CN116617993A - Device and method for preparing polymethylene polyphenyl polyurethane - Google Patents
Device and method for preparing polymethylene polyphenyl polyurethane Download PDFInfo
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- CN116617993A CN116617993A CN202310925795.6A CN202310925795A CN116617993A CN 116617993 A CN116617993 A CN 116617993A CN 202310925795 A CN202310925795 A CN 202310925795A CN 116617993 A CN116617993 A CN 116617993A
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- -1 polymethylene Polymers 0.000 title claims abstract description 67
- 229920006389 polyphenyl polymer Polymers 0.000 title claims abstract description 50
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 39
- 239000004814 polyurethane Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 45
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims abstract description 45
- 239000008346 aqueous phase Substances 0.000 claims abstract description 40
- 239000012071 phase Substances 0.000 claims abstract description 32
- IAGUPODHENSJEZ-UHFFFAOYSA-N methyl n-phenylcarbamate Chemical compound COC(=O)NC1=CC=CC=C1 IAGUPODHENSJEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 58
- 238000004945 emulsification Methods 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 238000009833 condensation Methods 0.000 claims description 22
- 230000005494 condensation Effects 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- 239000012022 methylating agents Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011324 bead Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 6
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 229940117389 dichlorobenzene Drugs 0.000 claims description 6
- 229920002866 paraformaldehyde Polymers 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- SCWKRWCUMCMVPW-UHFFFAOYSA-N phenyl n-methylcarbamate Chemical compound CNC(=O)OC1=CC=CC=C1 SCWKRWCUMCMVPW-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 229920003229 poly(methyl methacrylate) Polymers 0.000 abstract description 2
- 239000004926 polymethyl methacrylate Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- OTSJRHVZRARHBC-UHFFFAOYSA-N benzylbenzene;carbamic acid Chemical compound NC(O)=O.NC(O)=O.C=1C=CC=CC=1CC1=CC=CC=C1 OTSJRHVZRARHBC-UHFFFAOYSA-N 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- KBAAVEBMJBZPCJ-UHFFFAOYSA-N anilino formate Chemical compound O=CONC1=CC=CC=C1 KBAAVEBMJBZPCJ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009500 colour coating Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- BSCCSDNZEIHXOK-UHFFFAOYSA-N phenyl carbamate Chemical compound NC(=O)OC1=CC=CC=C1 BSCCSDNZEIHXOK-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002699 waste material Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/30—Micromixers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/80—Mixing plants; Combinations of mixers
- B01F33/81—Combinations of similar mixers, e.g. with rotary stirring devices in two or more receptacles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/80—Mixing plants; Combinations of mixers
- B01F33/836—Mixing plants; Combinations of mixers combining mixing with other treatments
- B01F33/8362—Mixing plants; Combinations of mixers combining mixing with other treatments with chemical reactions
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a device and a method for preparing polymethylene polyphenyl polyurethane, wherein the device comprises a first micromixer, a tubular reactor, a second micromixer, a kettle reactor and a centrifugal separator which are sequentially connected, and water phase components discharged by the centrifugal separator are returned to the first micromixer. According to the invention, by arranging the multistage micromixer and the reactor, the methyl anilinoformate oil phase solution and the methylene reagent aqueous phase solution can be more fully emulsified and condensed intensively, so that the conversion rate of methyl anilinoformate and the yield of polymethylene polyphenyl polymethylmethacrylate are improved, the device meets continuous operation conditions, and industrial application can be realized.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a device and a method for preparing polymethylene polyphenyl polyurethane.
Background
Isocyanate is an important raw material for synthesizing polyurethane, can also be used for synthesizing metal adhesives, glass fibers, color coatings and artificial leather, and is widely applied to the fields of buildings, automobiles, ships, aviation, shoemaking, daily necessities and the like at present. The isocyanate is mainly divided into aliphatic isocyanate and aromatic isocyanate, and can be synthesized by a phosgene method or a non-phosgene method.
The production of the aromatic isocyanate through the pyrolysis of the polymethylene polyphenyl aromatic carbamate is a green and clean method, and the efficient synthesis of the polymethylene polyphenyl aromatic carbamate is one of key links. Among them, the preparation of polymethylene polyphenyl polyurethane by condensation of carbamate with a methylating agent is becoming a current research focus.
CN 100528348A discloses a catalyst for preparing diphenyl methane dicarbamate by reacting phenyl carbamate with a methylene reagent and condensing in one step, in particular to synthesizing 4,4' -diphenyl methane dicarbamate. The catalyst takes inorganic acid as a catalyst and inorganic salt as a catalyst auxiliary agent. The yield of the diphenyl methane dicarbamate can reach 91 percent, the selectivity is 96 percent, and the MDC product can be separated after the reaction is finished and filtered and washed with water.
CN 101440048A discloses a method for liquid acid catalyzed synthesis of diphenylmethane dicarbamates, in particular synthesis of 4,4' -diphenylmethane dicarbamates, in a complex solvent system. In a composite component solvent system, the anilino formate and a methylene reagent are subjected to catalytic condensation by liquid inorganic acid, the composite component solvent can well promote the catalytic activity of the liquid acid, and in the process of synthesizing the diphenyl methane dicarbamate by one-step reaction, the conversion rate of the raw material anilino formate and the yield of the diphenyl methane dicarbamate are higher, and only a small amount of byproducts are generated.
The technical route reaction system for synthesizing the polymethylene polyphenyl polyurethane simultaneously has a multiphase complex process, which can cause the technical problem of complex subsequent product separation and purification, and the synthesis method has the important point that the catalyst preparation process is adopted to improve the conversion rate and selectivity of the reaction by improving the stability of the catalyst, but the selection of a reaction device is not involved, and the accurate regulation and control of the reaction process are difficult.
In view of the deficiencies of the prior art, it is desirable to provide a device that provides high selectivity and yield of product and allows for product separation.
Disclosure of Invention
The invention aims to provide a device and a method for preparing polymethylene polyphenyl polyurethane, which are characterized in that a multistage micromixer and a reactor are arranged, so that preparation raw materials can be fully emulsified and subjected to condensation reaction, the conversion rate of reactants and the yield of target products are improved, and the device meets continuous operation conditions, and can realize industrial application.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an apparatus for preparing polymethylene polyphenyl polyurethane, the apparatus comprising a first micromixer, a tubular reactor, a second micromixer, a tank reactor and a centrifugal separator connected in sequence, the aqueous phase component discharged from the centrifugal separator being returned to the first micromixer.
Compared with a single micromixer and a reactor, the device provided by the invention can enable the methyl anilinoformate oil phase solution and the methylene reagent aqueous phase solution to be more fully emulsified and condensed to be enhanced, thereby improving the conversion rate of methyl anilinoformate and the yield of polymethylene polyphenyl polyurethane, improving the market economy, meeting continuous operation conditions and realizing industrial application.
Preferably, the first micromixer is provided with an oil phase component inlet and a first aqueous phase component inlet;
the second micromixer is provided with a second aqueous phase component inlet.
Preferably, the first and second micromixers each independently comprise a T-type mixer and/or a Y-type mixer.
Preferably, the centrifugal separator comprises any one of a decanter centrifuge, a bowl centrifuge, or a rotary vane separator.
In a second aspect, the present invention provides a process for preparing polymethylene polyphenyl polymethylene carbamates using the apparatus of the first aspect, the process comprising the steps of:
the preparation method comprises the steps of carrying out first emulsification treatment, first condensation treatment, second emulsification treatment and second condensation treatment on an phenylmethyl carbamate oil phase solution and a methylene reagent aqueous phase solution, and separating an obtained emulsified mixture to obtain the methylene reagent aqueous phase solution and a polymethylene polyphenyl polymethylene carbamate oil phase solution; the resulting aqueous solution of the methyleneating agent is recycled back for use in the first emulsification process.
According to the method provided by the invention, the methyl anilino formate oil phase solution and the methylene reagent aqueous phase solution are adopted for alternate emulsification and condensation treatment, so that the emulsification effect can be improved, the condensation can be enhanced, the methyl anilino formate is efficiently converted into polymethylene polyphenyl polyurethane, meanwhile, the generated methylene reagent can be recycled, the cost of water resource treatment is reduced, the resource waste is also reduced, and the method has the characteristics of environmental friendliness, simplicity in operation and low cost.
Preferably, the solvent in the methyl anilinoformate oil phase solution comprises any one or a combination of at least two of toluene, ethylbenzene, chlorobenzene, dichlorobenzene, or xylene, typically but not limited to combinations comprising toluene and chlorobenzene, dichlorobenzene and xylene, or toluene, ethylbenzene, chlorobenzene, dichlorobenzene and xylene.
The mass concentration of the methyl anilinoate in the methyl anilinoate oil phase solution is 0.1-20%, for example, 0.1%, 1%, 3%, 5%, 10% or 20%, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the mass concentration of the methylating agent in the aqueous solution of methylating agent is 0.1-10%, for example, 0.1%, 0.6%, 1%, 1.5%, 4%, 7% or 10%, but not limited to the recited values, other non-recited values within the range of values are equally applicable;
the aqueous solution of the methylating agent comprises any one or a combination of at least two of formaldehyde, trioxymethylene or paraformaldehyde, and typical but non-limiting combinations include a combination of formaldehyde and trioxymethylene, a combination of trioxymethylene and paraformaldehyde, or a combination of formaldehyde, trioxymethylene and paraformaldehyde.
Preferably, the aqueous solution of the methyleneating agent includes a protonic acid solution, wherein the protonic acid includes any one or a combination of at least two of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, and hydrofluoric acid, and typical but non-limiting combinations include combinations of hydrochloric acid and sulfuric acid, combinations of phosphoric acid and hydrofluoric acid, combinations of hydrochloric acid, sulfuric acid, acetic acid, and phosphoric acid, or combinations of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, and hydrofluoric acid;
the mass fraction of the protonic acid in the protonic acid solution is 1-40%, for example, 1%, 10%, 20%, 30% or 40%, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable;
the molar ratio of methyl anilinoformate to the methyleneating agent is 1 (1-4), for example, 1:1, 1:1.5, 1:2, 1:3 or 1:4, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the temperatures of the first emulsification treatment, the first condensation treatment, the second emulsification treatment and the second condensation treatment are respectively 40-180 ℃, and the total time is 10-360min;
the second emulsification treatment is additionally supplemented with an aqueous solution of a methylating agent.
The aqueous solution of the additional methylating agent is used in an amount of 0.1 to 2 times the total molar amount of methyl anilinoformate, for example 0.1, 0.5, 0.8, 1, 1.5 or 2 times, but is not limited to the values recited, but other values not recited in the numerical range are equally applicable.
Fresh aqueous phase solution of the methylene reagent is additionally supplemented in the second emulsification treatment, so that the conversion rate of raw material methyl anilinoformate can be further improved, and the process design requirement is met.
The temperature is 40 to 180 ℃, for example, 40 ℃, 80 ℃, 120 ℃, 150 ℃ or 180 ℃, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable, preferably 80 to 150 ℃.
The temperature range is selected within a reasonable range, so that the emulsification and condensation reaction process can be promoted, and the conversion rate of reactants and the yield of target products can be reduced due to the fact that the temperature is too high or too low.
The total time is 10-360min, for example, 10min, 30min, 90min, 120min, 180min, 240min or 360min, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the beads in the emulsified mixture have a diameter of 1-1000 μm, for example, 1 μm, 10 μm, 100 μm, 500 μm or 1000 μm, but are not limited to the values recited, and other values not recited in the range of values are equally applicable;
the liquid beads comprise water beads and/or oil beads.
As a preferred embodiment of the method according to the second aspect of the present invention, the method comprises the steps of:
at 40-180 ℃, carrying out first emulsification treatment, first condensation treatment, second emulsification treatment and second condensation treatment on the methyl anilino formate oil phase solution and the methylene reagent aqueous phase solution, wherein the total time is 10-360min, additionally supplementing the methylene reagent aqueous phase solution in the second emulsification treatment, and separating an emulsified mixture with the obtained water drops and/or oil drops with the diameter of 1-1000 mu m to obtain the methylene reagent aqueous phase solution and the polymethylene polyphenyl polyurethane oil phase solution; the resulting aqueous solution of the methyleneating agent is recycled back for use in the first emulsification treatment;
the solvent in the methyl anilinoformate oil phase solution comprises any one or a combination of at least two of toluene, ethylbenzene, chlorobenzene, dichlorobenzene and xylene; the mass concentration of the methyl anilinoate in the methyl anilinoate oil phase solution is 0.1 to 20 percent;
the mass concentration of the methylene reagent in the aqueous solution of the methylene reagent is 0.1-10%; the aqueous solution of the methylene reagent comprises any one or a combination of at least two of formaldehyde, trioxymethylene or paraformaldehyde;
the aqueous solution of the methylene reagent comprises a protonic acid solution, wherein the protonic acid in the protonic acid solution comprises any one or a combination of at least two of hydrochloric acid, sulfuric acid, phosphoric acid and hydrofluoric acid; the mass fraction of the protonic acid in the protonic acid solution is 1-40%; the molar ratio of the methyl anilinoformate to the methyleneating agent is 1 (1-4).
Compared with the prior art, the invention has the following beneficial effects:
according to the device provided by the invention, the multistage micromixer and the reactor are arranged, so that compared with a single micromixer and a single micromixer, an oil phase solution of the methyl anilinoate and an aqueous phase solution of a methylene reagent are more fully emulsified and condensed intensively, the conversion rate of the methyl anilinoate and the yield of the polymethylene polyphenyl polyurethane are improved, the conversion rate of the methyl anilinoate is up to 100%, the yield of the polymethylene polyphenyl polyurethane is up to 100%, the selectivity of a target product of the polymethylene polyphenyl polyurethane is improved, the market economy is improved, the device accords with continuous operation conditions, and industrial application can be realized; the generated methylene reagent can be recycled, the cost of water resource treatment is reduced, and the method has the characteristics of environmental protection, simple operation and low cost.
Drawings
FIG. 1 is a schematic structural view of an apparatus for preparing polymethylene polyphenyl polyurethane provided by the present invention;
wherein: 1, a first micromixer; 2, a tubular reactor; 3, a second micromixer; 4, a kettle type reactor; 5, a centrifugal separator; 6, an oil phase component inlet; 7, a first aqueous phase component inlet; 8, a second aqueous phase component inlet.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a device for preparing polymethylene polyphenyl polyurethane, which is shown in figure 1, and comprises a first micromixer 1, a tubular reactor 2, a second micromixer 3, a kettle reactor 4 and a centrifugal separator 5 which are sequentially connected, wherein an aqueous phase component discharged by the centrifugal separator 5 is returned to the first micromixer 1;
the first micromixer 1 is provided with an oil phase component inlet 6 and a first aqueous phase component inlet 7; the second micromixer 3 is provided with a second aqueous phase component inlet 8;
the first micro mixer 1 and the second micro mixer 3 are respectively T-shaped mixers; the centrifugal separator 5 is a horizontal screw type centrifuge.
Example 2
The embodiment provides a device for preparing polymethylene polyphenyl polyurethane, which is shown in figure 1, and comprises a first micromixer 1, a tubular reactor 2, a second micromixer 3, a kettle reactor 4 and a centrifugal separator 5 which are sequentially connected, wherein an aqueous phase component discharged by the centrifugal separator 5 is returned to the first micromixer 1;
the first micromixer 1 is provided with an oil phase component inlet 6 and a first aqueous phase component inlet 7; the second micromixer 3 is provided with a second aqueous phase component inlet 8;
the first micro mixer 1 and the second micro mixer 3 are Y-shaped mixers respectively; the centrifugal separator 5 is a bowl centrifuge.
Example 3
The embodiment provides a device for preparing polymethylene polyphenyl polyurethane, which is shown in figure 1, and comprises a first micromixer 1, a tubular reactor 2, a second micromixer 3, a kettle reactor 4 and a centrifugal separator 5 which are sequentially connected, wherein an aqueous phase component discharged by the centrifugal separator 5 is returned to the first micromixer 1;
the first micromixer 1 is provided with an oil phase component inlet 6 and a first aqueous phase component inlet 7; the second micromixer 3 is provided with a second aqueous phase component inlet 8;
the first micro mixer 1 is a Y-shaped mixer, and the second micro mixer 3 is a T-shaped mixer; the centrifugal separator 5 is a rotary-vane separator.
Comparative example 1
This comparative example provides an apparatus for preparing polymethylene polyphenyl polyurethane, which is different from example 1 in that the tubeless reactor 2 and the second micromixer 3 are identical to example 1 in the rest.
Comparative example 2
This comparative example provides an apparatus for preparing polymethylene polyphenyl polymethylmethacrylate, which is different from example 1 in that the second micromixer 3 is not provided with the second aqueous phase component inlet 8, and the rest is the same as example 1.
Application example 1
The application example provides a method for preparing polymethylene polyphenyl polymethylene carbamate by using the device provided in the application example 1, which comprises the following steps:
at 120 ℃, the total time of the first emulsification treatment, the first condensation treatment, the second emulsification treatment and the second condensation treatment is 180min, wherein the second emulsification treatment is additionally supplemented with the aqueous phase solution of the methylene reagent, the molar quantity of which is 0.5 times of the total quantity of the methyl anilinoate, and the obtained emulsified mixture with the average diameter of the oil droplets of 100 mu m is separated to obtain the aqueous phase solution of the methylene reagent and the aqueous phase solution of the polymethylene polyphenyl polyurethane; the resulting aqueous solution of the methyleneating agent is recycled back for use in the first emulsification treatment;
the solvent in the methyl anilino formate oil phase solution is toluene; the mass concentration of the methyl anilinoate in the methyl anilinoate oil phase solution is 5%; the mass concentration of the methylene reagent in the aqueous solution of the methylene reagent is 1%; the methylene reagent in the aqueous solution of the methylene reagent is formaldehyde;
the aqueous solution of the methylene reagent comprises a protonic acid solution, wherein the protonic acid solution is hydrochloric acid with the mass fraction of 20%; the molar ratio of the methyl anilinoformate to the methyleneating agent is 1:1.
Application example 2
The application example provides a method for preparing polymethylene polyphenyl polymethylene carbamate by using the device provided in the application example 2, which comprises the following steps:
at 80 ℃, carrying out first emulsification treatment, first condensation treatment, second emulsification treatment and second condensation treatment on the methyl anilinoate oil phase solution and the methylene reagent aqueous phase solution, wherein the total time is 240min, the methylene reagent aqueous phase solution with the total mole number of 0.8 times of the total mole number of the methyl anilinoate is additionally supplemented in the second emulsification treatment, and the obtained emulsified mixture with the water droplet average diameter of 1 mu m is subjected to separation treatment to obtain the methylene reagent aqueous phase solution and the polymethylene polyphenyl polyurethane oil phase solution; the resulting aqueous solution of the methyleneating agent is recycled back for use in the first emulsification treatment;
the solvent in the methyl anilino formate oil phase solution is chlorobenzene; the mass concentration of the methyl anilinoate in the methyl anilinoate oil phase solution is 3%; the mass concentration of the methylene reagent in the aqueous solution of the methylene reagent is 0.6%; the methylene reagent in the aqueous solution of the methylene reagent is trioxymethylene;
the aqueous solution of the methylene reagent comprises a protonic acid solution, wherein the protonic acid solution is sulfuric acid with the mass fraction of 10%; the molar ratio of the methyl anilinoformate to the methyleneating agent is 1:2.
Application example 3
The application example provides a method for preparing polymethylene polyphenyl polymethylene carbamate by using the device provided in the application example 3, which comprises the following steps:
at 150 ℃, the total time of the first emulsification treatment, the first condensation treatment, the second emulsification treatment and the second condensation treatment is 60min, wherein the second emulsification treatment is additionally supplemented with the aqueous phase solution of the methylene reagent which is 1 time of the total mole number of the methyl anilinoate, and the obtained emulsified mixture with the average diameter of the oil droplets of 1000 mu m is separated to obtain the aqueous phase solution of the methylene reagent and the aqueous phase solution of the polymethylene polyphenyl polyurethane; the resulting aqueous solution of the methyleneating agent is recycled back for use in the first emulsification treatment;
the solvent in the methyl anilinoformate oil phase solution is dichlorobenzene; the mass concentration of the methyl anilinoate in the methyl anilinoate oil phase solution is 10%; the mass concentration of the methylene reagent in the aqueous solution of the methylene reagent is 1.5%; the methylene reagent in the aqueous solution of the methylene reagent is paraformaldehyde;
the aqueous solution of the methylene reagent comprises a protonic acid solution, wherein the protonic acid solution comprises acetic acid and hydrochloric acid with mass fraction of 40%; the molar ratio of the methyl anilinoformate to the methyleneating agent is 1:4.
Application example 4
The present application example provides a method for preparing polymethylene polyphenyl polyurethane using the apparatus provided in application example 1, which is different from application example 1 in that the temperature is adjusted to 40 ℃, the total time is adjusted to 360min, and the rest is the same as application example 1.
Application example 5
The present application example provides a method for preparing polymethylene polyphenyl polyurethane using the apparatus provided in application example 1, which is different from application example 1 in that the temperature is adjusted to 180 ℃, the total time is adjusted to 10min, and the rest is the same as application example 1.
Application example 6
The present application example provides a method for preparing polymethylene polyphenyl polymethylene carbamate by using the device provided in application example 1, which is different from application example 1 in that the molar ratio of the methylanilinoformate to the methyleneating agent is adjusted to be 1:0.5, and the rest is the same as application example 1.
Application example 7
The application example provides a method for preparing polymethylene polyphenyl polymethylene carbamate by using the device provided in application example 1, which is different from application example 1 in that the molar ratio of the methylanilinoformate to the methyleneating agent is adjusted to be 1:4.5, and the rest is the same as application example 1.
Comparative application example 1
The comparative application example provides a method for preparing polymethylene polyphenyl polyurethane using the apparatus provided in comparative example 1, which is different from application example 1 in that there is no step of the first condensation treatment and the second emulsification treatment, and the rest is the same as application example 1.
Comparative application example 2
The comparative application example provides a method for preparing polymethylene polyphenyl polyurethane using the apparatus provided in comparative example 2, which is different from application example 1 in that the aqueous solution of the methyleneating agent is not additionally supplemented in the second emulsification treatment, and the rest is the same as application example 1.
Polymethylene polyphenyl polyurethane was prepared by the methods provided in application examples 1 to 7 and comparative application examples 1 and 2, and the conversion of methylanilinoate, the yield and the selectivity of polymethylene polyphenyl polyurethane were calculated based on the amount of methylanilinoate fed, and the obtained results are shown in table 1.
TABLE 1
As can be seen from Table 1, the preparation of polymethylene polyphenyl polyurethane by the method provided by the invention can obtain higher reactant conversion rate and product yield, and simultaneously improve the selectivity of the target product of polymethylene polyphenyl polyurethane, and the obtained core product, namely 4, 4-dimethylene diphenyl polyurethane, is higher;
as can be seen from comparison of application example 1 with application examples 4 and 5, the treatment temperature is lower, and the conversion rate of reactants and the yield of products are reduced; the treatment temperature is lower, and the selectivity of the target product of the polymethylene polyphenyl polyurethane is reduced; as is clear from comparison of application example 1 with application examples 6 and 7, the molar ratio of methyl anilinoformate to the methyleneating agent is too high, and the conversion rate of reactants and the yield of products are reduced; the selectivity of the target product of polymethylene polyphenyl polyurethane is reduced when the molar ratio is too low;
as can be seen from the comparison of the application example 1 and the comparative application example 1, the direct one-step emulsification treatment and condensation treatment without a plurality of steps of treatment can greatly reduce the yield of the obtained core product, namely, 4-dimethylene diphenyl diamine methyl formate; as is clear from the comparison between the application example 1 and the comparative application example 2, the second emulsification treatment does not additionally supplement the methylene reagent, and the reactant conversion and the product yield and the target product selectivity of the polymethylene polyphenyl polyurethane are reduced.
In summary, by arranging the multistage micromixer and the reactor, compared with a single micromixer and a single reactor, the device provided by the invention can enable the methyl anilinoate oil phase solution and the methylene reagent aqueous phase solution to be more fully emulsified and condensed to be enhanced, so that the conversion rate of the methyl anilinoate and the yield of the polymethylene polyphenyl polyurethane are improved, the conversion rate of the methyl anilinoate is up to 100%, the yield of the polymethylene polyphenyl polyurethane is up to 100%, the selectivity of the target product of the polymethylene polyphenyl polyurethane is improved, the market economy is improved, the device accords with continuous operation conditions, and industrial application can be realized; the generated methylene reagent can be recycled, the cost of water resource treatment is reduced, and the method has the characteristics of environmental protection, simple operation and low cost.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.
Claims (10)
1. The device for preparing polymethylene polyphenyl polymethylene carbamate is characterized by comprising a first micromixer, a tubular reactor, a second micromixer, a kettle reactor and a centrifugal separator which are sequentially connected, wherein an aqueous phase component discharged by the centrifugal separator returns to the first micromixer.
2. The apparatus of claim 1, wherein the first micromixer is provided with an oil phase component inlet and a first aqueous phase component inlet;
the second micromixer is provided with a second aqueous phase component inlet.
3. The apparatus of claim 1, wherein the first and second micromixers each independently comprise a T-mixer and/or a Y-mixer.
4. The apparatus of claim 1, wherein the centrifugal separator comprises any one of a decanter centrifuge, a bowl centrifuge, or a rotary vane separator.
5. A process for preparing polymethylene polyphenyl polyurethane using the apparatus of any one of claims 1 to 4, comprising the steps of:
the preparation method comprises the steps of carrying out first emulsification treatment, first condensation treatment, second emulsification treatment and second condensation treatment on an phenylmethyl carbamate oil phase solution and a methylene reagent aqueous phase solution, and separating an obtained emulsified mixture to obtain the methylene reagent aqueous phase solution and a polymethylene polyphenyl polymethylene carbamate oil phase solution; the resulting aqueous solution of the methyleneating agent is recycled back for use in the first emulsification process.
6. The method of claim 5, wherein the solvent in the methyl anilinoformate oil phase solution comprises any one or a combination of at least two of toluene, ethylbenzene, chlorobenzene, dichlorobenzene, or xylene;
the mass concentration of the methyl anilinoate in the methyl anilinoate oil phase solution is 0.1 to 20 percent.
7. The method according to claim 6, wherein the mass concentration of the methylating agent in the aqueous solution of methylating agent is 0.1 to 10%;
the aqueous solution of the methylating agent comprises any one or a combination of at least two of formaldehyde, trioxymethylene or paraformaldehyde.
8. The method of claim 7, wherein the aqueous solution of the methyleneating agent comprises a protonic acid solution comprising any one or a combination of at least two of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, or hydrofluoric acid;
the mass fraction of the protonic acid in the protonic acid solution is 1-40%;
the molar ratio of the methyl anilinoformate to the methyleneating agent is 1 (1-4).
9. The method according to claim 5, wherein the first emulsification treatment, the first condensation treatment, the second emulsification treatment and the second condensation treatment are each at a temperature of 40-180 ℃ for a total time of 10-360min;
the second emulsification treatment is additionally supplemented with an aqueous solution of a methylating agent.
10. The method of claim 5, wherein the beads in the emulsified mixture have a diameter of 1-1000 μm;
the liquid beads comprise water beads and/or oil beads.
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