a styrene-butadiene resin with low gel content.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide styrene-butadiene resin and a preparation method and application thereof, wherein the preparation method comprises the steps of reacting an initiator, a solvent, styrene and butadiene to obtain a mixed glue solution; and respectively reacting with the mixed glue solution by virtue of an acidifying agent and a neutralizing agent under the condition of high-speed stirring, effectively removing precipitates of butyl lithium, and controlling the pH value of the glue solution to be neutral to obtain the styrene-butadiene resin with low gel content.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a styrene-butadiene resin, comprising the steps of:
(1) reacting an initiator, a solvent and styrene to obtain styrene glue solution;
(2) reacting the styrene glue solution obtained in the step (1), styrene and butadiene to obtain a mixed glue solution;
(3) reacting the mixed glue solution obtained in the step (2) with an acidifying agent under the condition of high-speed stirring to obtain an acidified glue solution;
(4) reacting the acidified glue solution obtained in the step (3) with a neutralizing agent under a high-speed stirring condition to obtain the styrene-butadiene resin;
the rotation speed of the high-speed stirring in the step (3) and the step (4) is 1000-2500 r/min, such as 1050r/min, 1100r/min, 1150r/min, 1200r/min, 1250r/min, 1300r/min, 1500r/min, 1550r/min, 1700r/min, 1850r/min, 1900r/min, 2000r/min, 2050r/min, 2100r/min, 2250r/min, 2300r/min, 2350r/min, 2400r/min or 2450r/min, and the specific point values between the above-mentioned point values are limited to space and are not exhaustive for the sake of simplicity.
The preparation method of the styrene-butadiene resin provided by the invention comprises the following steps of firstly, reacting an initiator, a solvent and styrene to obtain styrene glue solution; then reacting the styrene glue solution, styrene and butadiene to obtain a mixed glue solution; and (2) reacting the mixed glue solution with an acidifying agent under the high-speed stirring condition at the rotating speed of 1000-2500 r/min to obtain an acidified glue solution, wherein if the rotating speed is too low, the separation effect is poor, the gel data is greatly deviated, the rotating speed is too high, centrifugal phase separation occurs, the contact effect is poor, and the pickling effect is not obvious. Finally, reacting the acidified glue solution and the neutralizing agent under the high-speed stirring condition with the rotating speed of 1000-2500 r/min, wherein if the rotating speed is too low, the neutralizing effect is not ideal, the glue solution is unstable, and the gel data offset is too large; too high rotation speed, centrifugation, dispersion of glue solution in corners, and poor neutralization effect. (ii) a Obtaining the styrene-butadiene resin. Under the high-speed stirring at the rotating speed of 1000-2500 r/min, oxide generated by an initiator and peroxide generated in the reaction process are removed through an acidifying agent, and the purpose of reducing gel is achieved.
Preferably, the rotation speed of the high-speed stirring in the step (3) and the step (4) is 1500-2500 r/min, such as 1600r/min 1800r/min 2000r/min 2100r/min 2200r/min 2300r/min or 2400r/min, and the specific points between the above points are limited to space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the mass ratio of the initiator to the solvent in the step (1) is 1 (150-250), such as 1:160, 1:170, 1:180, 1:190, 1:200, 1:210, 1:220, 1:230, 1:240, and the like.
Preferably, the mass ratio of the initiator to the styrene in the step (1) is 1 (15-25), such as 1:17, 1:19, 1:21, 1:22, 1:23, 1:24 or 1: 25.
Preferably, the initiator in step (1) is n-butyllithium.
Preferably, the reaction time in step (1) is 5-10 min, such as 5.5min, 6min, 6.5min, 7min, 7.5min, 8min, 8.5min, 9min or 9.5min, and the specific values between the above-mentioned values are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the reaction in step (1) is carried out under the protection of inert gas.
Preferably, the inert gas comprises any one of nitrogen, helium or argon or a combination of at least two thereof.
Preferably, a structure regulator is also added in the reaction in the step (1).
Preferably, the structure modifier is tetrahydrofuran.
Preferably, the mass ratio of the structure regulator to the styrene in the step (1) is 1 (50-150), such as 1:60, 1:70, 1:80, 1:90, 1:100, 1:110, 1:120, 1:130, 1:140, etc.
Preferably, the mass ratio of the styrene in the step (2) to the styrene in the step (1) is 1 (0.35-0.6), such as 1:0.36, 1:0.38, 1:0.4, 1:0.42, 1:44, 1:0.46, 1:48, 1:0.5, 1:0.52, 1:0.54, 1:0.56 or 1: 0.58.
Preferably, the mass ratio of the butadiene in the step (2) to the styrene in the step (1) is 1 (0.5-1.5), for example, 1:0.52, 1:0.54, 1:0.66, 1:0.68, 1:0.8, 1:1, 1:1.3, 1:1.4, 1:1.5, etc.
Preferably, the reaction time of step (2) is 30-60 min, such as 32min, 34min, 36min, 38min, 40min, 42min, 44min, 46min, 48min, 50min, 52min, 54min, 56min or 58min, and the specific values therebetween are limited by space and for simplicity, and the invention is not exhaustive.
Preferably, the reaction temperature in the step (2) is 45-60 ℃, for example, 47 ℃, 49 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃ or 58 ℃, and the specific values therebetween are limited by space and simplicity, and the invention is not exhaustive list of the specific values included in the range, and more preferably 50-51 ℃.
Preferably, the solid content of the mixed glue solution in the step (2) is 20-30%, for example, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28% or 29%, and specific values therebetween are limited by space and for brevity, and the invention is not exhaustive of the specific values included in the range, and more preferably 25-28%.
Preferably, the mass ratio of the acidifying agent in the step (3) to the initiator in the step (1) is 1 (1-10), such as 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8 or 1: 9.
Preferably, the acidifying agent comprises an organic acid.
Preferably, the organic acid comprises any one or a combination of at least two of malic acid, citric acid, n-capric acid, octadecanoic acid or lauric acid, and further preferably citric acid and/or malic acid.
Preferably, the reaction time in step (3) is 5-15 min, such as 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min or 14 min.
More preferably 10 to 15 min.
Preferably, the reaction temperature in step (3) is 45-60 ℃, such as 47 ℃, 49 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃ or 58 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, deionized water is also added to the reaction in step (3).
As a preferred technical scheme of the invention, deionized water is added in the reaction in the step (3) to fully dissolve acid and alkali in water, so that the acid and alkali are fully contacted with the glue solution, and common water has other ions which can cause interference.
Preferably, the mass ratio of the deionized water to the mixed glue solution in the step (2) is 1 (0.2-1), such as 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8 or 1: 0.9.
Preferably, the mass ratio of the neutralizing agent in the step (4) to the acidifying agent in the step (3) is 1 (1-10), such as 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8 or 1: 9.
Preferably, the neutralizing agent comprises any one of lithium carbonate, sodium carbonate or potassium carbonate or a combination of at least two thereof, and further preferably sodium carbonate.
Preferably, the reaction time in step (4) is 5-10 min, such as 5.5min, 6min, 6.5min, 7min, 7.5min, 8min, 8.5min, 9min or 9.5min, and the specific values between the above-mentioned values are limited by the space and for the sake of brevity, and the invention is not exhaustive and the specific values included in the range are further preferably 7-8 min.
Preferably, the reaction temperature in the step (4) is 45-60 ℃, for example 46 ℃, 47 ℃, 48 ℃, 49 ℃, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 56 ℃ or 58 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range, and more preferably 50-55 ℃.
Preferably, the reaction in step (4) has a pH of 6.5 to 8, such as 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.3, 7.4, 7.6, 7.8 or 7.9, and specific values therebetween are not exhaustive, and for brevity, the invention does not include the specific values included in the range, and more preferably, the pH is 7 to 7.5.
Preferably, the method further comprises the steps of standing and adding an antioxidant after the reaction in the step (4) is finished.
As a preferred technical scheme of the invention, the acidifying agent and the neutralizing agent are used for reacting with the mixed glue solution under the condition of high-speed stirring, then the mixed glue solution is kept stand, and then the antioxidant is added, so that the anti-aging performance of the antioxidant is improved, and the intramolecular cross-linking probability of the glue solution in a high-temperature environment is reduced.
Preferably, the standing time is 10-20 min, such as 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min or 19min and the specific values therebetween, which are limited by space and for brevity, the invention does not exhaust the specific values included in the range, and is further preferably 15-20 min.
Preferably, the antioxidant comprises pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or tris (2, 4-di-tert-butylphenyl) phosphite.
Preferably, the content of the antioxidant in the styrene-butadiene resin is 1-3% by mass, such as 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6% or 2.8%, and more preferably 1-1.5%.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) reacting an initiator, a solvent, styrene and a structure regulator for 5-10 min under the protection of inert gas to obtain styrene glue solution; the mass ratio of the initiator to the solvent is 1 (150-250); the mass ratio of the initiator to the styrene is 1 (15-25);
(2) reacting the styrene glue solution obtained in the step (1), styrene and butadiene at 45-60 ℃ for 30-60 min to obtain a mixed glue solution with the solid content of 20-30%; (3) reacting the mixed glue solution obtained in the step (2), an acidifying agent and deionized water for 5-15 min under the conditions of high-speed stirring at the temperature of 45-60 ℃ and the rotating speed of 1000-2500 r/min to obtain an acidified glue solution; the mass ratio of the acidifying agent to the initiator in the step (1) is 1 (1-10), and the mass ratio of the deionized water to the mixed glue solution in the step (2) is 1 (0.2-1);
(4) reacting the acidified glue solution obtained in the step (3) with a neutralizing agent under the high-speed stirring conditions of 45-60 ℃, pH value of 6.5-8 and rotation speed of 1000-2500 r/min for 5-10 min, standing for 10-20 min, and adding an antioxidant to obtain the styrene-butadiene resin; the mass ratio of the neutralizing agent to the acidifying agent in the step (3) is 1 (1-10).
In a second aspect, the present invention provides a styrene-butadiene resin, wherein the styrene-butadiene resin is prepared by the preparation method according to the first aspect.
In a third aspect, the invention provides a use of the styrene-butadiene resin according to the second aspect in toys, packaging materials or medical devices.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of the styrene-butadiene resin, provided by the invention, the initiator, the solvent, the styrene and the butadiene are reacted to obtain a mixed glue solution, and then the mixed glue solution is reacted with an acidifier and a neutralizer under a high-speed stirring condition, so that oxides generated in the reaction and storage processes of the initiator and peroxides generated in the reaction process are effectively removed, the purpose of reducing gel is achieved, and the purpose of reducing the residual solvent in the polymer is realized; the styrene-butadiene resin prepared by the preparation method of the styrene-butadiene resin provided by the invention has less gel; specifically, the present invention providesThe styrene-butadiene resin is 0.1-0.5 mm2The number of gels in the range of 56 to 110, 0.5 to 0.7mm2The number of gels in the range of 12 to 100, 0.7 to 500mm2The number of gels in the range is 10-160, and is reduced by 20-563% compared with the number of gels (180-398) in the range of 0.1-0.5 mm2, the number of gels (150-390) in the range of 0.5-0.7 mm2 and the number of gels (190-400) in the range of 0.7-500 mm2 in the prior art, respectively, by 19-3900%; and the preparation method has simple process and convenient operation, and is suitable for mass production and use.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A preparation method of styrene-butadiene resin specifically comprises the following steps:
(1) under the protection of high-purity nitrogen, adding 4500g of cyclohexane/n-hexane (the mass ratio of cyclohexane to n-hexane is 8:1) mixed solvent, 4g of Tetrahydrofuran (THF), 400g of styrene and 21g of n-butyl lithium into a 10L reaction kettle in sequence, and reacting for 7.5min to obtain styrene glue solution;
(2) adding 400g of butadiene and 800g of styrene into the styrene glue solution obtained in the step (1), and reacting for 45min at the temperature of 52.5 ℃ to obtain a mixed glue solution with the solid content of 26.2%;
(3) putting the mixed glue solution with the solid content of 26.2% obtained in the step (2) into a 10L high-speed stirring kettle, and adding deionized water, wherein the mass ratio of the deionized water to the mixed glue solution is 5: 1; adding citric acid, wherein the mass ratio of the citric acid to the n-butyllithium is 1:3, and reacting for 5min at the rotation speed of 2000r/min and the temperature of 50 ℃ to obtain an acidified glue solution;
(4) adding sodium carbonate into the acidified glue solution obtained in the step (3), wherein the mass ratio of the sodium carbonate to citric acid is 1:1, reacting for 10min at the rotation speed of 2000r/min and the temperature of 50 ℃, standing for 10min, then layering, transferring an upper layer emulsion, adding a mixed antioxidant of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010) and tris (2, 4-di-tert-butylphenyl) phosphite (168) into the emulsion, wherein the mixed antioxidant accounts for 1.5% by mass in the emulsion, and the mass ratio of 1010 to 168 in the mixed antioxidant is 1:1, so as to obtain the styrene-butadiene resin.
Examples 2 and 3
The preparation method of the styrene-butadiene resin is different from that of the example 1 only in that the mass ratio of the deionized water to the mixed glue solution in the step (3) is 2:1 (example 2) and 4:1 (example 3), and other conditions, the use amount and the steps are the same as those in the example 1, so that the styrene-butadiene resin is obtained.
Examples 4 and 5
A preparation method of a styrene-butadiene resin, which is different from example 1 only in that the citric acid and n-butyllithium in the step (3) are in a mass ratio of 1:10 (example 4) and 1:1.11 (example 5), and other conditions, amounts and steps are the same as those of example 1, to obtain the styrene-butadiene resin.
Examples 6 to 8
A preparation method of styrene-butadiene resin, which is different from example 1 only in that the mass ratio of sodium carbonate to citric acid in step (4) is 1:10 (example 6), 1:5 (example 7) and 1:1.11 (example 8), and other conditions, amounts and steps are the same as those in example 1, to obtain the styrene-butadiene resin.
Examples 9 and 10
A preparation method of styrene-butadiene resin is different from that of the embodiment 1 only in that the rotation speed of the step (3) and the rotation speed of the step (4) are both 1000r/min (the embodiment 9) and 1500r/min (the embodiment 10), and other conditions, the use amount and the steps are the same as those of the embodiment 1, so that the styrene-butadiene resin is obtained.
Example 11
A preparation method of styrene-butadiene resin specifically comprises the following steps:
(1) under the protection of high-purity nitrogen, adding 4500g of cyclohexane/n-hexane (the mass ratio of cyclohexane to n-hexane is 8:1) mixed solvent, 4g of Tetrahydrofuran (THF), 450g of styrene and 30g of n-butyl lithium into a 10L reaction kettle in sequence, and reacting for 5min to obtain styrene glue solution;
(2) adding 300g of butadiene and 750g of styrene into the styrene glue solution obtained in the step (1), and reacting for 30min at the temperature of 45 ℃ to obtain a mixed glue solution;
(3) putting the mixed glue solution with the solid content of 25% obtained in the step (2) into a 10L high-speed stirring kettle, and adding deionized water, wherein the mass ratio of the deionized water to the mixed glue solution is 5: 1; adding citric acid, wherein the mass ratio of the citric acid to the n-butyllithium is 1:1, and reacting for 5min at the rotating speed of 2000r/min and the temperature of 45 ℃ to obtain an acidified glue solution;
(4) adding lithium carbonate into the acidified glue solution obtained in the step (3), wherein the mass ratio of lithium carbonate to citric acid is 1:1, reacting for 5min at the rotation speed of 2000r/min and the temperature of 45 ℃, standing for 15min, layering, transferring an upper layer emulsion, and adding an antioxidant 1010 and a antioxidant 168 mixed antioxidant into the emulsion, wherein the mass percentage of the mixed antioxidant in the emulsion is 1.5%, and the mass ratio of the antioxidant 1010 to the antioxidant 168 in the mixed antioxidant is 1: 1; and finally, transferring to a devolatilization machine for removing, pelletizing and film drawing through a casting film machine to obtain the styrene-butadiene resin.
Example 12
A preparation method of styrene-butadiene resin specifically comprises the following steps:
(1) under the protection of high-purity nitrogen, 4500g of cyclohexane/n-hexane mixed solvent, 3g of Tetrahydrofuran (THF), 450g of styrene and 18g of n-butyl lithium are sequentially added into a 10L reaction kettle, and the mixture reacts for 15min to obtain styrene glue solution;
(2) adding 225g of butadiene and 1500g of styrene into the styrene glue solution obtained in the step (1), and reacting for 60min at the temperature of 60 ℃ to obtain a mixed glue solution;
(3) putting the mixed glue solution with the solid content of 30% obtained in the step (2) into a 10L high-speed stirring kettle, and adding deionized water, wherein the mass ratio of the deionized water to the mixed glue solution is 10: 1; adding malic acid, wherein the mass ratio of citric acid to n-butyllithium is 1:5, and reacting for 15min at the rotation speed of 2500r/min and the temperature of 60 ℃ to obtain an acidified glue solution;
(4) adding sodium carbonate into the acidified glue solution obtained in the step (3), wherein the mass ratio of the sodium carbonate to the malic acid is 1:10, reacting for 7min at the rotation speed of 2000r/min and the temperature of 60 ℃, standing for 20min, layering, transferring the upper emulsion, adding an antioxidant 1010 and a antioxidant 168 mixed antioxidant into the emulsion, wherein the mixed antioxidant is 3% in the emulsion by mass, and the mass ratio of the antioxidant 1010 to the optometry 168 in the mixed antioxidant is 1: 2; and finally, transferring to a devolatilization machine for removing, pelletizing and film drawing through a casting film machine to obtain the styrene-butadiene resin.
Example 13
A preparation method of styrene-butadiene resin, which is different from the embodiment 1 only in that deionized water is not added in the step (3), citric acid is directly added, and other conditions, dosage and steps are the same as the embodiment 1, so as to obtain the styrene-butadiene resin.
Comparative example 1
A preparation method of styrene-butadiene resin is different from that of example 1 only in that the rotation speed in the step (3) and the rotation speed in the step (4) are both 500r/min, and other conditions, the using amount and the steps are the same as those of example 1, so that the styrene-butadiene resin is obtained.
Comparative example 2
A preparation method of styrene-butadiene resin is different from that of the embodiment 1 only in that the rotating speed of the step (3) and the rotating speed of the step (4) are 3100r/min, and other conditions, the using amount and the steps are the same as those of the embodiment 1, so that the styrene-butadiene resin is obtained.
Comparative examples 3 and 4
A preparation method of styrene-butadiene resin is different from that of example 1 only in that the rotation speed of step (3) is 500r/min (comparative example 3) and 3100r/min (comparative example 4), respectively, and other conditions, amounts and steps are the same as those of example 1, to obtain the styrene-butadiene resin.
Comparative examples 5 and 6
A method for preparing styrene-butadiene resin, which is different from example 1 only in that the rotation speeds of step (4) are 500r/min (comparative example 5) and 3100r/min (comparative example 6), respectively, and other conditions, amounts and steps are the same as those of example 1, to obtain the styrene-butadiene resin.
Comparative example 7
A preparation method of styrene-butadiene resin is different from that of the embodiment 1 only in that sodium carbonate is not added in the step (4), and the mixture is directly kept still for 10min, and other conditions, use amounts and steps are the same as those of the embodiment 1, so that the styrene-butadiene resin is obtained.
Comparative example 8
A preparation method of styrene-butadiene resin, which is different from example 1 only in that citric acid is not added in step (3) and other conditions, amounts and steps are the same as example 1 to obtain the styrene-butadiene resin.
Comparative example 9
A preparation method of styrene-butadiene resin, which is different from example 1 only in that citric acid is not added in step (3) and sodium carbonate is not added in step (4), and other conditions, amounts and steps are the same as example 1 to obtain the styrene-butadiene resin.
And (3) performance testing:
(1) the gel amount: the styrene-butadiene resins obtained in the examples 1-13 and the comparative examples 1-9 are subjected to film removal, grain cutting and film drawing by a film casting machine, and then a surface defect detection system (CCD surface defect detection system, model CXA01-01) is used for analyzing the film-forming styrene-butadiene resin (the sample film width is 25cm, and the film length is 170 cm); the method comprises the following specific operation steps: firstly, a casting film machine is cleaned by using a low-gel material, a sample is added, the sample is washed for 20 minutes, then, a surface defect detection system instrument is used for shooting gel points through a camera, and then, the gel points are classified according to sizes, so that the number of gels in the gel number is counted.
The styrene-butadiene resins obtained in examples 1 to 13 and comparative examples 1 to 9 were tested according to the above test method, and the test results are shown in table 1:
TABLE 1
As can be seen from the data in table 1:
the styrene-butadiene resin prepared by the preparation method of the styrene-butadiene resin provided by the invention has less gel; specifically, the styrene-butadiene resins provided in examples 1 to 13 were 0.1 to 0.5mm in thickness2The number of gels in the range of 60 to 150, in the range of 0.5 to 0.7mm2The number of gels in the range of 12 to 100, 0.7 to 500mm2The number of gels in the range of 10 to 160, compared to styrene-butadiene resins provided in comparative examples 1 to 9, is 0.1 to 0.5mm2The number of gels (180-398) in the range is reduced by 20-563% and is 0.5-0.7 mm2The number of gels (150-390 gels) in the range is reduced by 50-3150%, 0.7-500 mm2The number of gels (190-400 gels) in the range is reduced by 19-3900%, and the fact that the acidifying agent and the neutralizing agent react with the mixed glue solution under the condition of high-speed stirring is proved to effectively reduce the number of gels in the preparation and storage processes of the styrene-butadiene resin.
The applicant states that the present invention is illustrated by the above examples to describe a styrene-butadiene resin and a preparation method and an applied process method thereof, but the present invention is not limited to the above process steps, i.e., it does not mean that the present invention must be implemented by relying on the above process steps. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. The preparation method of the styrene-butadiene resin is characterized by comprising the following steps of:
(1) reacting an initiator, a solvent and styrene to obtain styrene glue solution;
(2) reacting the styrene glue solution obtained in the step (1), styrene and butadiene to obtain a mixed glue solution;
(3) reacting the mixed glue solution obtained in the step (2) with an acidifying agent under the condition of high-speed stirring to obtain an acidified glue solution;
(4) reacting the acidified glue solution obtained in the step (3) with a neutralizing agent under a high-speed stirring condition to obtain the styrene-butadiene resin;
and (4) the rotating speed of the high-speed stirring in the step (3) and the step (4) is 1000-2500 r/min respectively and independently.
2. The method according to claim 1, wherein the high-speed stirring in step (3) and step (4) is performed at a rotation speed of 1500 to 2500 r/min.
3. The preparation method according to claim 1 or 2, wherein the mass ratio of the initiator to the solvent in the step (1) is 1 (150-250);
preferably, the mass ratio of the initiator to the styrene in the step (1) is 1 (15-25);
preferably, the initiator in step (1) is n-butyllithium;
preferably, the reaction time in the step (1) is 5-10 min;
preferably, the reaction in the step (1) is carried out under the protection of inert gas;
preferably, the inert gas comprises any one or a combination of at least two of nitrogen, helium, or argon;
preferably, a structure regulator is also added in the reaction in the step (1);
preferably, the structure modifier is tetrahydrofuran;
preferably, the mass ratio of the structure regulator to the styrene in the step (1) is 1 (50-150).
4. The production method according to any one of claims 1 to 3, wherein the mass ratio of the styrene in the step (2) to the styrene in the step (1) is 1 (0.35 to 0.6);
preferably, the mass ratio of the butadiene in the step (2) to the styrene in the step (1) is 1 (0.5-1.5);
preferably, the reaction time in the step (2) is 30-60 min;
preferably, the reaction temperature in the step (2) is 45-60 ℃, and further preferably 50-51 ℃;
preferably, the solid content of the mixed glue solution in the step (2) is 20-30%, and more preferably 25-28%.
5. The method according to any one of claims 1 to 4, wherein the mass ratio of the acidifying agent in step (3) to the initiator in step (1) is 1 (1 to 10);
preferably, the acidifying agent comprises an organic acid;
preferably, the organic acid comprises any one or combination of at least two of malic acid, citric acid, n-capric acid, octadecanoic acid or lauric acid, and is further preferably citric acid and/or malic acid;
preferably, the reaction time in the step (3) is 5-15 min, and more preferably 10-15 min;
preferably, the reaction temperature in the step (3) is 45-60 ℃;
preferably, deionized water is also added into the reaction in the step (3);
preferably, the mass of the deionized water and the mixed glue solution in the step (2) is 1 (0.2-1).
6. The method according to any one of claims 1 to 5, wherein the mass ratio of the neutralizing agent in the step (4) to the acidifying agent in the step (3) is 1 (1 to 10);
preferably, the neutralizing agent comprises any one or a combination of at least two of lithium carbonate, sodium carbonate or potassium carbonate, and further preferably sodium carbonate;
preferably, the reaction time in the step (4) is 5-10 min, and more preferably 7-8 min;
preferably, the reaction temperature in the step (4) is 45-60 ℃, and further preferably 50-55 ℃;
preferably, the pH value of the reaction in the step (4) is 6.5-8; more preferably 7 to 7.5.
7. The preparation method according to any one of claims 1 to 6, characterized by further comprising the steps of standing and adding an antioxidant after the reaction in the step (4);
preferably, the standing time is 10-20 min, and further preferably 15-20 min;
preferably, the antioxidant comprises pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or tris (2, 4-di-tert-butylphenyl) phosphite;
preferably, the mass percentage of the antioxidant in the styrene-butadiene resin is 1-3%, and more preferably 1-1.5%.
8. The production method according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) reacting an initiator, a solvent, styrene and a structure regulator for 5-10 min under the protection of inert gas to obtain styrene glue solution; the mass ratio of the initiator to the solvent is 1 (150-250); the mass ratio of the initiator to the styrene is 1 (15-25);
(2) reacting the styrene glue solution obtained in the step (1), styrene and butadiene at 45-60 ℃ for 30-60 min to obtain a mixed glue solution with the solid content of 20-30%;
(3) reacting the mixed glue solution obtained in the step (2), an acidifying agent and deionized water for 5-15 min under the conditions of high-speed stirring at the temperature of 45-60 ℃ and the rotating speed of 1000-2500 r/min to obtain an acidified glue solution; the mass ratio of the acidifying agent to the initiator in the step (1) is 1 (1-10), and the mass ratio of the deionized water to the mixed glue solution in the step (2) is 1 (0.2-1);
(4) reacting the acidified glue solution obtained in the step (3) with a neutralizing agent under the high-speed stirring conditions of 45-60 ℃, pH value of 6.5-8 and rotation speed of 1000-2500 r/min for 5-10 min, standing for 10-20 min, and adding an antioxidant to obtain the styrene-butadiene resin; the mass ratio of the neutralizing agent to the acidifying agent in the step (3) is 1 (1-10).
9. Styrene-butadiene resin, characterized in that the styrene-butadiene resin is prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the styrene-butadiene resin according to claim 9 in toys, packaging materials or medical devices.
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| CN114106272A (en) * | 2021-12-27 | 2022-03-01 | 广东众和高新科技有限公司 | Anti-scratch styrene-butadiene resin and preparation method thereof |
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