CN114573744A - Method for reducing residual styrene-acrylonitrile copolymer resin and application - Google Patents
Method for reducing residual styrene-acrylonitrile copolymer resin and application Download PDFInfo
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- CN114573744A CN114573744A CN202210244527.3A CN202210244527A CN114573744A CN 114573744 A CN114573744 A CN 114573744A CN 202210244527 A CN202210244527 A CN 202210244527A CN 114573744 A CN114573744 A CN 114573744A
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- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 title claims abstract description 78
- 229920005989 resin Polymers 0.000 title claims abstract description 74
- 239000011347 resin Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 35
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 29
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 19
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000155 melt Substances 0.000 claims abstract description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 54
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 239000002002 slurry Substances 0.000 claims description 44
- 239000000178 monomer Substances 0.000 claims description 32
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 30
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000005453 pelletization Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 125000003367 polycyclic group Chemical group 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 24
- 239000002994 raw material Substances 0.000 description 18
- 238000010992 reflux Methods 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 8
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- UPMAOXLCTXPPAG-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalen-2-ol Chemical compound C1CCCC2CC(O)CCC21 UPMAOXLCTXPPAG-UHFFFAOYSA-N 0.000 description 5
- AFKMHDZOVNDWLO-UHFFFAOYSA-N 4-cyclohexylcyclohexan-1-ol Chemical compound C1CC(O)CCC1C1CCCCC1 AFKMHDZOVNDWLO-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000006200 vaporizer Substances 0.000 description 3
- OGTQKBVGJXAEIQ-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalene-2-thiol Chemical compound C1CCCC2CC(S)CCC21 OGTQKBVGJXAEIQ-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- -1 2-bicyclo [2.2.1]Heptanol (Heptan) Chemical compound 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- NVCAPSBEHAGNSO-UHFFFAOYSA-N bicyclo[3.1.0]hexan-6-ol Chemical compound C1CCC2C(O)C21 NVCAPSBEHAGNSO-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000010812 external standard method Methods 0.000 description 2
- 238000003988 headspace gas chromatography Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
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- 150000003573 thiols Chemical class 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 1
- ZTVJNQUORIPHGY-UHFFFAOYSA-N 4-cyclohexylcyclohexane-1-thiol Chemical compound C1CC(S)CCC1C1CCCCC1 ZTVJNQUORIPHGY-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- VPIAKHNXCOTPAY-UHFFFAOYSA-N Heptane-1-thiol Chemical compound CCCCCCCS VPIAKHNXCOTPAY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- IOPZYMJYUACERA-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3-thiol Chemical compound C1CC2C(S)CC1C2 IOPZYMJYUACERA-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- CMKBCTPCXZNQKX-UHFFFAOYSA-N cyclohexanethiol Chemical compound SC1CCCCC1 CMKBCTPCXZNQKX-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- ZQTYQMYDIHMKQB-UHFFFAOYSA-N exo-norborneol Chemical compound C1CC2C(O)CC1C2 ZQTYQMYDIHMKQB-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- 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 method for reducing residual styrene-acrylonitrile copolymer (SAN) resin and application thereof. By adopting the mercaptan with a special structure as a chain transfer agent and introducing a fat polycyclic structure at the chain end of a macromolecule chain, the mutual entanglement of the molecular chains of the resin is reduced in the heating process of the resin, and the melt flowability and devolatilization effect are improved, so that the residue of the SAN resin product is obviously reduced, and the resin can be further used for preparing low-residue ABS resin.
Description
Technical Field
The invention belongs to the technical field of SAN resin, and particularly relates to a method for reducing residual styrene-acrylonitrile copolymer (SAN) resin and application thereof.
Background
The styrene-acrylonitrile copolymer (SAN) resin is a styrene and acrylonitrile copolymer and is mainly used for further preparing ABS resin by blending with ABS rubber powder containing polybutadiene rubber, and the resin is widely applied to a plurality of application fields such as transportation, electronic appliances and the like because the three monomers respectively endow the ABS with excellent performance.
Although ABS resin has the above various advantages, it still has the problems of large processing odor and contact migration of toxic residues. The literature 'research on ABS/AS plastic food contact material regulations at home and abroad' (Chengming, food safety quality inspection report, 2013, 4(4)) indicates that public attention to the sanitation safety problem of the ABS/AS plastic food contact material is obviously improved. In addition, strict standards are established for the content of residual monomers, particularly the content of acrylonitrile, in the material in Korea in the United states of Europe and America (the transfer volume of acrylonitrile is required to be less than 0.01mg/kg in European Union, and the residual amount of acrylonitrile is required to be less than 50mg/kg in China).
In general, ABS is based on > 70% SAN resin, so that controlling the residual in the raw material SAN can effectively improve the ABS residual index. In the existing SAN polymerization process, the conversion rate of polymerization reaction is about 60-80%, and the residual monomers are removed by stripping devolatilization and other modes; the monomer residues in the resin are therefore closely related to the devolatilization effect of the resin melt. It is worth noting that ABS resin is very easy to be yellowed obviously under high temperature condition, see "Thermal Styrene-co-acrylic dispersion purifying solution: The Role of Sequence dispersion and Oligomers" (D.S. Allan, Macromolecules 1993, 26, 6068-.
The fundamental reason for analyzing the method is that because the polymer melt devolatilization process is limited by multiple factors such as viscosity, temperature, vacuum degree, equipment specific surface area updating effect, retention time and the like of a process system, when the content of the residual monomer is reduced to the ppm level, the concentration difference is difficult to further improve the mass transfer effect, so that the further reduction of the residual monomer becomes more difficult.
The prior art also tries to improve the problem, such as CN 109467870A adopts a multi-stage devolatilization mode to improve the resin residual sheet and the odor thereof, wherein the residual sheet amount can be further reduced by adopting a stripping mode. In the literature, "research on a process for reducing ABS resin residue" (Liushuang, oil refining and chemical engineering, 2010, 21(03)) optimization of resin residue is performed by optimizing another raw material ABS rubber powder process, and the research content does not include SAN resin residue optimization part.
In the prior art, SAN resin residual index is improved by adopting a strengthening devolatilization method, and the hue of the resin and the low residual of a finished product cannot be considered at the same time.
Therefore, it is necessary to provide a process method to improve the gas phase mass transfer during the devolatilization process and reduce the residual resin content.
Disclosure of Invention
The invention aims to provide a preparation method of SAN resin with low residue, which fundamentally improves gas phase mass transfer in the devolatilization process and reduces the residue content of the resin.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for reducing the residual styrene-acrylonitrile copolymer (SAN) resin, comprising the steps of:
s1: mixing styrene, acrylonitrile, a chain transfer agent and a solvent to obtain a monomer mixed solution;
s2: adding the monomer mixed solution into a first reactor for polymerization reaction to obtain slurry A, and continuously adding the slurry A into a second reactor for continuous polymerization reaction to obtain slurry B;
s3: continuously feeding the slurry B into a devolatilization device, removing unreacted monomers and solvents, and pelletizing the melt to obtain SAN resin;
wherein the chain transfer agent is aliphatic polycyclic tertiary mercaptan with 5-20 carbon atoms, preferably aliphatic polycyclic tertiary mercaptan with 6-18 carbon atoms, more preferably the chain transfer agent structure is R-SH, wherein R is one or more of the following structures:
according to the invention, the special mercaptan with the aliphatic polycyclic tertiary group structure is used as a chain transfer agent, the polymerization reaction cyclic residue of the mercaptan is remained at one end of a high molecular chain, and the mercaptan plays a role in reducing molecular chain entanglement in the subsequent devolatilization process of a high molecular weight polymer melt, so that the system viscosity is obviously reduced, and the effects of improving devolatilization mass transfer and reducing melt residue are achieved. In the present invention, the residual is the residual raw material styrene, acrylonitrile and solvent in the resin.
In the invention, the addition amount of each component in the monomer mixed solution of S1 is as follows: 60-85 parts of styrene, 15-40 parts of acrylonitrile, 0.05-0.5 part of chain transfer agent and 5-20 parts of solvent; preferably, the amount of the chain transfer agent added is preferably 0.05 to 0.3 wt% of the total amount of the monomers; preferably, the solvent is one or more of toluene, ethylbenzene, tetrahydrofuran, dichloromethane, preferably toluene and/or ethylbenzene.
In the invention, the first reactor and the second reactor of S2 are full mixed flow reactors; preferably, the first reactor and the second reactor are connected in series.
In the invention, the temperature of the first reactor of S2 is 145-165 ℃, preferably 150-160 ℃, the residence time is 0.5-3h, preferably 1-2h, and the outlet conversion rate is 40-60%.
In the invention, the temperature of the second reactor of S2 is 145-165 ℃, preferably 150-160 ℃, the residence time is 0.5-3h, preferably 1-2h, and the outlet conversion rate is 60-80%.
In the invention, the melt temperature of the devolatilizer of S3 is controlled to be 250 ℃ minus 180 ℃, preferably 230 ℃ minus 210 ℃, and the absolute pressure is controlled to be less than or equal to 5KPa, preferably less than or equal to 3 KPa.
In the method provided by the invention, any type of additives with any content commonly used in the field, including but not limited to release agents, ultraviolet absorbers, antioxidants, colorants and the like, can be added in the process according to the required properties of the SAN resin.
It is another object of the present invention to provide a low residue SAN resin.
A low residual SAN resin is prepared by the method for reducing the residual of styrene-acrylonitrile copolymer (SAN) resin, wherein the residual content of the SAN resin is 350-1200ppm, preferably 400-1000 ppm.
It is yet another object of the present invention to provide a use of a low residue SAN resin.
Use of a low residual SAN resin obtained by the above-described method for reducing residual styrene-acrylonitrile copolymer (SAN) resin for blending to produce a low residual ABS resin.
Compared with the prior art, the invention has the advantages that:
(1) compared with the conventional process, the preparation method of the SAN resin provided by the invention has the advantages that the product has lower residual and monomer contents (the residual content in the resin can be reduced to 400-1000ppm), and can meet higher sanitary standard requirements in the application fields of food contact, medical use, refrigerator liners and the like.
(2) The preparation method provided by the invention has simple and convenient process, can be directly implemented in the existing device, and is very suitable for large-scale industrial production.
Drawings
FIG. 1 is a schematic view of a system for preparing a styrene-acrylonitrile copolymer according to the present invention;
FIG. 2 shows the thiol prepared in example 11H NMR spectrum;
FIG. 3 is a graph comparing shear viscosity of SAN resins prepared in example 1 and comparative example 1.
Detailed description of the preferred embodiments
The invention is further illustrated by the following examples and comparative examples, which, however, do not limit the scope of the invention as claimed.
Raw material specification:
| raw materials/specification | Manufacturer of the product | Specification of |
| Styrene (meth) acrylic acid ester | Qilu petrochemical | Industrial grade |
| Acrylonitrile | Jilin petrochemical | >98.5％ |
| 6-bicyclo [3.1.0]HexOH | Merck | >99％ |
| 2-bicyclo [2.2.1]Heptanol (Heptan) | Merck | >97％ |
| 9-tricyclo [4.3.3.0]Decanol | Merck | >97％ |
| 4-Cyclohexylcyclohexanol | Sigma-Aldrich | >98.5％ |
| Decahydro-2-naphthol | Sigma-Aldrich | >97％ |
| Toluene | Shandongjing medicine | Industrial grade |
| Ethylbenzene production | Koimeu tea | Reagent grade |
| HR181 gelatin powder | Korea Jinhu lake | 60% gum content |
| EBS | Huanhao chemical industry | Granular material |
| Antioxidant agent | Lianlong medicine | Optimally matched B7077G |
Experimental equipment:
the analysis method comprises the following steps:
in the examples and comparative examples of the present invention, the first reactor and the second reactor were all a total mixed flow reactor.
In the examples and comparative examples of the present invention, the monomer conversion rate during polymerization, the molecular weight of the final SAN resin, and the residual test method of the final blended ABS resin were as follows:
resin content (reaction conversion) test: an Agilent 7697A headspace gas chromatography is adopted to test the content of unreacted styrene and acrylonitrile in SAN reaction liquid, and a DMF dissolution sample and an external standard method are adopted to test the conversion rate of monomer content conversion in the feeding composition.
SAN resin molecular weight: using methylene chloride as a solvent, and using a Shimadzu Japan 20AD gel permeation chromatograph to test the molecular weight of the SAN resin;
shear viscosity: testing by Malvern MH2000 capillary rheometer200℃、100S-1Shear viscosity of lower resin melt.
SAN/ABS resin residual test: an Agilent 7697A headspace gas chromatography is adopted, the determination of solvents such as residual styrene, acrylonitrile, toluene, ethylbenzene and the like in resin is carried out by referring to GB/T5009.152-2003 determination of styrene-acrylonitrile copolymer for food packaging, rubber modified acrylonitrile-butadiene-styrene resin and residual acrylonitrile monomer in molded products thereof, DMF is adopted to dissolve samples, and external standard method test is carried out.
NMR measurement: using CDCl3The samples were dissolved and subjected to hydrogen spectroscopy on synthetic thiols by a Bruker 400MHz NMR instrument.
Example 1
Decahydro-2-naphthol is used as a raw material to prepare decahydro-naphthalene-2-thiol. MCM-41 molecular sieve is used as catalyst and filled in
In a fixed bed reactor (the reactor is connected with H)2S high-pressure steel cylinder, plunger pump and gasifier are used for feeding raw material decahydro-2-naphthol), the set temperature of the fixed bed reactor is 290 ℃, decahydro-2-naphthol is conveyed into the gasifier through the plunger pump and gasified at 260 ℃, and H is reacted with decahydro-2-naphthol2S is prepared from the following components in percentage by mass 1: 0.35, mixing evenly, feeding into a fixed bed reactor, and controlling the gas velocity of 1-1.5MPaG in the reaction process for 65h-1Cooling the product by a condenser, separating liquid, and absorbing non-condensable gas by using a 20% NaOH solution; the reaction solution obtained by liquid separation is further refined by reduced pressure distillation (batch operation, the reflux/extraction ratio at the top of the tower is maintained at 4:1, and the fraction with the temperature of 191-192 ℃ under 8KPaA is collected) to obtain the decalin-2-mercaptan with the purity of 99.2 percent, and a nuclear magnetic spectrum chart is shown in figure 2.
80Kg of styrene, 20Kg of acrylonitrile, 12Kg of toluene and 0.1Kg of the above self-made chain transfer agent, decahydronaphthalene-2-thiol, were added to a 200L compounding tank and mixed well.
Referring to fig. 1, the above raw material mixture was fed into a first reactor R101 having a capacity of 30L at a feed rate of 10kg/h, and the temperature of R101 was controlled to be 160 ℃ by adjusting the amount of gas phase condensate reflux, and the average residence time of the material in R101 was 1h, to obtain slurry a. The monomer conversion of slurry a was tested to be 50%.
Continuously conveying the slurry A into a fully-mixed flow polymerization kettle R102 with the volume of 30L and good heat preservation at the feeding speed of 10L/h, controlling the temperature of the R102 to be 160 ℃ by adjusting the gas phase condensation reflux quantity, and controlling the average residence time of the materials in the R101 to be 1h to obtain the slurry B. The monomer conversion of slurry B was tested to be 70%.
Feeding the slurry B into a falling strip devolatilizer D101, controlling the temperature of the melt in the devolatilizer to be 220 ℃ and the pressure to be 1.5 KPaA. And water-cooling and pelletizing the devolatilized polymer melt to obtain a granular SAN product.
After the operation is stable, mixing the finished SAN resin, HR181 rubber powder, EBS and antioxidant by a double-screw extruder (type: Kedoulong STS50 MC11) according to the mass ratio of 75:25:2:1 under the following conditions (the maximum temperature of a cylinder is 200 ℃, the head temperature is 220 ℃, the screw rotating speed is 400rpm, the feeding frequency is 20Hz, the current is 35A, the torque is 75-80%), cooling by a water tank, and granulating to further prepare the ABS resin.
The SAN resin prepared by the test has the molecular weight distribution of Mw 126995 and PDI 2.94 and the shear viscosity of 1033 Pa.S (200 ℃, 100S)-1). The residual contents of the SAN resin are respectively styrene: 444.32ppm, acrylonitrile: 25.75ppm, toluene: 375.93 ppm. The residual contents in the further prepared ABS resin are respectively styrene: 477.46ppm, acrylonitrile: 32.11ppm, toluene: 402.55 ppm.
Example 2
4-cyclohexyl cyclohexanol is adopted as a raw material to prepare 4-cyclohexyl mercaptan, MCM-41 molecular sieve is adopted as a catalyst, and the catalyst is filled in
In a fixed bed reactor (the reactor is connected with H)2S high-pressure steel cylinder, plunger pump and gasifier are used for feeding raw material 4-cyclohexyl cyclohexanol), the set temperature of the fixed bed reactor is 286 ℃, 4-cyclohexyl cyclohexanol is conveyed to the gasifier through the plunger pump and gasified at 260 ℃, and H is reacted with the 4-cyclohexyl cyclohexanol2S is prepared from the following components in percentage by mass 1: 0.5, mixing evenly, feeding into a fixed bed reactor, and controlling the reaction process1-1.5MPaG gas velocity of 88h-1Cooling the product by a condenser, separating liquid, and absorbing non-condensable gas by using a 20% NaOH solution; the reaction liquid obtained by liquid separation is further refined by vacuum distillation (batch operation, the reflux/extraction ratio at the top of the tower is maintained at 4:1, and the fraction at 233-.
75Kg of styrene, 25Kg of acrylonitrile, 8Kg of ethylbenzene and 0.2Kg of the above self-made chain transfer agent 4-cyclohexylcyclohexanethiol were added to a 200L compounding tank and mixed uniformly.
Referring to fig. 1, the above raw material mixture was fed into a first reactor R101 having a capacity of 30L at a feed rate of 10kg/h, and the temperature of R101 was controlled to be about 150 ℃ by adjusting the amount of gas phase condensate reflux, and the average residence time of the material in R101 was 1h, thereby obtaining a slurry a. The monomer conversion of slurry a was tested to be 43%.
The slurry A is continuously conveyed into a fully-mixed flow polymerization kettle R102 with the volume of 30L and good heat preservation at the feeding speed of 10L/h, the temperature of the R102 is controlled to be about 155 ℃ by adjusting the gas phase condensation reflux quantity, and the average residence time of the material in the R101 is 1h, so that the slurry B is obtained. Slurry B monomer conversion was tested to be 64%.
Feeding the slurry B into a falling strip devolatilizer D101, controlling the temperature of a melt in the devolatilizer to be 210 ℃ and the pressure to be 1 KPaA. And water-cooling and pelletizing the devolatilized polymer melt to obtain a granular SAN product.
After the operation is stable, the finished SAN resin, HR181 rubber powder, EBS and antioxidant are taken and blended by a double screw extruder according to the mass ratio of 75:25:2:1 to further prepare the ABS resin (the method is the same as the example 1).
The SAN resin prepared by tests has the molecular weight distribution of Mw 129344 and PDI 2.87 and the shear viscosity of 1176Pa & S (200 ℃, 100S)-1). The residual contents of the SAN resin are respectively styrene: 465.73ppm, acrylonitrile: 31.22ppm, ethylbenzene: 405.39 ppm. The residual contents of the further prepared ABS resin are respectively styrene: 488.38ppm, acrylonitrile: 37.24ppm, ethylbenzene: 433.51 ppm.
Example 3
2-bicyclo [2.2 ] is used.1]Production of 2-bicyclo [2.2.1] using heptanol as starting material]Heptamercaptan, MCM-41 molecular sieve is used as catalyst and filled in
In a fixed bed reactor (the reactor is connected with H)2S high-pressure steel cylinder, plunger pump and gasifier for raw material 2-bicyclo [2.2.1]Heptanol feed), the fixed bed reactor is set at 290 ℃, decahydro-2-naphthol is conveyed into a vaporizer through a plunger pump and gasified at 260 ℃, and H2S is prepared from the following components in percentage by mass 1: 0.45, mixing evenly, feeding into a fixed bed reactor, and controlling the gas velocity of 1.2-1.5MPaG in the reaction process for 77h-1Cooling the product by a condenser, separating liquid, and absorbing non-condensable gas by using a 20% NaOH solution; the reaction liquid obtained by liquid separation is further refined by vacuum distillation (batch operation, the reflux/extraction ratio at the top of the tower is maintained at 4:1, and the fraction with the temperature of 103 ℃ and 104 ℃ under 20KPaA is collected) to obtain 2-bicyclo [2.2.1] with the purity of 98.9 percent]Heptanethiol.
60Kg of styrene, 40Kg of acrylonitrile, 16Kg of ethylbenzene and 0.45Kg of the above self-made chain transfer agent 2-bicyclo [2.2.1] heptanethiol were added to a 200L compounding tank and mixed uniformly.
Referring to fig. 1, the above raw material mixture was fed into a first reactor R101 having a capacity of 30L at a feed rate of 10kg/h, and the temperature of R101 was controlled to be about 155 ℃ by adjusting the amount of gas phase condensate reflux, and the average residence time of the material in R101 was 2 hours, thereby obtaining a slurry a. Slurry a monomer conversion was tested to 57%.
Continuously conveying the slurry A into a fully-mixed flow polymerization kettle R102 with the volume of 30L and good heat preservation at the feeding speed of 5L/h, controlling the temperature of the R102 to be about 160 ℃ by adjusting the gas phase condensation reflux quantity, and controlling the average residence time of the material in the R101 to be 2h to obtain the slurry B. Slurry B monomer conversion was tested to be 78%.
Feeding the slurry B into a falling strip devolatilizer D101, and controlling the temperature of a melt in the devolatilizer to be 225 ℃ and the pressure to be 2 KPaA. And water-cooling and pelletizing the devolatilized polymer melt to obtain a granular SAN product.
After the operation is stable, the finished SAN resin, HR181 rubber powder, EBS and antioxidant are taken and mixed by a double-screw extruder according to the mass ratio of 75:25:2:1 to further prepare the ABS resin (the method is the same as the method in example 1).
The SAN resin prepared by tests has the molecular weight distribution of Mw 110239 and PDI 2.91 and the shear viscosity of 1097Pa & S (200 ℃, 100S)-1). The residual contents of the SAN resin are respectively styrene: 285.11ppm, acrylonitrile: 17.26ppm, ethylbenzene: 135.27 ppm. The residual contents of the further prepared ABS resin are respectively styrene: 528.37ppm, acrylonitrile: 42.28ppm, ethylbenzene: 455.99 ppm.
Example 4
Using 9-tricyclo [4.3.3.0]Preparation of 9-tricyclo [4.3.3.0] using decanol as starting material]Decyl mercaptan, MCM-41 molecular sieve is used as catalyst and filled in
In a fixed bed reactor (the reactor is connected with H)2S high-pressure steel cylinder, plunger pump and gasifier used as raw material 9-tricyclo [4.3.3.0]Decanol feed), fixed bed reactor set temperature 288 ℃, 9-tricyclo [4.3.3.0]Delivering decanol to a vaporizer via a plunger pump, vaporizing decanol at 260 deg.C, and reacting with H2S is prepared from the following components in percentage by mass 1: 0.73, evenly mixed, then enters a fixed bed reactor, and the gas velocity of MPaG in the reaction process is controlled to be 1.5 to 1.8 for 50 hours-1Cooling the product by a condenser, separating liquid, and absorbing non-condensable gas by using a 20% NaOH solution; the reaction solution obtained by liquid separation is further refined by reduced pressure distillation (batch operation, the reflux/extraction ratio at the top of the tower is maintained at 4:1, and 167-169 ℃ fractions under 8KPaA are collected) to obtain the 9-tricyclo [4.3.3.0] with the purity of 98.8 percent]Decyl mercaptan.
80Kg of styrene, 20Kg of acrylonitrile, 10Kg of ethylbenzene and 0.15Kg of the above self-made chain transfer agent, 9-tricyclo [4.3.3.0] decanethiol, were added to a 200L compounding tank and mixed well.
Referring to fig. 1, the above raw material mixture was fed into a first reactor R101 having a capacity of 30L at a feed rate of 8kg/h, and the temperature of R101 was controlled to be about 150 ℃ by adjusting the amount of gas phase condensate reflux, and the average residence time of the material in R101 was 1.5h, thereby obtaining a slurry a. Slurry a monomer conversion was tested to 49%.
Continuously conveying the slurry A into a fully mixed flow polymerization kettle R102 with the volume of 30L and good heat preservation at the feeding speed of 5L/h, controlling the temperature of the R102 to be maintained at about 160 ℃ by adjusting the gas phase condensation reflux quantity, and controlling the average retention time of the material in the R101 to be 1.5h to obtain the slurry B. Slurry B monomer conversion was tested to 68%.
Feeding the slurry B into a falling strip devolatilizer D101, and controlling the temperature of a melt in the devolatilizer to be 230 ℃ and the pressure to be 2.5 KPaA. And water-cooling and pelletizing the devolatilized polymer melt to obtain a granular SAN product.
After the operation is stable, the finished SAN resin, HR181 rubber powder, EBS and antioxidant are taken and blended by a double screw extruder according to the mass ratio of 75:25:2:1 to further prepare the ABS resin (the method is the same as the example 1).
The SAN resin prepared by the test has the molecular weight distribution of Mw 128659 and PDI 2.78, and the shear viscosity of 1107 Pa.S (200 ℃, 100S)-1). The residual contents of the SAN resin are respectively styrene: 305.17ppm, acrylonitrile: 17.29ppm, ethylbenzene: 295.33 ppm. The residual contents of the further prepared ABS resin are respectively styrene: 358.29ppm, acrylonitrile: 22.48ppm, ethylbenzene: 355.63 ppm.
Example 5
Using 6-bicyclo [3.1.0]Preparation of 6-bicyclo [3.1.0] hexanol as starting Material]Hexanethiol, MCM-41 molecular sieve is used as catalyst and is filled in
In a fixed bed reactor (the reactor is connected with H)2S high-pressure steel cylinder, plunger pump and gasifier for raw material 6-bicyclo [3.1.0]Hexanol feed), fixed bed reactor set point temperature 270 ℃, 6-bicyclo [3.1.0]Feeding hexanol to a vaporizer via a plunger pump, vaporizing at 260 deg.C, and reacting with H2S is prepared from the following components in percentage by mass 1: 0.52, mixing evenly, feeding the mixture into a fixed bed reactor, and controlling the gas velocity of 1-1.5MPaG in the reaction process for 40h-1Cooling the product by a condenser, separating liquid, and absorbing non-condensable gas by using a 20% NaOH solution; the reaction solution obtained by liquid separation was further refined by reduced pressure distillation (batch operation, maintaining the overhead reflux/recovery ratio of 4:1, collecting 104-105 ℃ fraction under 20 KPaA) to obtain 6-bicyclo [3.1 ] with a purity of 99.2%.0]Hexanethiol.
70Kg of styrene, 30Kg of acrylonitrile, 10Kg of toluene and 0.25Kg of the above self-made chain transfer agent 6-bicyclo [3.1.0] hexanethiol were added to a 200L compounding tank and mixed uniformly.
Referring to fig. 1, the above raw material mixture was fed into a first reactor R101 having a capacity of 30L at a feed rate of 8kg/h, and the temperature of R101 was controlled to be about 150 ℃ by adjusting the amount of gas phase condensate reflux, and the average residence time of the material in R101 was 1.5h, thereby obtaining a slurry a. Slurry a monomer conversion was tested to 47%.
Continuously conveying the slurry A into a fully-mixed flow polymerization kettle R102 with the volume of 30L and good heat preservation at the feeding speed of 5L/h, controlling the temperature of the R102 to be about 160 ℃ by adjusting the gas phase condensation reflux quantity, and controlling the average residence time of the material in the R101 to be 1.5h to obtain the slurry B. Slurry B monomer conversion was tested to be 66%.
Feeding the slurry B into a falling strip devolatilizer D101, and controlling the temperature of a melt in the devolatilizer to be 230 ℃ and the pressure to be 2.5 KPaA. And water-cooling and pelletizing the devolatilized polymer melt to obtain a granular SAN product.
After the operation is stable, the finished SAN resin, HR181 rubber powder, EBS and antioxidant are taken and blended by a double screw extruder according to the mass ratio of 75:25:2:1 to further prepare the ABS resin (the method is the same as the example 1).
The SAN resin prepared by the test has the molecular weight distribution of Mw 133869 and PDI 2.88 and the shear viscosity of 1322Pa & S (200 ℃, 100S)-1). The residual content in SAN resin is respectively styrene: 295.18ppm, acrylonitrile: 28.76ppm, toluene: 178.62 ppm. The residual contents of the further prepared ABS resin are respectively styrene: 348.66ppm, acrylonitrile: 36.78ppm, toluene: 285.33 ppm.
Comparative example 1
The comparative example is prior art and does not use the special mercaptan of the technical scheme of the invention.
80Kg of styrene, 20Kg of acrylonitrile, 12Kg of toluene and 0.1Kg of tertiary dodecyl mercaptan as a chain transfer agent were added to a 200L tank and mixed uniformly.
Referring to fig. 1, the above raw material mixture was fed into a first reactor R101 having a volume of 30L at a feed rate of 10L/h, and the temperature of R101 was maintained at about 160 ℃ by adjusting the amount of gas phase condensate reflux, and the average residence time of the material in R101 was 1h, thereby obtaining a slurry a. The monomer conversion of slurry a was tested to be 50%.
Continuously conveying the slurry A into a fully-mixed flow polymerization kettle R102 with the volume of 30L and good heat preservation at the feeding speed of 10L/h, controlling the temperature of the R102 to be about 160 ℃ by adjusting the gas phase condensation reflux quantity, and controlling the average residence time of the material in the R101 to be 1h to obtain the slurry B. Slurry B monomer conversion was tested to 70%.
Feeding the slurry B into a falling strip devolatilizer D101, controlling the temperature of the melt in the devolatilizer to be 220 ℃ and the pressure to be 1.5 KPaA. And water-cooling and pelletizing the devolatilized polymer melt to obtain a granular SAN product.
After the operation is stable, the finished SAN resin, HR181 rubber powder, EBS and antioxidant are taken and blended by a double screw extruder according to the mass ratio of 75:25:2:1 to further prepare the ABS resin (the method is the same as the example 1).
The SAN resin prepared by the test has the molecular weight distribution of Mw 129975 and PDI 2.88 and the shear viscosity of 1684Pa & S (200 ℃, 100S)-1). The residual contents of the SAN resin are respectively styrene: 1057.87ppm, acrylonitrile: 49.24ppm, toluene: 852.03 ppm. The residual contents in the further prepared ABS resin are respectively styrene: 1251.38ppm, acrylonitrile: 62.27ppm, toluene: 949.75 ppm.
Therefore, the mercaptan with a special structure is used as a chain transfer agent in the SAN polymerization process, the viscosity of SAN resin melt is reduced, the devolatilization mass transfer effect of the SAN resin is improved in the process of preparing the SAN resin, and after the SAN resin is further blended to obtain the ABS resin, the residual monomers and the solvent of the resin are obviously reduced.
It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (6)
1. A method for reducing the residual content of styrene-acrylonitrile copolymer (SAN) resin, comprising the steps of:
s1: mixing styrene, acrylonitrile, a chain transfer agent and a solvent to obtain a monomer mixed solution;
s2: adding the monomer mixed solution into a first reactor for polymerization reaction to obtain slurry A, and continuously adding the slurry A into a second reactor for polymerization reaction to obtain slurry B;
s3: continuously feeding the slurry B into a devolatilization device, removing unreacted monomers and solvents, and pelletizing the melt to obtain SAN resin;
wherein the chain transfer agent is aliphatic polycyclic tertiary mercaptan with 5-20 carbon atoms, preferably aliphatic polycyclic tertiary mercaptan with 6-18 carbon atoms, more preferably the chain transfer agent structure is R-SH, wherein R is one or more of the following structures:
2. the method of claim 1, wherein the monomer mixture of S1 comprises the following components: 60-85 parts of styrene, 15-40 parts of acrylonitrile, 0.05-0.5 part of chain transfer agent and 5-20 parts of solvent;
preferably, the amount of the chain transfer agent added is preferably 0.05 to 0.3 wt% of the total amount of the monomers;
preferably, the solvent is one or more of toluene, ethylbenzene, tetrahydrofuran, dichloromethane, preferably toluene and/or ethylbenzene.
3. The method of claim 1, wherein the first reactor and the second reactor of S2 are all mixed flow reactors;
preferably, the first reactor and the second reactor are connected in series;
and/or S2, wherein the first reactor temperature is 145-165 ℃, preferably 150-160 ℃, the residence time is 0.5-3h, preferably 1-2h, and the outlet conversion rate is 40-60%;
and/or the temperature of the second reactor of S2 is 145-165 ℃, preferably 150-160 ℃, the retention time is 0.5-3h, preferably 1-2h, and the outlet conversion rate is 60-80%.
4. The method of claim 1, wherein S3 the devolatilizer melt temperature is controlled at 250 ℃, preferably at 210 ℃ and 230 ℃, and the absolute pressure is controlled at 5KPa, preferably at 3 KPa.
5. A low residual SAN resin obtained by the method for reducing residual styrene-acrylonitrile copolymer (SAN) resin according to any one of claims 1 to 4, wherein the residual content in the SAN resin is 350-1200ppm, preferably 400-1000 ppm.
6. Use of a low residual SAN resin produced by the method for reducing residual styrene-acrylonitrile copolymer (SAN) resin according to any one of claims 1 to 4 or a SAN resin according to claim 5 for blending to produce a low residual ABS resin.
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