CN108671867A - A kind of device and method thereof preparing solid propenoic acid resin - Google Patents
A kind of device and method thereof preparing solid propenoic acid resin Download PDFInfo
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- CN108671867A CN108671867A CN201810575598.5A CN201810575598A CN108671867A CN 108671867 A CN108671867 A CN 108671867A CN 201810575598 A CN201810575598 A CN 201810575598A CN 108671867 A CN108671867 A CN 108671867A
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- reactor
- monomer
- polymerization
- acid resin
- propenoic acid
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- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000007787 solid Substances 0.000 title claims abstract description 21
- 239000011347 resin Substances 0.000 title claims abstract description 20
- 229920005989 resin Polymers 0.000 title claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 50
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 6
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 6
- 125000005395 methacrylic acid group Chemical group 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 71
- 238000006116 polymerization reaction Methods 0.000 claims description 62
- 239000000463 material Substances 0.000 claims description 58
- 238000012546 transfer Methods 0.000 claims description 37
- 239000003999 initiator Substances 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 6
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- LMAUULKNZLEMGN-UHFFFAOYSA-N 1-ethyl-3,5-dimethylbenzene Chemical compound CCC1=CC(C)=CC(C)=C1 LMAUULKNZLEMGN-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- -1 t-amyl peroxy hexamethylene Chemical group 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 229940117958 vinyl acetate Drugs 0.000 claims description 2
- SFPNZPQIIAJXGL-UHFFFAOYSA-N 2-ethoxyethyl 2-methylprop-2-enoate Chemical class CCOCCOC(=O)C(C)=C SFPNZPQIIAJXGL-UHFFFAOYSA-N 0.000 claims 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims 1
- 238000012662 bulk polymerization Methods 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000002932 luster Substances 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 150000001451 organic peroxides Chemical class 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011346 highly viscous material Substances 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1862—Stationary reactors having moving elements inside placed in series
-
- 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
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The present invention relates to a kind of device and method thereof preparing solid propenoic acid resin, solve the problems, such as that the conveying of technique of continuous bulk polymerization medium-high viscosity, stirring and heat and mass are difficult.This method is according to technical recipe, coordinate corresponding equipment, it is added without solvent, by acrylic compounds and methacrylic monomer, vinyl monomer and function monomer mixture, under the conditions of existing for organic peroxide and molecular weight regulator, by multiple series connection and the plunger flow reactor of multistage independence temperature control, copolymerization is carried out, products obtained therefrom color and luster is uniform, and molecular weight distribution is smaller.
Description
Technical field
The present invention relates to the preparation method of acrylic resin, specifically, is related to a kind of solid propenoic acid resin for preparing
Device and method thereof.
Background technology
Solid propenoic acid resin be with vinyl monomers such as (methyl) acrylate, (methyl) acrylic acid, styrene and
Other function monomers are the copolymer of main Material synthesis.The resinoid is shallow with color, protects color, protects light, is weather-proof, corrosion-resistant and resistance to
The characteristics of pollution, is widely used in automobile, aircraft, mechano-electronic, furniture, building, leather, timber, papermaking, printing and dyeing, industry modeling
The fields such as material and day product covering with paint.
The polymerization technique of acrylic resin mainly has：Polymerisation in solution, suspension polymerisation, emulsion polymerization and bulk polymerization, each
Polymerization technique all respectively has its advantage.For bulk technique, monomer, initiator and molecular-weight adjusting is only added in polymerization process
Agent is added without or is added on a small quantity solvent, and production efficiency is high, manufacturing cost is low, emits no waste water, environmental-friendly, and product color
Pool is uniform, product quality consistency is good, is increasingly becoming the polymerization technique for encouraging development；Simultaneously as in bulk polymerisation process
High viscosity and heat transfer, mass transfer difficulty, monomer conversion is low, more demanding to reactor apparatus and process control procedure, this
Limit the practical application of bulk technique in production.
In acrylic resin field, bulk technique initially continuously stirs slot (CSTR) from one-pot and develops.One-pot
Slot bulk technique is continuously stirred, has many advantages, such as small investment, is produced flexible；Due to the limitation of technique, the technique conversion ratio
Only 50%, low production efficiency.
Later, but developed two kettles series connection continuously stir slot (CSTR) bulk technique.First reaction kettle does pre-polymerization
It closes, when conversion ratio 30~40%, enters in second reactor, final product conversion ratio can be to 60% or more.Two kettle strings
Connection continuously stirs slot (CSTR) bulk technique, has the heat transfer area of opposite bigger, can use lower quantity of solvent.
In bulk technique, in order to reduce polymerization system viscosity and control rate of polymerization, using 5%~40% it is molten
Agent, such as toluene, ethylbenzene.The use of solvent is needed under devolatilization system, vacuum and hot conditions, is detached, and consumption is more
Heat.Moreover, inevitable residual solvent in product, also limits the application of acrylic resin.In order to realize that addition is a small amount of molten
Agent, or even it is added without solvent, the purpose of high monomer conversion is obtained, polymerization reaction late stage is especially worked as, conversion ratio is higher, material
Viscosity sharply increases, and stirring, conveying and exchanging heat becomes particularly difficult, has developed the phase after polymerization again later, using tubular type
Or tower reactor, it is highly viscous to solve the problems, such as.
Patent CN200810026505 provides a kind of water soluble acrylic resin's bulk polymerization, is pressed in head tank
Various monomers and initiator mixture is added in formula, reaction mixture is then pumped into reaction kettle with high-pressure pump, 200~300
DEG C, 0.1~10Mpa, material reaction soaking time be continuous feed, discharging under 5~30 minutes high-temperature and high-pressure conditions, then
Discharging fusant enters devolatilization tank devolatilization, then extruded molding, obtains finished product.
Patent CN104311726B describes a kind of preparation method of solid propenoic acid resin, by all monomers and initiation
Agent, chain-transferring agent and helper component are added in reaction kettle after stirring and dissolving is uniform in material pot, with 120~180 DEG C,
Polymerisation is carried out under 0.1Mpa~1Mpa；When the monomer conversion in reaction kettle reaches 40~50%, start to store up solvent
Retarder thinner in tank, which is gradually dropped in reaction kettle, carries out viscosity reduction, keep reaction kettle in the good flow regime of material, when turn
After rate reaches 70~80%, by resulting material, further polymerisation in tubular reactor is continuously squeezed into through high-pressure pump, is reacted
150~240 DEG C of temperature, 2~40 minutes residence times；Subsequently into volatilization tower, the material by devolatilization is arranged from volatilization tower lower part
It removes, obtains solid propenoic acid resin.
Patent US4414370 describes a kind of this preparation of the acrylate of molecular weight narrow ditribution, by all lists
Body and initiator be added to 1 gallon, the interior continuously stirred tank reactor (CSTR) for setting conduction oil cooling coil, inlet amount 0.2~
0.8lbs/min, reaction temperature are increased to 190~310 DEG C, 5~30 minutes residence times, 90% or more monomer conversion.Then
Material enters in stirring devolatilization slot, and 270 DEG C of devolatilization temperature deviates from unreacted monomer, then condensed recycling.Products obtained therefrom point
Son amount distribution is less than 2.
In above-mentioned patent, polymerization reaction time is shorter, and production efficiency will be very high.Meanwhile the reaction time is shorter, it is meant that
The heat of unit interval is higher, and the removal of polymerization process heat becomes more difficult.It is less than one hour or even several in the reaction time
Under conditions of minute, the unit interval needs the heat number value removed very big, if to realize the industrial production of typical products in mass production,
It is also to be solved with the relevant many engineering problems that conduct heat.
Roehm house journals US7368094B2 discloses a kind of continuous polymerization technique of tubular reactor：Monomer, initiation
The mixtures such as agent, into a vertically arranged tubular reactor bottom, tubular reactor is divided into 4 sections, and every section can independent control
Temperature, the feed rate of material in the reactor are 0.1~50cm/sec.Finally discharge from tubular reactor topmost, conversion
Rate can reach 97% or more.
In patent US7368094B2, reactor is mediated using LIST automatically cleanings by Evonik companies, in 110~130 DEG C of conditions
Under, acrylic acid (ester) monomer mixture reacts 20min~1hr in polymer reactor, then enters degassing by Melt Pump
In kneader, then extruded pelletizing, finished product.Products obtained therefrom residual monomer content is low.
The LIST automatically cleanings mentioned in patent US7368094B2 mediate reactor, popular understanding, and similar mixer is pinched
Effect is closed, material obtains good mixing and Surface Renewal, is suitble to highly viscous material polymerization and kneading process.Reactor presss from both sides
Set, agitating paddle and agitating shaft can admittance deep fat, there is relatively large heat transfer area.Due to being limited by reactor agitating paddle
And the inner members such as agitating shaft, fluid flow resistance is big, and flow velocity is limited, this can reduce the heat transfer coefficient in actual polymerisation process, remove
Thermal energy power is insufficient, and reaction temperature is difficult to accurately control.The patent is also mentioned, in production application, 10~15 DEG C of temperature fluctuation.
More relevant surely belong to above-mentioned 2 patents with the present invention.Patent US7368094B2 uses tubular reactor, and divides
For four independent temperature-controlled areas, the rate of polymerization of monomer material can effectively be controlled, be realize bulk polymerisation process compared with
Good technique.Also to see, monomer mixture since reaction start zero-turn rate, to finally close to 99% high conversion,
The two differences in viscosity is completed polymerization process in a reactor, is answered in actual industrial production up to tens thousand of or even ten tens of thousands of times
In, operating flexibility very little is unfavorable for the regulation and control of technique.Bulk technique in patent US7368094B2, in equipment
On, especially in terms of the polymerization process for realizing high-viscosity material, the limitation of high viscosity range is breached, even if material viscosity reaches
More than 50 million centipoise, it can also realize kneading and melting extrusion in the reactor.Its inside reactor, chuck and agitating paddle can be with
Admittance deep fat, but designed by its internal inner member complexity of mediating, it is difficult to obtain the comparatively ideal coefficient of heat transfer, heat transfer efficiency by
To limitation.For the kneading reactor in production application, reaction temperature fluctuates 10~15 DEG C.
Invention content
To solve the problems, such as that the conveying of technique of continuous bulk polymerization medium-high viscosity, stirring and heat and mass are difficult, the present invention carries
For a kind of equipment and its side preparing solid propenoic acid resin using the plunger flow reactor of multi-stage series, continuous bulk technique
Method, reaction process stable temperature control, products obtained therefrom color and luster is uniform, and molecular weight distribution is smaller.
To reach this purpose, technical solution provided by the invention is as follows：
A kind of device and method thereof preparing solid propenoic acid resin, the equipment include material-compound tank, metering pump, preheating
Device, pre-polymerization reactor, second reactor, third reactor and devolatilization extruder, the material-compound tank top are provided with feed inlet,
Pipeline connects the metering pump, preheater and pre-polymerization reactor, the pre-polymerization reactor lower tube to bottom discharge mouth successively
Road connects the second reactor, and the second reactor bottom pipe connects the third reactor, the third reactor
Bottom discharge mouth connects the devolatilization extruder by pressure-control valve pipeline, the pre-polymerization reactor, second reactor, the
Three reactor heads are provided with exhaust outlet, and if inside be both provided with dried layer heat transfer stirring layer, it is equal that layer is stirred in every layer of heat transfer
Several heat-transfer pipes are horizontally installed with, agitating paddle is installed between the heat transfer stirring layer；
It the described method comprises the following steps：
Parts by weight are respectively 0~15% molecular weight regulator, 0.01~0.6% initiator, 30% by step 1
~100% methacrylic monomer, acrylic monomer and 0~55% vinyl monomer, 0~50% other classes
The material-compound tank is added in monomer, is sufficiently mixed into monomer mixture；
Step 2, by the monomer mixture by the metering pump accurate measurement, with the speed of 0.6kg~1.0kg/hr
It is transported in the pre-polymerization reactor through the preheater；
Step 3, the pre-polymerization reactor speed of agitator are 20~100rpm, and inlet pressure is 3~12bar, reaction temperature
Degree is 90~120 DEG C, and monomer conversion is 35~50%, and the monomer mixture is after the pre-polymerization reactor, the bottom of from
The material of portion outlet enters second reactor upper entrance through feed-line；
Step 4, the second reactor speed of agitator are 20~100rpm, and reaction temperature is 100~130 DEG C, and monomer turns
Rate is 45~85%, after material filling is full, then through feed-line, enters third reactor upper entrance；
Step 5, the third reactor speed of agitator are 0~15rpm, and reaction temperature is 140~200 DEG C, monomer conversion
Rate is 98% or more the pressure-control valve for eventually passing through the third reactor outlet, enters the devolatilization extruder.
The initiator includes peroxidized t-butyl perbenzoate, bis 25 vulcanizing agent, dibenzoyl peroxide, tertiary pentyl mistake
Oxidizing ethyle alkyl.
The molecular weight regulator is n-dodecyl mercaptan.
The methacrylic monomer includes：Methacrylic acid, methyl methacrylate, ethyl methacrylate, first
Base n-butyl acrylate, Isobutyl methacrylate, hydroxyethyl methacrylate, lauryl methacrylate, methacrylic acid
Ethoxy ethyl ester；
The acrylic monomer includes：Acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid
Isobutyl ester, sec-butyl acrylate, tert-butyl acrylate, n-propyl, lauryl acrylate, Isooctyl acrylate monomer；
The vinyl monomer includes：Styrene, acrylonitrile, vinylacetate, acrylamide；
Other described class monomers include：2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, methacrylic acid -2-
Hydroxy methacrylate, methacrylic acid -2- hydroxy propyl esters, glycidyl methacrylate, maleic anhydride, maleic acid.
The pre-polymerization reactor, second reactor, third reactor, reactor shell and diameter draw ratio L/D
=5~12.
The pre-polymerization reactor, second reactor, third reactor are divided into 2~4 independent temperature-controlled areas.
The number of plies of the agitating paddle and heat-transfer pipe is 8~100 layers, and the diameter of stirring paddle and the prepolymerization
Device, second reactor, third reactor inside diameter ratio are 0.85~0.96, and the heat transfer pipe diameter D is 6~25mm.
Need to solve 1) how to remove reaction heat in time during solid propenoic acid resin continuous bulk polymerization, accurately control
Reaction temperature；2) phase after the reaction, when conversion ratio is more than 90%, mass-and heat-transfer of the material under high viscosity state.
Timely removal for reaction heat and reaction temperature control, the present invention is according to the calculating of reaction heat in formula, rationally
The residence time of material in the reactor is set, the rate of polymerization of each reaction zone of every reactor is controlled, realizes and removes in time
The purpose for the heat that each reaction zone is released.Multilayer heat-transfer pipe is arranged in inside reactor, and heat transfer area is big, in heat-transfer pipe and chuck
Portion's admittance deep fat, for heating or removing heat.Under agitation, the higher coefficient of heat transfer can be obtained, under the temperature difference of appropriateness,
Each stage of reaction can be removed in time, and the reaction heat of releasing accurately controls reaction temperature.
Solid propenoic acid resin molecular weight and glass transition temperature are relatively low, and polymerization process is less than 80% in solid holdup
When, under the conditions of corresponding polymeric reaction temperature, material viscosity is relatively low；When 90% or more conversion ratio, material viscosity increases rapidly
Add, can reach million mpa.s or more, stirring becomes extremely difficult.To solve this problem, in the solution of the present invention, reactor
With larger draw ratio, diameter of stirring paddle is relatively small；It controls simultaneously into 85% or more third reactor content conversion ratio,
Content of monomer is low, and rate of polymerization is not high, it is only necessary to maintain very low speed of agitator, keep the temperature in each area of reactor molten in material
Melt temperature or more.Accordingly even when in high viscosity, stir required torque and little, realize high-viscosity material conveying and
Mass-and heat-transfer.
Compared with prior art, the beneficial effects of the invention are as follows：
1, in the reaction of solid propenoic acid resin continuous bulk polymerization, function division is carried out by polymerization process, in prepolymerization
In reactor, it is characterized in that content of monomer is high, material viscosity is very low, and rate of polymerization is more difficult to control, maintains higher speed of agitator；
In third reactor, materials conversion rate is high, and viscosity drastically increases, the temperature in each area of control reactor material melting temperature with
On, and the lower rotating speed of reactor is maintained, material can still carry out the polymerisation of temperature-controllable, significantly under high viscosity state
Improve monomer conversion.
2, the reactor in the present invention, built-in multilayer heat-transfer pipe have larger heat transfer area, in sufficient radial mixing
Under, good heat and mass effect is obtained, removes reaction heat in time, each reaction zone polymerization temperature accurately controls, and realizes each anti-
Answer the monomer conversion of demands.
3, since there is the reactor in the present invention larger draw ratio, reactor stirring to have radially good mixed
It closes, realizes the radially identical rate of polymerization of reaction mass, but in the axial direction, back-mixing is few, obtained product, there is relatively narrow point
The distribution of son amount and the uniform feature of quality.
Description of the drawings
Fig. 1 is the equipment connection diagram of the present invention；
Fig. 2 is the sectional top view of heat transfer stirring layer.
In attached drawing：1. material-compound tank；2. metering pump；3. preheater；4. pre-polymerization reactor；5. second reactor；6. third
Reactor；7. devolatilization extruder；8. devolatilizer；9. heat transfer stirring layer；10. heat-transfer pipe；11. agitating paddle；12. pressure-control valve；
13. exhaust outlet.
Specific implementation mode
As Fig. 1 is special to a kind of device and method thereof preparing solid propenoic acid resin shown in Fig. 2 in Figure of description
Sign is：Equipment includes material-compound tank 1, metering pump 2, preheater 3, pre-polymerization reactor 4, second reactor 5 and third reactor 6
And devolatilization extruder 7,1 top of material-compound tank are provided with feed inlet, pipeline connects metering pump 2,3 and of preheater to bottom discharge mouth successively
Pre-polymerization reactor 4,4 bottom pipe of pre-polymerization reactor connect second reactor 5,5 bottom pipe of second reactor connection the
Three reactors 6,6 bottom discharge mouth of third reactor connect devolatilization extruder 7 or devolatilizer 8 by 12 pipeline of pressure-control valve,
Pre-polymerization reactor, second reactor, third reactor head are provided with exhaust outlet 13, and inside is both provided with several heat transfers and stirs
Layer 9 is mixed, every layer of heat transfer stirring layer 9 is mounted on heat-transfer pipe 10 and agitating paddle 11, and agitating paddle 11 is mounted on every layer of heat transfer and stirs layer 9
Center, every layer heat transfer stirring layer 9 or so and lower section in the middle part of be arranged demarcation strip, 10 bottom of left side heat-transfer pipe connect conduction oil into
Mouthful, heat-transfer pipe 10 bottom in right side connects conduction oil outlet, and the unidirectional Oil Guide heat supply of cycle is formed with this.
Example given below is for further illustrating the present invention, but the limitation not to feature disclosed herein.
Embodiment 1
Methyl methacrylate 20kg, methacrylic acid -2- hydroxy methacrylates 16kg, metering system are added in material-compound tank 1
Acid butyl ester 13.5kg, methacrylic acid 0.5kg, molecular weight regulator n-dodecyl mercaptan 3.5kg, initiator benzoyl peroxide first
Tert-butyl acrylate 0.05kg；
The material mixed is entered by metering pump 2, preheated device 3 in pre-polymerization reactor 4.The preheated device of material 3
60 DEG C are first to heat to, inlet amount 1000ml/hr.Reacting system pressure~0.45Mpa；Material is completely filled in three reactors
State.
Three temperature-controlled areas R11, R12, R13 of pre-polymerization reactor 4, temperature control respectively 92 DEG C, 98 DEG C, 102
℃；Reactor speed of agitator 20rpm；Reaction time 3.5hr.
By the material of pre-polymerization reactor 4, conversion ratio 45%, then into second reactor 5, second reactor 5
Three temperature-controlled areas R21, R22, R23, temperature are controlled respectively at 108 DEG C, 116 DEG C, 128 DEG C；Reactor speed of agitator
20rpm.Reaction time 3.5hr.
By the material of second reactor 5, conversion ratio 88%, then into third reactor 6, third reactor 6 three
A temperature-controlled area R31, R32, R33, temperature are controlled respectively at 135 DEG C, 146 DEG C, 155 DEG C；Reactor speed of agitator 5rpm.Instead
3hr between seasonable.6 outlet material conversion ratio 98~99% of third reactor.
Embodiment 2
Methyl methacrylate 24.5kg, isobornyl methacrylate 24.5kg, metering system are added in material-compound tank 1
Sour 1kg, molecular weight regulator n-dodecyl mercaptan 2.8kg, initiator peroxidized t-butyl perbenzoate 0.05kg；
The material mixed is entered by metering pump 2, preheated device 3 in pre-polymerization reactor 4.The preheated device of material 3
60 DEG C are first to heat to, inlet amount 1000ml/hr.Reacting system pressure~0.55Mpa；Material is completely filled in three reactors
State.
Three temperature-controlled areas R11, R12, R13 of pre-polymerization reactor 4, temperature control respectively 92 DEG C, 96 DEG C, 100
℃；Reactor speed of agitator 25rpm；Reaction time 3hr.
By the material of pre-polymerization reactor 4, conversion ratio 43%, then into second reactor 5, second reactor 5
Three temperature-controlled areas R21, R22, R23, temperature are controlled respectively at 108 DEG C, 116 DEG C, 125 DEG C；Reactor speed of agitator
25rpm.Reaction time 3.5hr.
By the material of second reactor 5, conversion ratio 87%, then into third reactor 6, third reactor 6 three
A temperature-controlled area R31, R32, R33, temperature are controlled respectively at 136 DEG C, 148 DEG C, 162 DEG C；Reactor speed of agitator 4rpm.Instead
3.5hr between seasonable.6 outlet material conversion ratio 98~99% of third reactor.
Embodiment 3
Methyl methacrylate 2.5kg, styrene 13kg, α-methylstyrene 16.5, acrylic acid are added in material-compound tank 1
Different monooctyl ester 1kg, molecular weight regulator n-dodecyl mercaptan 6.2kg, initiator peroxidized t-butyl perbenzoate 0.065kg；
The material mixed is entered by metering pump 2, preheated device 3 in pre-polymerization reactor 4.The preheated device of material 3
60 DEG C are first to heat to, inlet amount 800ml/hr.Reacting system pressure~0.60Mpa；Material is completely filled in three reactors
State.
Three temperature-controlled areas R11, R12, R13 of pre-polymerization reactor 4, temperature control respectively 92 DEG C, 95 DEG C, 98
℃；Reactor speed of agitator 28rpm；Reaction time 3.5hr.
By the material of pre-polymerization reactor 4, conversion ratio 46%, then into second reactor 5, second reactor 5
Three temperature-controlled areas R21, R22, R23, temperature are controlled respectively at 108 DEG C, 116 DEG C, 126 DEG C；Reactor speed of agitator
28rpm.Reaction time 3.5hr.
By the material of second reactor 5, conversion ratio 89%, then into third reactor 6, third reactor 6 three
A temperature-controlled area R31, R32, R33, temperature are controlled respectively at 137 DEG C, 150 DEG C, 165 DEG C；Reactor speed of agitator 4rpm.Instead
3.5hr between seasonable.6 outlet material conversion ratio 98~99% of third reactor.
Embodiment 4
Styrene 17kg, α-methylstyrene 12, acrylic acid 21kg, molecular weight regulator positive ten are added in material-compound tank 1
Dialkyl group mercaptan 6.4kg, initiator peroxidized t-butyl perbenzoate 0.060kg；
The material mixed is entered by metering pump 2, preheated device 3 in pre-polymerization reactor 4.The preheated device of material 3
60 DEG C are first to heat to, inlet amount 800ml/hr.Reacting system pressure~0.60Mpa；Material is completely filled in three reactors
State.
Three temperature-controlled areas R11, R12, R13 of pre-polymerization reactor 4, temperature control respectively 92 DEG C, 95 DEG C, 98
℃；Reactor speed of agitator 28rpm；Reaction time 3.5hr.
By the material of pre-polymerization reactor 4, conversion ratio 46%, then into second reactor 5, second reactor 5
Three temperature-controlled areas R21, R22, R23, temperature are controlled respectively at 108 DEG C, 116 DEG C, 126 DEG C；Reactor speed of agitator
28rpm.Reaction time 3.5hr.
By the material of second reactor 5, conversion ratio 89%, then into third reactor 6, third reactor 6 three
A temperature-controlled area R31, R32, R33, temperature are controlled respectively at 137 DEG C, 150 DEG C, 165 DEG C；Reactor speed of agitator 4rpm.Instead
3.5hr between seasonable.6 outlet material conversion ratio 98~99% of third reactor.
Embodiment 5
Methyl esters methyl acrylate 20kg, butyl methacrylate 25kg, acrylic acid 5kg, molecular weight are added in material-compound tank 1
Conditioning agent n-dodecyl mercaptan 0.43kg, initiator peroxidized t-butyl perbenzoate 0.054kg, double two or five vulcanizers
0.024kg；
The material mixed is entered by metering pump 2, preheated device 3 in pre-polymerization reactor 4.The preheated device of material 3
55 DEG C are first to heat to, inlet amount 800ml/hr.Reacting system pressure~0.85Mpa；Material is completely filled in three reactors
State.
Three temperature-controlled areas R11, R12, R13 of pre-polymerization reactor 4, temperature control respectively 94 DEG C, 97 DEG C, 104
℃；Reactor speed of agitator 30rpm；Reaction time 3.5hr.
By the material of pre-polymerization reactor 4, conversion ratio 46%, then into second reactor 5, second reactor 5
Three temperature-controlled areas R21, R22, R23, temperature are controlled respectively at 112 DEG C, 128 DEG C, 136 DEG C；Reactor speed of agitator
25rpm.Reaction time 3.5hr.
By the material of second reactor 5, conversion ratio 89%, then into third reactor 6, third reactor 6 three
A temperature-controlled area R31, R32, R33, temperature are controlled respectively at 150 DEG C, 162 DEG C, 185 DEG C；Reactor speed of agitator 1rpm.Instead
3.5hr between seasonable.6 outlet material conversion ratio 98~99% of third reactor.
30 DEG C≤glass transition temperature of resulting polymers product Tg≤75 DEG C, molecular weight 4,000≤Mw≤120,000g/mol,
Molecular weight distribution 1.8~2.4.
The result of embodiment is summarized as follows table：
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Molecular weight Mw, g/mol | 5,250 | 8,330 | 18,340 | 19,525 | 54,600 |
| Molecular weight distribution PDI | 2.3 | 2.2 | 2.4 | 2.2 | 2.1 |
| Monomer conversion, % | 98.8 | 98.5 | 99 | 98.2 | 98.2 |
To sum up, only presently preferred embodiments of the present invention is not used for limiting the scope of implementation of the present invention, Fan Yibenfa
Equivalent changes and modifications carried out by the shape of bright right, construction, feature and spirit should all be included in the power of the present invention
In sharp claimed range.
Claims (7)
1. a kind of device and method thereof preparing solid propenoic acid resin, it is characterised in that：The equipment includes material-compound tank, metering
Pump, preheater, pre-polymerization reactor, second reactor, third reactor and devolatilization extruder, the material-compound tank top are provided with
Feed inlet, pipeline connects the metering pump, preheater and pre-polymerization reactor, the pre-polymerization reactor to bottom discharge mouth successively
Bottom pipe connects the second reactor, and the second reactor bottom pipe connects the third reactor, the third
Reactor bottom discharge port connects the devolatilization extruder by pressure-control valve pipeline, and the pre-polymerization reactor, second are instead
Answer device, third reactor head to be provided with exhaust outlet, and if inside be both provided with dried layer heat transfer stirring layer, every layer it is described heat transfer stir
It mixes layer and is horizontally installed with several heat-transfer pipes, agitating paddle is installed between the heat transfer stirring layer；
It the described method comprises the following steps：
Step 1, by parts by weight be respectively 0~15% molecular weight regulator, 0.01~0.6% initiator, 30%~
100% methacrylic monomer, acrylic monomer and 0~55% vinyl monomer, 0~50% other class lists
The material-compound tank is added in body, is sufficiently mixed into monomer mixture；
Step 2, by the monomer mixture by the metering pump accurate measurement, with the speed of 0.6kg~1.0kg/hr through institute
Preheater is stated to be transported in the pre-polymerization reactor；
Step 3, the pre-polymerization reactor speed of agitator are 20~100rpm, and inlet pressure is 3~12bar, and reaction temperature is
90~120 DEG C, monomer conversion is 35~50%, and the monomer mixture goes out after the pre-polymerization reactor from bottom
The material of mouth enters second reactor upper entrance through feed-line；
Step 4, the second reactor speed of agitator are 20~100rpm, and reaction temperature is 100~130 DEG C, monomer conversion
It is 45~85%, after material filling is full, then through feed-line, enters third reactor upper entrance；
Step 5, the third reactor speed of agitator are 0~15rpm, and reaction temperature is 140~200 DEG C, and monomer conversion is
98% or more eventually passes through the pressure-control valve of the third reactor outlet, enters the devolatilization extruder.
2. a kind of device and method thereof preparing solid propenoic acid resin according to claim 1, it is characterised in that：It is described
Initiator includes peroxidized t-butyl perbenzoate, bis 25 vulcanizing agent, dibenzoyl peroxide, t-amyl peroxy hexamethylene.
3. a kind of device and method thereof preparing solid propenoic acid resin according to claim 1, it is characterised in that：It is described
Molecular weight regulator is n-dodecyl mercaptan.
4. a kind of device and method thereof preparing solid propenoic acid resin according to claim 1, it is characterised in that：It is described
Methacrylic monomer includes：The positive fourth of methacrylic acid, methyl methacrylate, ethyl methacrylate, methacrylic acid
Ester, Isobutyl methacrylate, hydroxyethyl methacrylate, lauryl methacrylate, ethoxyethyl methacrylates；
The acrylic monomer includes：Acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl
Ester, sec-butyl acrylate, tert-butyl acrylate, n-propyl, lauryl acrylate, Isooctyl acrylate monomer；
The vinyl monomer includes：Styrene, acrylonitrile, vinylacetate, acrylamide；
Other described class monomers include：2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, methacrylic acid -2- hydroxyls
Ethyl ester, methacrylic acid -2- hydroxy propyl esters, glycidyl methacrylate, maleic anhydride, maleic acid.
5. a kind of device and method thereof preparing solid propenoic acid resin according to claim 1, it is characterised in that：It is described
Pre-polymerization reactor, second reactor, the cylinder of third reactor and diameter draw ratio L/D=5~12.
6. a kind of device and method thereof preparing solid propenoic acid resin according to claim 1, it is characterised in that：It is described
Pre-polymerization reactor, second reactor, third reactor are divided into 2~4 independent temperature-controlled areas.
7. a kind of device and method thereof preparing solid propenoic acid resin according to claim 1, it is characterised in that：It is described
The number of plies of heat-transfer pipe is 8~100 layers, and the diameter of stirring paddle is reacted with the pre-polymerization reactor, second reactor, third
Device internal diameter ratio is 0.85~0.96, and the heat transfer pipe diameter D is 6~25mm.
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| CN115197377A (en) * | 2022-07-20 | 2022-10-18 | 浙江卫星新材料科技有限公司 | Continuous bulk polymerization high-absorptivity resin preparation system |
| CN115703863A (en) * | 2021-08-06 | 2023-02-17 | 中国石油化工股份有限公司 | Flame-retardant acrylate rubber and preparation method and application thereof |
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Application publication date: 20181019 |