CN114409839B - SAN resin and preparation method thereof - Google Patents
SAN resin and preparation method thereof Download PDFInfo
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- CN114409839B CN114409839B CN202210097355.1A CN202210097355A CN114409839B CN 114409839 B CN114409839 B CN 114409839B CN 202210097355 A CN202210097355 A CN 202210097355A CN 114409839 B CN114409839 B CN 114409839B
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- 239000011347 resin Substances 0.000 title claims abstract description 56
- 229920005989 resin Polymers 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims description 50
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 22
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 6
- GNURAXCIBMZJOG-UHFFFAOYSA-N 9h-fluorene-9-thiol Chemical compound C1=CC=C2C(S)C3=CC=CC=C3C2=C1 GNURAXCIBMZJOG-UHFFFAOYSA-N 0.000 claims description 5
- BCZADNSFSRFPNJ-UHFFFAOYSA-N 9h-xanthene-9-thiol Chemical compound C1=CC=C2C(S)C3=CC=CC=C3OC2=C1 BCZADNSFSRFPNJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- IYLBYXJQNPUFQJ-UHFFFAOYSA-N 1,2,3,4-tetrahydronaphthalene-1-thiol Chemical compound C1=CC=C2C(S)CCCC2=C1 IYLBYXJQNPUFQJ-UHFFFAOYSA-N 0.000 claims description 2
- PKQBWNQTZHKMDR-UHFFFAOYSA-N 1h-indene-1-thiol Chemical compound C1=CC=C2C(S)C=CC2=C1 PKQBWNQTZHKMDR-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 abstract description 16
- 238000012546 transfer Methods 0.000 abstract description 9
- 125000004122 cyclic group Chemical group 0.000 abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 229920000638 styrene acrylonitrile Polymers 0.000 description 49
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- 239000003963 antioxidant agent Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 230000003078 antioxidant effect Effects 0.000 description 14
- 238000009833 condensation Methods 0.000 description 14
- 230000005494 condensation Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 238000010992 reflux Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000012808 vapor phase Substances 0.000 description 8
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- -1 oxazole-thiazole heterocyclic compounds Chemical class 0.000 description 4
- 150000003573 thiols Chemical class 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RFCQDOVPMUSZMN-UHFFFAOYSA-N 2-Naphthalenethiol Chemical compound C1=CC=CC2=CC(S)=CC=C21 RFCQDOVPMUSZMN-UHFFFAOYSA-N 0.000 description 2
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical group CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- JAAJQSRLGAYGKZ-UHFFFAOYSA-N 1,2,3,4-tetrahydronaphthalen-1-ol Chemical compound C1=CC=C2C(O)CCCC2=C1 JAAJQSRLGAYGKZ-UHFFFAOYSA-N 0.000 description 1
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 description 1
- JRJBVWJSTHECJK-PKNBQFBNSA-N 3-Methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one Chemical compound CC(=O)C(\C)=C\C1C(C)=CCCC1(C)C JRJBVWJSTHECJK-PKNBQFBNSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- AWCDPBVIEITASD-UHFFFAOYSA-N C1(=CC=CC=C1)S.S1C=NC2=C1C=CC=C2 Chemical compound C1(=CC=CC=C1)S.S1C=NC2=C1C=CC=C2 AWCDPBVIEITASD-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000012988 Dithioester Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical class [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000005022 dithioester group Chemical group 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- AFMVESZOYKHDBJ-UHFFFAOYSA-N fluoren-9-ol Chemical compound C1=CC=C2C(O)C3=CC=CC=C3C2=C1 AFMVESZOYKHDBJ-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZVEZMVFBMOOHAT-UHFFFAOYSA-N nonane-1-thiol Chemical group CCCCCCCCCS ZVEZMVFBMOOHAT-UHFFFAOYSA-N 0.000 description 1
- 238000013027 odor testing Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- JFRMYMMIJXLMBB-UHFFFAOYSA-N xanthydrol Chemical compound C1=CC=C2C(O)C3=CC=CC=C3OC2=C1 JFRMYMMIJXLMBB-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- GAWWVVGZMLGEIW-UHFFFAOYSA-L zinc;12-hydroxyoctadec-9-enoate Chemical compound [Zn+2].CCCCCCC(O)CC=CCCCCCCCC([O-])=O.CCCCCCC(O)CC=CCCCCCCCC([O-])=O GAWWVVGZMLGEIW-UHFFFAOYSA-L 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
- C08F212/10—Styrene with nitriles
-
- 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
- C08L25/12—Copolymers of styrene with unsaturated nitriles
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses SAN resin and a preparation method thereof. By adopting tertiary group ring mercaptan with 8-16 carbon atoms, a substance with at least one phenyl group in the structure is used as a chain transfer agent. When the benzene ring substituted cyclic mercaptan is used as a chain transfer agent, the olfactory threshold is obviously increased, the lower molecular radius improves the chain transfer efficiency of the polymerization reaction, and the rigid cyclic structure reduces the migration rate of residual mercaptan in the resin, so that the problem of residual mercaptan with low olfactory threshold is avoided, and the odor problem of the resin is obviously improved.
Description
Technical Field
The invention belongs to the technical field of resins, and particularly relates to a low-odor SAN resin and a preparation method thereof.
Background
The ABS resin is divided into two production processes of emulsion grafting-bulk SAN blending method and bulk method according to synthetic route. The emulsion grafting-bulk SAN blending method is characterized in that the grafting powder and SAN are produced respectively, and ABS resin products with different performances such as impact resistance, glossiness and the like can be prepared by adjusting the blending process proportion of the rear-section double screw. Owing to the emulsion grafting-bulk SAN blending process with flexible technology and variable product types, nearly 9 suppliers all adopt the process to produce ABS.
Although the ABS resin prepared by the emulsion grafting-bulk SAN blending method has more excellent performance compared with the bulk method, the ABS resin has the problem of large smell in the processing and using processes, and is not well popularized in the application fields of automobile, aircraft interior trim and the like.
The root cause of the analysis is that ABS resin monomer, chain transfer agent and initiator have lower olfactory threshold (monomer-styrene 0.047ppm, acrylonitrile 1.6ppm, butadiene 0.45ppm, chain transfer agent-tert-dodecyl mercaptan 0.0008ppm, initiator and decomposition products thereof-cumene hydroperoxide 0.03ppm and cumene 0.06ppm, data are shown in Compilations of odour threshold values in air, water and other media-L.J.vanGemert), and trace substances migrate out under the conditions of material post-processing and heating such as automobile interior decoration exposure and the like to cause uncomfortable odor in the automobile. Of these, tertiary dodecyl mercaptan plays the most important role in odor generation by having an extremely low olfactory threshold.
The problem of the high odor of ABS materials has been well recognized in the prior art and attempts have been made to propose solutions from different angles. For example, patent CN101759950A, CN107236239a proposes adding fillers such as carbon black and attapulgite at the blending end, and removing the peculiar smell in the resin by physical adsorption; and patent CN111138798A, CN 109467870A, CN101318972A adopts spices such as magnesium/silicon/zinc/boron/calcium hydrate salt, 12-hydroxy-9-octadecenoic acid zinc salt, alpha-isomethyl ionone and the like, and reduces the peculiar smell of the material by utilizing the odor covering property of the spices.
In terms of improvement of production process, patent CN109354653a, "low odor/low VOC content green ABS resin preparation, li Yonghua, chinese plastic, 33 (6), 24-30" proposes the use of non-thiol chain transfer agents such as dithioesters, alpha-methylstyrene linear dimers, etc.; CN108276528A proposes to reduce the amount of t-dodecyl mercaptan added, raise the polymerization-devolatilization temperature to destroy the initiator as much as possible and remove residual mercaptans.
The method is limited by different degrees in practical application, such as the problems of color introduction and product performance reduction caused by the adoption of an adsorbent; the scheme of adopting the smell covering agent belongs to an olfactory deception mode, and the mode not only can not achieve the aim of reducing VOC, but also can increase the value, and does not meet the technical requirements of part of applications (such as HJT-2007 in-vehicle volatile organic compound test).
In terms of process improvement, since SAN resins are susceptible to coloring of the resin due to cyclization of acrylonitrile, a large number of different-colored particles appear, and it is apparent that a scheme for lowering the addition amount of thiol to raise the polymerization-devolatilization temperature is highly undesirable; the literature 'preparation of low-odor/low-VOC environment-friendly ABS resin, li Yonghua, chinese plastics, 33 (6), 24-30' also shows that the use of non-mercaptan chain transfer agent has the problem of low efficiency, the requirement of correspondingly increasing the addition amount of the transfer agent (the addition amount of the chain transfer agent is 3 times of the addition amount of tertiary dodecyl mercaptan after the process optimization in the literature), and the problem of poor quality of the final product. The root cause is that the existing mercaptan chain transfer agent has optimal chain transfer efficiency in a styrene bulk polymerization system, and can keep the concentration ratio of the mercaptan chain transfer agent to the monomer unchanged in a wider conversion range, so that the molecular weight distribution of a reaction product is controlled (see second edition of polymer emulsion synthesis principle performance and application, cao Tongyu, P328).
In terms of chain transfer agents containing mercapto groups of different structures, some documents such as CN102482478A, CN106094435a have proposed that naphthalene rings containing mercapto groups or oxazole-thiazole heterocyclic compounds (e.g. 2-naphthalene thiol, 2-mercaptobenzene-oxazole, 2-mercaptobenzene-benzothiazole, 4-methyl-4H-3-mercapto-1, 2,4 triazole) can be used for chain transfer reactions of free radical polymerization. The mercapto compound has obvious problems when being used for bulk polymerization of styrene and acrylonitrile, such as N-containing heterocyclic compounds are easy to cause resin yellowing to be aggravated, and the 2-naphthalene thiol structure after forming free radicals has increased stability due to pi bond of naphthalene ring, which does not meet the high efficiency requirement of bulk polymerization reaction.
Therefore, there is a need for new chain transfer agents which have at least equivalent chain transfer efficiency to the existing chain transfer agent t-dodecyl mercaptan, while having a higher olfactory threshold, and which do not cause additional problems such as darkening of color, and which are useful in the production of low odor ABS resins.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method of low-odor SAN resin, which adopts mercaptan with a special structure and a high olfactory threshold value as a chain transfer agent, so that odor problem of the SAN resin in the processing and using processes caused by residual mercaptan is reduced; further, when the resin is blended to prepare the ABS resin, the odor problem of a finished product is also remarkably improved in the using process.
Specifically, the invention provides a preparation method of low-odor SAN resin, which comprises the following steps:
1) Mixing styrene, acrylonitrile, chain transfer agent and solvent to obtain mixed solution;
2) Introducing the mixed solution obtained in the step 1) into a first reactor, and carrying out polymerization reaction at 145-165 ℃ for 0.5-3h under the condition of residence time to obtain slurry A;
3) Continuously adding the slurry A into a second reactor, and carrying out polymerization reaction at 145-165 ℃ and under the condition of 0.5-3h residence time to obtain slurry B;
4) Continuously feeding the slurry B obtained in the step 3) into a devolatilizer to remove unreacted monomers; extruding and granulating the devolatilized melt to obtain SAN resin.
In the present invention, the chain transfer agent is a tertiary polycyclic thiol having 9 to 16 carbon atoms, preferably having at least 1 benzene ring in its structure, more preferably, the chain transfer agent is selected from one or more of the following structural formulas:
a is-O-, -CH 2 -、-CH 2 -CH 2 -、-CH 2 ＝CH 2 -
The dashed line indicates the presence or absence of a benzene ring.
As a preferred embodiment, the chain transfer agent of the present invention is one or more of 1-indenethiol, tetrahydro-1-naphthalenethiol, 9-mercaptofluorene, 9-mercaptoxanthene, and 2-benzocycloheptatriene-5-thiol.
In the present invention, the first reactor and the second reactor are all-mixed flow reactors, and preferably, the first reactor and the second reactor are connected in series.
As a preferred embodiment, the first reactor temperature is 150-160 ℃, the residence time is 1-2h, and the outlet conversion rate is 40-60%.
As a preferred embodiment, the second reactor temperature is 150-160 ℃, the residence time is 1-2h, and the outlet conversion rate is 60-80%.
In the invention, the raw materials in the step 1) are as follows: 60-85 parts of styrene, 15-40 parts of acrylonitrile, 0.05-0.3 part of chain transfer agent and 5-20 parts of solvent.
The solvent of the invention can be one or more of toluene, ethylbenzene, tetrahydrofuran and methylene dichloride, and is preferably toluene and/or ethylbenzene.
The addition amount of the chain transfer agent is preferably 0.05 to 0.3 weight percent of the total amount of styrene and acrylonitrile.
In the preparation method of the invention, the melt temperature of the devolatilization unit is generally controlled between 180 and 250 ℃, preferably between 210 and 230 ℃. The absolute pressure in the devolatilizer is controlled to be within 5KPa, preferably within 3KPa.
In the preparation method of the invention, any content and any type of auxiliary agent common in the field can be added in the technical process according to the required SAN resin performance, including but not limited to release agents, ultraviolet absorbers, antioxidants, colorants and the like.
The invention also provides SAN resin which is prepared by the preparation method according to any one of the technical schemes, and can be further used for preparing low-odor ABS resin by blending.
The smell of the mercaptan is related to the molecular structure, and particularly when methyl, ethyl and the like exist in C atoms within 2 covalent bonds of S atoms on the molecular chain of the mercaptan, the smell threshold is extremely low, so that the smell of the finished resin is obviously influenced. When the benzene ring substituted cyclic mercaptan is used as a chain transfer agent, the olfactory threshold is obviously increased, the lower molecular radius improves the chain transfer efficiency of the polymerization reaction, and the rigid cyclic structure reduces the migration rate of residual mercaptan in the resin, so that the odor problem of the resin is obviously improved.
Compared with the conventional process, the SAN resin preparation method provided by the invention has lower odor grade, and can meet the higher odor index requirement of downstream automobile interior manufacturers when preparing low-odor ABS products. In addition, 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 diagram of a system for preparing a styrene-acrylonitrile copolymer according to an embodiment of the present invention;
FIG. 2 is a chart of the 1H NMR spectrum of thiol of example 1;
FIG. 3 is a 1H NMR spectrum of thiol of example 2.
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.
The sources of the raw materials are shown in Table 1.
TABLE 1 sources of raw materials
The experimental facilities are shown in Table 2.
Table 2 Experimental apparatus
The analysis method comprises the following steps:
in the examples and comparative examples of the present invention, the monomer conversion during polymerization, the molecular weight of the finished SAN resin and the odor test method of the final blended ABS resin were as follows:
resin content (conversion) test: 1g of reaction solution is weighed and placed in tinfoil paper (the tinfoil paper is weighed in advance), and is placed in a vacuum oven at 160 ℃, absolute pressure is controlled to be less than 1KPa, the reaction solution is vacuumized for 0.5h, taken out, cooled at room temperature, and the weight of dried resin is weighed. The resin content can be calculated by dividing the mass of the dry resin by the mass of the reaction liquid.
SAN resin molecular weight: using dichloromethane as solvent, and testing SAN resin molecular weight by gel chromatography;
odor grade test of the finished ABS resin: according to the standard of VW50180 experiments of mass automobiles, placing the resin sheet in a tasteless glass bottle, heating in an oven at 80 ℃ for 2 hours, taking out, cooling to 60 ℃, and then testing by 5 odor judges, and feeding back the following odor grades;
grade 1 = no off-flavor; grade 2 = slightly off-flavor; grade 3 = tasty but not irritating;
grade 4 = pungent odor; grade 5 = strong pungent odor; grade 6 = intolerable odor;
transmittance/haze: the prepared SAN resin sample is injection molded into a 3mm sample wafer, and a haze meter is adopted to test indexes of light transmittance and haze of the sample according to GB/T2410-2008;
in the examples and comparative examples of the present invention, the first reactor and the second reactor were all mixed flow reactors.
Example 1
1-indene mercaptan is prepared by using 1-indene alcohol as a raw material, and the process is optimized by reference to the document 'dodecyl alcohol substitution for n-dodecyl mercaptan, tian Yong, chemical engineer, 2010 (4), 62-65'. The purity of the prepared 2-indene mercaptan is 98.9%, and the nuclear magnetic spectrum is shown in figure 2.
80Kg of Styrene (SM), 20Kg of acrylonitrile, 12Kg of toluene and 0.1Kg of the above chain transfer agent 1-indene thiol were charged into a 200L mixed monomer 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 10kg/h, and the temperature of R101 was controlled to be kept at about 160℃by adjusting the amount of vapor phase condensation reflux, and the average residence time of the material in R101 was 1h, to obtain a slurry A. The slurry a monomer conversion was tested to be 50%.
And continuously conveying the slurry A into a second reactor 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 materials in the R102 to be 1h to obtain the slurry B. The slurry B monomer conversion was tested to be 70%.
And (3) feeding the slurry B into a falling strip devolatilizer, wherein the temperature of a melt in the devolatilizer is controlled to be 220 ℃ and the pressure is controlled to be 1.5KPa. And (3) carrying out water-cooling granulation on the devolatilized polymer melt to obtain a granular SAN product.
After stable operation, taking finished SAN resin, HR181 rubber powder, EBS and antioxidant, and blending the SAN resin, the HR181 rubber powder, the EBS and the antioxidant by a double-screw extruder according to the mass ratio of 75:25:2:1 to further prepare the ABS resin;
the SAN resin obtained by the test has a light transmittance of 90.36% and a haze of 2.02. The odor grade of the ABS resin after injection molding and tabletting is 2.
Example 2
The process for preparing tetrahydro-1-naphthalene thiol by using tetrahydro-1-naphthol as raw material is the same as in example 1. The purity of the prepared tetrahydro-1-naphthalene thiol is 99.3%, and the nuclear magnetic spectrum is shown in figure 3.
75Kg of styrene, 25Kg of acrylonitrile, 8Kg of ethylbenzene and 0.2Kg of the self-made chain transfer agent tetrahydro-1-naphthalene thiol are added into a 200L mixed monomer storage tank and uniformly mixed.
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 10kg/h, and the temperature of R101 was controlled to be maintained at about 150℃by adjusting the amount of vapor phase condensation reflux, and the average residence time of the material in R101 was 1h, to obtain a slurry A. The slurry a monomer conversion was tested to be 43%.
Slurry A was continuously fed into a second reactor R102 having a capacity of 30L and good heat preservation at a feed rate of 10L/h, and the temperature of R102 was maintained at about 155℃by adjusting the amount of vapor phase condensation reflux, and the average residence time of the material in R102 was 1h, to obtain slurry B. The slurry B monomer conversion was tested to be 64%.
And (3) feeding the slurry B into a falling strip devolatilizer, wherein the temperature of a melt in the devolatilizer is controlled to be 210 ℃ and the pressure is controlled to be 1KPa. And (3) carrying out water-cooling granulation on the devolatilized polymer melt to obtain a granular SAN product.
After stable operation, taking finished SAN resin, HR181 rubber powder, EBS and antioxidant, and blending the SAN resin, the HR181 rubber powder, the EBS and the antioxidant by a double-screw extruder according to the mass ratio of 75:25:2:1 to further prepare the ABS resin;
the SAN resin obtained by the test has a light transmittance of 90.77% and a haze of 1.94. The odor grade of the ABS resin after injection molding and tabletting is 2.
Example 3
9-mercaptofluorene was prepared from 9-hydroxyfluorene as a raw material by the same process as in example 1. The purity of the prepared 9-mercaptofluorene is 98.9%.
60Kg of styrene, 40Kg of acrylonitrile, 16Kg of ethylbenzene and 0.05Kg of chain transfer agent 9-mercaptofluorene were added to a 200L mixed monomer 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 10kg/h, and the temperature of R101 was controlled to be kept at about 155℃by adjusting the amount of vapor phase condensation reflux, and the average residence time of the material in R101 was 2 hours, to obtain a slurry A. The slurry a monomer conversion was tested to be 57%.
And continuously conveying the slurry A into a second reactor 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 materials in the R102 to be 2h to obtain the slurry B. The slurry B monomer conversion was tested to be 78%.
And (3) feeding the slurry B into a falling strip devolatilizer, wherein the temperature of a melt in the devolatilizer is controlled to be 225 ℃ and the pressure is controlled to be 2KPa. And (3) carrying out water-cooling granulation on the devolatilized polymer melt to obtain a granular SAN product.
After stable operation, taking finished SAN resin, HR181 rubber powder, EBS and antioxidant, and blending the SAN resin, the HR181 rubber powder, the EBS and the antioxidant by a double-screw extruder according to the mass ratio of 75:25:2:1 to further prepare the ABS resin;
the SAN resin obtained by the test has a light transmittance of 90.97% and a haze of 1.64. The odor grade of the ABS resin after injection molding and tabletting is 1 grade.
Example 4
The procedure of example 1 was followed to prepare the corresponding thiol using 9-hydroxyxanthene as starting material. The purity of the prepared 9-mercaptoxanthene is 98.7 percent.
To a 200L compounding tank were added 85Kg of styrene, 15Kg of acrylonitrile, 5Kg of ethylbenzene and 0.3Kg of a chain transfer agent 9-mercaptoxanthene, and mixed well.
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 10kg/h, and the temperature of R101 was controlled to be maintained at about 150℃by adjusting the amount of vapor phase condensation reflux, and the average residence time of the material in R101 was 1h, to obtain a slurry A. The slurry a monomer conversion was tested to be 47%.
And continuously conveying the slurry A into a second reactor 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 155 ℃ by adjusting the gas phase condensation reflux quantity, and controlling the average residence time of materials in the R102 to be 1h to obtain the slurry B. The slurry B monomer conversion was tested to be 68%.
And (3) feeding the slurry B into a falling strip devolatilizer, wherein the temperature of a melt in the devolatilizer is controlled to be 200 ℃ and the pressure is controlled to be 3KPa. And (3) carrying out water-cooling granulation on the devolatilized polymer melt to obtain a granular SAN product.
After stable operation, taking finished SAN resin, HR181 rubber powder, EBS and antioxidant, and blending the SAN resin, the HR181 rubber powder, the EBS and the antioxidant by a double-screw extruder according to the mass ratio of 75:25:2:1 to further prepare the ABS resin;
the SAN resin obtained by the test has a light transmittance of 90.96% and a haze of 1.07. The odor grade of the ABS resin after injection molding and tabletting is 2.
Example 5
2-Benzocycloheptatrien-5-thiol was prepared using 2-Benzocycloheptatrien-5-ol as a starting material in the same manner as in example 1. The purity of the prepared 2-benzocycloheptatriene-5-mercaptan is 99.2%.
To a 200L compounding tank were added 70Kg of styrene, 30Kg of acrylonitrile, 10Kg of toluene, and 0.15Kg of the chain transfer agent 2-benzocycloheptatriene-5-thiol, and mixed well.
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 10kg/h, and the temperature of R101 was controlled to be maintained at about 150℃by adjusting the amount of vapor phase condensation reflux, and the average residence time of the material in R101 was 2 hours, to obtain a slurry A. The slurry a monomer conversion was tested to be 55%.
And continuously conveying the slurry A into a second reactor 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 materials in the R102 to be 2h to obtain the slurry B. The slurry B monomer conversion was tested to be 76%.
And (3) feeding the slurry B into a falling strip devolatilizer, wherein the temperature of a melt in the devolatilizer is controlled to be 215 ℃ and the pressure is controlled to be 2KPa. And (3) carrying out water-cooling granulation on the devolatilized polymer melt to obtain a granular SAN product.
After stable operation, taking finished SAN resin, HR181 rubber powder, EBS and antioxidant, and blending the SAN resin, the HR181 rubber powder, the EBS and the antioxidant by a double-screw extruder according to the mass ratio of 75:25:2:1 to further prepare the ABS resin;
the SAN resin obtained by the test has 90.55% transmittance and 1.22 haze. The odor grade of the ABS resin after injection molding and tabletting is 1 grade.
Comparative example 1
80Kg of Styrene (SM), 20Kg of acrylonitrile, 12Kg of toluene and 0.1Kg of the chain transfer agent tert-dodecyl mercaptan were added to a 200L formulation and mixed well.
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 controlled to be kept at about 160℃by adjusting the amount of vapor phase condensation reflux, and the average residence time of the material in R101 was 1h, to obtain a slurry A. The slurry a monomer conversion was tested to be 50%.
And continuously conveying the slurry A into a second reactor 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 materials in the R102 to be 1h to obtain the slurry B. The slurry B monomer conversion was tested to be 70%.
And (3) feeding the slurry B into a falling strip devolatilizer, wherein the temperature of a melt in the devolatilizer is controlled to be 220 ℃ and the pressure is controlled to be 1.5KPa. And (3) carrying out water-cooling granulation on the devolatilized polymer melt to obtain a granular SAN product.
After stable operation, taking finished SAN resin, HR181 rubber powder, EBS and antioxidant, and blending the SAN resin, the HR181 rubber powder, the EBS and the antioxidant by a double-screw extruder according to the mass ratio of 75:25:2:1 to further prepare the ABS resin;
the SAN resin obtained by the test has the light transmittance of 89.64% and the haze of 3.11. The odor grade of the ABS resin after injection molding and tabletting is 4.
Comparative example 2
80Kg of Styrene (SM), 20Kg of acrylonitrile, 12Kg of toluene and 0.1Kg of the chain transfer agent 2-mercaptobenzoxazole 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 volume of 30L at a feed rate of 10L/h, and the temperature of R101 was controlled to be kept at about 160℃by adjusting the amount of vapor phase condensation reflux, and the average residence time of the material in R101 was 1h, to obtain a slurry A. The slurry a monomer conversion was tested to be 37%.
And continuously conveying the slurry A into a second reactor 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 materials in the R102 to be 1h to obtain the slurry B. The slurry B monomer conversion was 53% as tested.
And (3) feeding the slurry B into a falling strip devolatilizer, wherein the temperature of a melt in the devolatilizer is controlled to be 220 ℃ and the pressure is controlled to be 1.5KPa. And (3) carrying out water-cooling granulation on the devolatilized polymer melt to obtain a granular SAN product.
After stable operation, taking finished SAN resin, HR181 rubber powder, EBS and antioxidant, and blending the SAN resin, the HR181 rubber powder, the EBS and the antioxidant by a double-screw extruder according to the mass ratio of 75:25:2:1 to further prepare the ABS resin;
the SAN resin obtained by the test has light transmittance of 81.32% and haze of 16.27. The odor grade of the ABS resin after injection molding and tabletting is 4.
From the above, it can be seen that the invention adopts mercaptan with special structure as chain transfer agent in SAN polymerization process, which has higher olfactory threshold, and the odor problem of the finished product is obviously improved after SAN resin is further blended to obtain ABS resin.
Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (10)
1.A method for preparing SAN resin, comprising the steps of:
1) Mixing styrene, acrylonitrile, tertiary group cyclomercaptan chain transfer agent and solvent to obtain mixed solution;
2) Introducing the mixed solution obtained in the step 1) into a first reactor for polymerization reaction to obtain slurry A;
3) Continuously adding the slurry A into a second reactor for polymerization reaction to obtain slurry B;
4) Continuously feeding the slurry B obtained in the step 3) into a devolatilizer to remove unreacted monomers; extruding and granulating the devolatilized melt to obtain SAN resin;
the chain transfer agent is selected from one or more of the following structural formulas:
wherein A is-O-, -CH 2 -、-CH 2 -CH 2 -、-CH 2 ＝CH 2 The dashed line indicates the presence or absence of a benzene ring.
2. The method of claim 1, wherein the first reactor and the second reactor are fully mixed flow reactors.
3. The method of claim 1, wherein the reaction temperature in step 2) is 145 to 165 ℃ and the residence time is 0.5 to 3 hours.
4. The process of claim 1, wherein the first reactor temperature is 150 to 160 ℃ and the residence time is 1 to 2 hours; the outlet conversion rate is 40-60%.
5. The method of claim 1, wherein the step 3) is performed at a reaction temperature of 145 to 165 ℃ and a residence time of 0.5 to 3 hours.
6. The process of claim 1, wherein the second reactor temperature is 150-160 ℃ and the residence time is 1-2 hours; the outlet conversion is 60-80%.
7. The method of claim 1 wherein said chain transfer agent is one or more of 1-indenethiol, tetrahydro-1-naphthalenethiol, 9-mercaptofluorene, 9-mercaptoxanthene, 2-benzocycloheptatriene-5-thiol.
8. The method of claim 1 wherein the chain transfer agent is added in an amount of 0.05 to 0.3 weight percent based on the total amount of styrene and acrylonitrile.
9. The method according to claim 1, wherein the raw materials in the step 1) are used in the following amounts: 60-85 parts of styrene, 15-40 parts of acrylonitrile, 0.05-0.3 part of chain transfer agent and 5-20 parts of solvent.
10. A SAN resin prepared according to the method of any one of claims 1-9.
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