CN108409681A - A kind of serialization prepares the device and method of benzoxazine - Google Patents
A kind of serialization prepares the device and method of benzoxazine Download PDFInfo
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- CN108409681A CN108409681A CN201810497033.XA CN201810497033A CN108409681A CN 108409681 A CN108409681 A CN 108409681A CN 201810497033 A CN201810497033 A CN 201810497033A CN 108409681 A CN108409681 A CN 108409681A
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- Prior art keywords
- benzoxazine
- water
- blending tank
- material blending
- tank
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- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 119
- 238000002156 mixing Methods 0.000 claims abstract description 114
- 238000006243 chemical reaction Methods 0.000 claims abstract description 105
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000012528 membrane Substances 0.000 claims abstract description 54
- 239000000919 ceramic Substances 0.000 claims abstract description 52
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 238000010438 heat treatment Methods 0.000 claims abstract description 47
- 238000001802 infusion Methods 0.000 claims abstract description 47
- 238000000926 separation method Methods 0.000 claims abstract description 24
- 239000002351 wastewater Substances 0.000 claims abstract description 18
- 238000009826 distribution Methods 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 221
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 121
- 150000003384 small molecules Chemical class 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 22
- 150000001412 amines Chemical class 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 14
- 238000013517 stratification Methods 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000011017 operating method Methods 0.000 claims description 11
- 238000006068 polycondensation reaction Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 125000005605 benzo group Chemical group 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 7
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- 230000035484 reaction time Effects 0.000 abstract description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 47
- 229930040373 Paraformaldehyde Natural products 0.000 description 36
- 229920002866 paraformaldehyde Polymers 0.000 description 36
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 28
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 18
- 150000001299 aldehydes Chemical group 0.000 description 16
- 229940106691 bisphenol a Drugs 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- ZYIFLKPDFLWFAE-UHFFFAOYSA-N aniline;toluene Chemical compound CC1=CC=CC=C1.NC1=CC=CC=C1 ZYIFLKPDFLWFAE-UHFFFAOYSA-N 0.000 description 2
- 150000005130 benzoxazines Chemical class 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 208000037805 labour Diseases 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 150000004893 oxazines Chemical class 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- -1 primary amine compound Chemical group 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical group 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
- C07D265/36—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings condensed with one six-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the device and method that a kind of serialization prepares benzoxazine, which includes：At least two material blending tanks, microwave heating equipment, tubular reactor, ceramic membrane separation device, oil water separator, scraper film evaporator, waste water tank and controller；Liquid level gauge and buzzer are set on material blending tank.Open microwave heating, mixed reaction solution in one material blending tank is pumped into tubular reactor, when liquid level reaches minimum buzzer warning in tank, close the infusion pump in work, and open another infusion pump and continue to convey mixed reaction solution to tubular reactor, make reaction solution is continual to enter pipeline reactor；Reacting rear material is pumped into isolated benzoxazine head product in ceramic membrane separation device, then is pumped into scraper film evaporator and is purified, and obtains benzoxazine.The method of the present invention is continuous reaction, has the reaction time short, and yield is high, and speed of production is fast, benzoxazine narrow molecular weight distribution, the high feature of purity.
Description
Technical field
The invention belongs to chemical fields, and in particular to a kind of serialization prepares the device and method of benzoxazine.
Background technology
Pass through the benzo hexa-member heterocycle of Mannich reaction synthesis by raw material of phenolic compound, primary amine compound and aldehyde
Ring-opening polymerization can occur under heating and (or) catalyst action and form spatial networks knot for compound -- benzoxazine monomer
Structure.Benzoxazine is released during forming and hardening without small molecule, and product porosity is low, is shunk close to zero.With excellent
High temperature resistance, glass transition temperature (Tg) is at 150 DEG C or more；After benzoxazine ring-opening polymerisation, there is good electrical insulating property
Energy；Benzoxazine under the appropriate temperature conditions can solidified forming, have good mechanical performance.
Benzoxazine is widely used in copper-clad plate, laminate；Refractory material；Suitable for RTM, SMC, hand paste, pultrusion, winding
Etc. techniques composite material；The fields such as medication chemistry.
Benzoxazine is to use intermittent preparation method at present, its main feature is that once being filled required raw material react
Enter reactor, then reacted wherein, after the regular hour, reaches the required extent of reaction just removal total overall reaction
Material, wherein mainly reaction product and a small amount of raw material not being converted, belongs to the intermittent production method of mass, the party
Method is complicated for operation, consumes a large amount of labours, low production efficiency, and production capacity is limited.
Invention content
The purpose of the present invention is insufficient existing for the method for existing batch production benzoxazine, providing one kind can connect
Continuous serialization prepares the device of benzoxazine, and the method for preparing benzoxazine using the device.
Above-mentioned serialization prepares the device of benzoxazine, and structure composition includes：At least two material blending tanks, microwave
Heating device, tubular reactor, ceramic membrane separation device, oil water separator, waste water tank and controller.Wherein,
Liquid level gauge is set on the material blending tank and buzzer, controller are connect with liquid level gauge and buzzer respectively, is controlled
Device processed controls being turned on and off for buzzer based on the liquid level information that liquid level gauge detects.Each material blending tank is anti-with tubular type
It answers the feed inlet of device to connect, infusion pump and flow is equipped on the connecting line between each material reaction tank and tubular reactor
Meter.The microwave heating equipment includes microwave generator and heating chamber, and tubular reactor is arranged in heating chamber.Tubular type is anti-
The discharge port of device is answered to connect ceramic membrane separation device, ceramic membrane separation device bottom liquid outlet connects oil water separator, top setting production
Object benzoxazine exports, benzoxazine outlet connection scraper film evaporator, the setting charging of scraper film evaporator top
Mouthful, bottom is arranged benzoxazine and exports, and refined benzoxazine is obtained by scraper film evaporator.The side of oil water separator
Face top, lower part are equipped with oil outlet, and bottom is equipped with water outlet, and two oil outlets are connected by woven hose and a material blending tank
It connects, water outlet connects waste water tank.
Preferably, the controller is also connect with each infusion pump, the liquid level information control detected based on liquid level gauge
Infusion pump is turned on and off.
Preferably, the tubular reactor is connected in series by more reaction tubes.
Preferably, the ceramic membrane separation device is vertical tubular ceramic membrane separator.The ceramics membrane aperture can
By maximum molecular weight Mn be no more than 200 or 400.
The device that benzoxazine is prepared using above-mentioned serialization prepares the method for benzoxazine, includes the following steps：
S1, toluene is added into each material blending tank as solvent, sequentially adds reactant phenol, aldehyde, amine, phenol：Aldehyde：
Amine molar ratio is 1:2:1, stirring is opened, so that each component is uniformly mixed and is dissolved in toluene solvant, obtains mixed reaction solution；
S2, microwave heating equipment is opened, makes the control of heating chamber indoor temperature at 70-80 DEG C, then by one of material
Mixed reaction solution in blending tank is pumped into tubular reactor, and Mancini polycondensation reaction generation occurs in tubular reactor for reaction solution
Benzoxazine and water, benzoxazine are dissolved in toluene solvant；When liquid level reaches minimum buzzer unlatching report in material blending tank
When alert, the infusion pump in work is closed, and the infusion pump for opening another material blending tank continues to convey mixing to tubular reactor
Reaction solution makes mixed reaction solution is continual to enter pipeline reactor；During this, according to the operating method of step S1 to sky
Material blending tank in supplement mixed reaction solution；When buzzer sounds again, then replace another material blending tank；It is so past
It is multiple, realize that serialization inputs mixed reaction solution into tubular reactor；
S3, the material after tubular reactor reacts is pumped into ceramic membrane separation device, by UF membrane by macromolecular
Benzoxazine is detached with small molecule toluene, water and unreacted phenol, aldehyde, amine, obtains benzoxazine head product；
S4, the benzoxazine head product that step S3 is obtained is pumped into scraper film evaporator, by negative-pressure vacuum and
Heating, makes remaining a small amount of small molecule toluene, water and free phenol, aldehyde, amine further be detached with benzoxazine, is purified
Refined benzoxazine；
S5, step S3 isolated small molecule toluene, water and unreacted phenol, aldehyde, amine mixed liquor enter grease
In separator, stratification, the toluene on upper layer and unreacted phenol, aldehyde, amine mixing oil phase material mixing is pumped by oil outlet
Recycling, the water phase of lower layer enter waste water tank in tank.Water phase in waste water tank contains a small amount of phenol, aldehyde, amine, which passes through
Discharge after biochemical treatment COD is up to standard.
Preferably, further include the operation that catalyst sodium hydroxide is added in the step S1, make catalyst and each raw material
Component is sufficiently mixed.Toluene dosage accounts for 30% of all reaction mass gross masses in tank in the material blending tank.
Preferably, there are two the material blending tanks, material blending tank A and material blending tank B, they are anti-with tubular type
It answers device to connect, infusion pump A is installed on the pipeline that material blending tank A is connect with tubular reactor, material blending tank B and tubular type are anti-
It answers and infusion pump B is installed on the pipeline of device connection.Step S2 concrete operations are：Microwave heating equipment is opened, is made in heating chamber
Temperature is controlled at 70-80 DEG C, is then turned on infusion pump A and the mixed reaction solution in material blending tank A is pumped into tubular reactor, instead
Answering liquid to occur in tubular reactor, Mancini polycondensation reaction generates benzoxazine and water, benzoxazine are dissolved in toluene solvant；
When liquid level reaches the unlatching alarm of minimum buzzer in material blending tank A, the infusion pump A in work is closed, and open material
The infusion pump B of blending tank B continues to convey mixed reaction solution to tubular reactor, keeps mixed reaction solution continual anti-into pipeline
Answer device；During this, mixed reaction solution is supplemented into empty material blending tank A according to the operating method of step S1；Work as buzzing
When device sounds again, then it is changed to material blending tank A；And so on, realize that serialization inputs mixing into tubular reactor instead
Answer liquid.
Preferably, in the step S3, by selecting the tubular ceramic membrane of special pore size distribution size, unreacted small molecule
Phenol, aldehyde, amine and toluene and the water of generation permeation ceramic membrane under pressure, enter grease by the liquid outlet of separator bottom
The benzoxazine of separator, macromolecular is discharged by the outlet at the top of separator.
The phenol contains phenolic hydroxyl group for phenol, bisphenol-A, Bisphenol F, bisphenol S, phenolic resin and phenol-formaldehyde resin modified etc., and
And the phenol and its mixture at least one vacancy of the ortho position of phenolic hydroxyl group.It is preferred that phenol.
The aldehyde is formaldehyde, paraformaldehyde, the aromatic series such as benzaldehyde aldehyde compound and its mixture.It is preferred that formaldehyde or more
Polyformaldehyde.
The amine is aniline, and diaminodiphenylmethane etc. contains-NH2The amine of structure.It is preferred that aniline.
The invention has the beneficial effects that：
(1) present invention is without the batch reactor using routine, but uses pipeline reactor and added by microwave
The mode of heat keeps raw material reaction more abundant.Microwave heating is advantageous in that microwave is to pass through polarity to the heating of substance
Dipole effect occurs between molecule, referred to as interior heating, system is heated evenly, the movement of polar molecule can be made to aggravate, increased
The effective collision frequency between reactant molecule is added, it is made to reach the state of activation within the extremely short time, to significantly improve
Reaction speed between material, and common heating is realized by convection current and conduction, there are apparent temperature heating gradients.
Therefore microwave heating has the reaction time short, and yield is high, material can be made fully to react, and improves the spy of yield and speed of production
Point,
(2) tubular ceramic membrane separation technique is used, its Main Basis " screening " is theoretical, and tubular ceramic membrane tube wall gathers micro-
Hole, under pressure, material penetrate film in film Bottomhole pressure, small-molecule substance, and macromolecular substances are rejected by, to reach
The purpose of separation, concentration, purifying and environmental protection.The material molecule diameter difference permeated within the scope of certain membrane aperture then permeability
Difference is motive force using pressure at right angle difference, allows small-molecule substance by ceramic membrane, and macromolecular substances are then trapped,
To realize small molecule and generation macromolecular benzoxazine separation.Tubular ceramic membrane have separative efficiency height, effect stability,
Chemical stability is good, acid and alkali-resistance, organic solvent-resistant, resistance to bacterium, high temperature resistant, antipollution, high mechanical strength, regenerability is good, detaches
Numerous advantages such as process is simple, low energy consumption, simple and convenient operation and maintenance, service life length.Select aperture different according to this theory
Tubular ceramic membrane obtains the benzoxazine of different molecular weight.
(3) use scraper film evaporator that can further purify benzoxazine under heating and suction function.
(4) production technology of serialization is used, each link of production operation is continuous, is carried out at the same time, continual production, output
Product greatly improves production efficiency, reduces manual labor, achievees the purpose that serialization prepares benzoxazine.
(5) it can be recycled as the toluene of solvent, reduce secondary pollution.
Description of the drawings
Fig. 1, serialization prepare the structural schematic diagram of the device of benzoxazine.
Figure label：
1- materials blending tank, 2- microwave heating equipments, 3- tubular reactors, 4- ceramic membrane separations device, 5- oil water separators,
6- waste water tanks, 7- controllers, 8- liquid level gauges, 9- buzzers, 10- infusion pumps, 11- flowmeters, 21- microwave generators, 22- heating
Chamber, 51- oil outlets, 52- water outlets, 53- valve switch, 12- scraper film evaporators, 13- blenders.
Specific implementation mode
Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1
As shown in Figure 1, the serialization of the present invention prepares the device of benzoxazine, structure composition includes：At least two objects
Expect blending tank 1, microwave heating equipment 2, tubular reactor 3, ceramic membrane separation device 4, oil water separator 5, waste water tank 6, controller 7
With scraper film evaporator 12.Wherein, liquid level gauge 8 and buzzer 9 be set on the material blending tank 1, controller 7 respectively with
Liquid level gauge 8 and buzzer 9 connect, and controller controls being turned on and off for buzzer based on the liquid level information that liquid level gauge detects.
Blender 13 is equipped in each material blending tank.Each material blending tank is connect with the feed inlet of tubular reactor, each object
It is equipped with infusion pump 10 and flowmeter 11 on connecting line between material retort and tubular reactor.The tubular reactor by
More reaction tubes are connected in series.The microwave heating equipment includes microwave generator 21 and heating chamber 22, and tubular reactor is set
It sets in heating chamber；The discharge port of tubular reactor connects ceramic membrane separation device, and the ceramic membrane separation device is vertical pipe
Formula ceramic membrane separation device.It is described ceramics membrane aperture can by maximum molecular weight Mn be no more than 200 or 400.Ceramic membrane separation
Device bottom liquid outlet connects oil water separator, and top is arranged product benzoxazine and exports.Connection scraper-type in benzoxazine outlet is thin
Feed inlet is arranged in film evaporator 12, scraper film evaporator top, and bottom is arranged benzoxazine and exports, and passes through wipe film
Evaporator obtains refined benzoxazine.The side surface upper part of oil water separator, lower part are equipped with oil outlet 51, and bottom is equipped with water outlet
52, two oil outlets are connect by woven hose with a material blending tank, and water outlet connects waste water tank.It is fuel-displaced with side lower
On the woven hose of mouthful connection, and valve switch 53 is respectively arranged on the woven hose that is connect with bottom liquid outlet.
In another embodiment, there are two the material blending tanks 1, respectively material blending tank A and material blending tank B, object
Expect to be equipped with liquid level gauge A and buzzer A in blending tank A, liquid level gauge B and buzzer B is equipped in material blending tank B.Material blending tank A
Infusion pump A is installed on the pipeline being connect with tubular reactor, is installed on the pipeline that material blending tank B is connect with tubular reactor
There is infusion pump B.Concrete operating principle process is：When liquid level gauge A detects that reaction solution liquid level reaches minimum in material blending tank A
When, controller 7 controls buzzer A alarms, reminds operating personnel to supplement addition reaction solution into material blending tank A, or replace
For material blending tank B；Then, before reaction solution is finished in material blending tank B, the supplement addition reaction into material blending tank A
Liquid, it is spare, ensure that mixed reaction solution is continual and enters pipeline reactor.
In another embodiment, there are two the material blending tanks 1, respectively material blending tank A and material blending tank B, object
Expect to be equipped with liquid level gauge A and buzzer A in blending tank A, liquid level gauge B and buzzer B is equipped in material blending tank B.Material blending tank A
Infusion pump A is installed on the pipeline being connect with tubular reactor, is installed on the pipeline that material blending tank B is connect with tubular reactor
There is infusion pump B.The controller 7 is connect with liquid level gauge A and B, buzzer A and B, infusion pump A and B simultaneously.Controller is based on liquid
The liquid level information control buzzer that position meter detects is turned on and off, and controls being turned on and off for infusion pump.Specific work
Making principle process is：When liquid level gauge A detects that the liquid level in material blending tank A reaches minimum, controller control buzzer A is opened
Alarm is opened, infusion pump A is simultaneously closed off, opens infusion pump B, ensures that mixed reaction solution is continual and enters pipeline reactor.Operation
Personnel hear that alarm sound is known that in material blending tank A that reaction solution is finished, and is replenished in time reaction solution, spare.As material blending tank B
Interior reaction solution is finished, and with the blending tank A that more reloads again, is so recycled, and realizes that serialization prepares benzoxazine.
Embodiment 2
The device that benzoxazine is prepared using above-mentioned serialization prepares the method for benzoxazine, includes the following steps：
Step S1, prepare raw material：Add respectively into two material blending tanks (material blending tank A and material blending tank B)
Enter toluene as solvent；Sequentially add phenol, formaldehyde and aniline；Toluene dosage accounts for all anti-in tank in the material blending tank
The 30% of material gross mass is answered, the mass ratio of phenol, formaldehyde and aniline is according to 94:60:93, stirring is opened, raw material is fully mixed
Merging is dissolved in toluene solvant.
Step S2, microwave heating equipment is opened, makes the control of heating chamber indoor temperature at 70 DEG C, the material that step S1 is obtained
Mixed reaction solution is continuously squeezed into tubular reactor by infusion pump A after blending tank A adjustment flows；Due at such a temperature,
Mancini polycondensation reaction can occur for phenol, aldehyde, amine three, and the benzoxazine of generation is dissolved in toluene solvant, while generating water.Material
The buzzer of setting lowest order in blending tank closes infusion pump A, and unlatching infusion pump B makes material immediately after buzzer A is rung
Mixed reaction solution in blending tank B is continual to pass through tubular reactor.It prepares to material and mixes according still further to step 1 operating method
Reaction mass is added in tank A, prepares mixed reaction solution.After buzzer B is rung, infusion pump B is closed, opens infusion pump A.According still further to
Prepared by step 1 operating method is added reaction mass into material blending tank A, prepares mixed reaction solution.And so on, it can realize
Continual that reaction solution is inputted into tubular reactor, reaction solution, which reacts to each other, generates benzoxazine.
Step S3, by containing benzoxazine, water, the Yi Jiwei being dissolved in toluene in the mixed liquor of tubular reactor discharge
The mixed liquor is pumped into vertical tubular ceramic membrane separator by phenol, formaldehyde, the aniline of reaction by transfer tube.Pass through choosing
With ceramic membrane aperture can by maximum molecular weight Mn be no more than 200 ceramic membrane.Unreacted phenol, formaldehyde, aniline with
And the small molecules such as toluene and the water of generation under pressure will permeation ceramic membrane enter oil water separator；Macromolecular Ben Bing Evil
Piperazine cannot then pass through ceramic membrane.Thus can by macromolecular benzoxazine and small molecule toluene, water and unreacted phenol,
Formaldehyde, aniline separate, and obtain benzoxazine head product.Also be mingled in the benzoxazine head product a small amount of toluene, water with
And the small molecules such as free phenol, formaldehyde, aniline.
S4, the benzoxazine head product that step S3 is obtained is pumped into scraper film evaporator, by negative-pressure vacuum and
Heating, makes remaining a small amount of toluene, water and free phenol, formaldehyde, aniline further be detached with benzoxazine, is purified
Refined benzoxazine.
S5, step S3 isolated small molecule toluene, water and unreacted phenol, formaldehyde, aniline mixed liquor into
Enter in oil water separator, stratification, the toluene on upper layer and unreacted phenol, formaldehyde, aniline mixing oil phase by oil outlet
It is pumped into recycling, the water phase of lower layer in material blending tank and enters waste water tank.Water phase in waste water tank contains a small amount of phenol, first
Aldehyde, aniline, the water phase are discharged after biochemical treatment COD is up to standard.
Comparative example 1
First, toluene solvant is added into individual reaction kettle, adds phenol, maintain reaction kettle at 40 DEG C, the object
Toluene dosage accounts for 30% of all reaction mass gross masses in tank in material blending tank；It is then turned on stirring, formaldehyde and aniline is added,
Phenol, formaldehyde, aniline mass ratio according to 94：60：93, it starts to warm up, is warming up within 30 minutes 70 DEG C, stop heating, remain anti-
It is 70 DEG C to answer liquid temperature, and maintains reaction 3 hours；After completion of the reaction, 60 DEG C are cooled to, stops stirring stratification, by upper layer
Water is discharged；Start water washing operations again, maintain 60 DEG C of temperature in the kettle, open stirring, and the pure water of 2 times of phenol quality is added, stirs
After twenty minutes, stratification is then exhausted from upper water；Reaction kettle is finally changed to dewatering state, starts to warm up dehydration, by toluene and
Remaining water evaporation, which is fallen, just obtains pure benzoxazine.
Embodiment 3
The device that benzoxazine is prepared using serialization prepares the method for benzoxazine, includes the following steps：
Step S1, prepare raw material：Add respectively into two material blending tanks (material blending tank A and material blending tank B)
Enter toluene as solvent；Sequentially add bisphenol-A, paraformaldehyde and aniline；Toluene dosage accounts in tank in the material blending tank
The 30% of all reaction mass gross masses, bisphenol-A, paraformaldehyde, aniline mass ratio 228:120:186, stirring is opened, it will be former
Material is sufficiently mixed and is dissolved in toluene solvant.
Step S2, microwave heating equipment is opened, makes the control of heating chamber indoor temperature at 75 DEG C, the material that step S1 is obtained
Mixed reaction solution is continuously squeezed into tubular reactor by infusion pump A after blending tank A adjustment flows；Due at such a temperature,
Mancini polycondensation reaction can occur for phenol, aldehyde, amine three, and the benzoxazine of generation is dissolved in toluene solvant, while generating water.Material
The buzzer of setting lowest order in blending tank closes infusion pump A, and unlatching infusion pump B makes material immediately after buzzer A is rung
Mixed reaction solution in blending tank B is continual to pass through tubular reactor.It prepares to material and mixes according still further to step 1 operating method
Reaction mass is added in tank A, prepares mixed reaction solution.After buzzer B is rung, infusion pump B is closed, opens infusion pump A.According still further to
Prepared by step 1 operating method is added reaction mass into material blending tank A, prepares mixed reaction solution.And so on, it can realize
Continual that reaction solution is inputted into tubular reactor, reaction solution, which reacts to each other, generates benzoxazine.
Step S3, by containing benzoxazine, water, the Yi Jiwei being dissolved in toluene in the mixed liquor of tubular reactor discharge
The mixed liquor is pumped into vertical tubular ceramic membrane separator by bisphenol-A, paraformaldehyde, the aniline of reaction by transfer tube.It is logical
Cross Ceramics membrane aperture can by maximum molecular weight Mn be no more than 400 ceramic membrane.Unreacted bisphenol-A, poly first
The small molecules such as aldehyde, aniline and toluene and the water of generation under pressure will permeation ceramic membrane enter oil water separator；Greatly
Molecule benzoxazine cannot then pass through ceramic membrane.Thus can be by macromolecular benzoxazine and small molecule toluene, water and not
Bisphenol-A, paraformaldehyde, the aniline of reaction separate, and obtain benzoxazine head product.Also it is mingled in the benzoxazine head product
The small molecules such as a small amount of toluene, water and free bisphenol-A, paraformaldehyde, aniline.
S4, the benzoxazine head product that step S3 is obtained is pumped into scraper film evaporator, by negative-pressure vacuum and
Heating, makes remaining a small amount of toluene, water and free bisphenol-A, paraformaldehyde, aniline further be detached with benzoxazine, obtains
The benzoxazine refined to purifying.
The mixing of S5, step S3 isolated small molecule toluene, water and unreacted bisphenol-A, paraformaldehyde, aniline
Liquid enters in oil water separator, stratification, the mixing oil phase of the toluene on upper layer and unreacted bisphenol-A, paraformaldehyde, aniline
It is pumped into material blending tank and is recycled by oil outlet, the water phase of lower layer enters waste water tank.Water phase in waste water tank contains on a small quantity
Unreacted bisphenol-A, paraformaldehyde, aniline, which discharges after biochemical treatment COD is up to standard.
Comparative example 2
First, toluene solvant is added into individual reaction kettle, adds bisphenol-A, maintain reaction kettle at 40 DEG C, the object
Toluene dosage accounts for 30% of all reaction mass gross masses in tank in material blending tank；Be then turned on stirring, be added paraformaldehyde and
Aniline, bisphenol-A：Paraformaldehyde：The mass ratio 228 of aniline：120：186, it starts to warm up, is warming up within 30 minutes 75 DEG C, stop rising
Temperature, it is 75 DEG C to maintain reacting liquid temperature, and maintains reaction 4 hours；After completion of the reaction, 60 DEG C are cooled to, stirring standing point is stopped
Layer, upper water is discharged；Start water washing operations again, maintain 60 DEG C of temperature in the kettle, opens stirring, and 2 times of bisphenol-A quality is added
Pure water, after twenty minutes, stratification is then exhausted from upper water for stirring；Reaction kettle is finally changed to dewatering state, is started to warm up de-
Water falls toluene and remaining water evaporation just to obtain pure benzoxazine.
Embodiment 4
The device that benzoxazine is prepared using serialization prepares the method for benzoxazine, includes the following steps：
Step S1, prepare raw material：Add respectively into two material blending tanks (material blending tank A and material blending tank B)
Enter toluene as solvent；Sequentially add phenol, paraformaldehyde, diaminodiphenylmethane；Toluene is used in the material blending tank
Amount accounts for 30% of all reaction mass gross masses in tank, phenol, paraformaldehyde, diaminodiphenylmethane mass ratio 188:120:
198, stirring is opened, raw material is sufficiently mixed and is dissolved in toluene solvant.
Step S2, microwave heating equipment is opened, makes the control of heating chamber indoor temperature at 80 DEG C, the material that step S1 is obtained
Mixed reaction solution is continuously squeezed into tubular reactor by infusion pump A after blending tank A adjustment flows；Due at such a temperature,
Mancini polycondensation reaction can occur for phenol, aldehyde, amine three, and the benzoxazine of generation is dissolved in toluene solvant, while generating water.Material
The buzzer of setting lowest order in blending tank closes infusion pump A, and unlatching infusion pump B makes material immediately after buzzer A is rung
Mixed reaction solution in blending tank B is continual to pass through tubular reactor.It prepares to material and mixes according still further to step 1 operating method
Reaction mass is added in tank A, prepares mixed reaction solution.After buzzer B is rung, infusion pump B is closed, opens infusion pump A.According still further to
Prepared by step 1 operating method is added reaction mass into material blending tank A, prepares mixed reaction solution.And so on, it can realize
Continual that reaction solution is inputted into tubular reactor, reaction solution, which reacts to each other, generates benzoxazine.
Step S3, by containing benzoxazine, water, the Yi Jiwei being dissolved in toluene in the mixed liquor of tubular reactor discharge
The mixed liquor is pumped into vertical tubular ceramic membrane point by the phenol of reaction, paraformaldehyde, diaminodiphenylmethane by transfer tube
From in device.By Ceramics membrane aperture can by maximum molecular weight Mn be no more than 400 ceramic membrane.Unreacted benzene
The small molecules such as phenol, paraformaldehyde, diaminodiphenylmethane and toluene and the water of generation will penetrate ceramics under pressure
Film enters oil water separator；Macromolecular benzoxazine cannot then pass through ceramic membrane.Thus can by macromolecular benzoxazine with
Small molecule toluene, water and unreacted phenol, paraformaldehyde, diaminodiphenylmethane separate, and obtain benzoxazine primiparity
Product.Also it is mingled with a small amount of toluene, water and free phenol, paraformaldehyde, diamino hexichol in the benzoxazine head product
The small molecules such as methane.
S4, the benzoxazine head product that step S3 is obtained is pumped into scraper film evaporator, by negative-pressure vacuum and
Heating makes remaining a small amount of toluene, water and free phenol, paraformaldehyde, diaminodiphenylmethane and benzoxazine into one
Step separation obtains the refined benzoxazine of purifying.
S5, step S3 isolated small molecule toluene, water and unreacted phenol, paraformaldehyde, diamino hexichol
The mixed liquor of methane enters in oil water separator, stratification, the toluene on upper layer and unreacted phenol, paraformaldehyde, diamino
The mixing oil phase of base diphenyl-methane, which is pumped by oil outlet in material blending tank, to recycle, and the water phase of lower layer enters waste water tank.It is useless
Water phase in water pot contains a small amount of unreacted phenol, paraformaldehyde, diaminodiphenylmethane, which passes through biochemical treatment
Discharge after COD is up to standard.
Comparative example 3
First, toluene solvant is added into individual reaction kettle, adds phenol, maintain reaction kettle at 40 DEG C, the object
Toluene dosage accounts for 30% of all reaction mass gross masses in tank in material blending tank；Be then turned on stirring, be added paraformaldehyde and
Diaminodiphenylmethane, phenol, paraformaldehyde, diaminodiphenylmethane mass ratio 188:120:198, it starts to warm up, 30 points
Clock is warming up to 80 DEG C, stops heating, and it is 80 DEG C to maintain reacting liquid temperature, and maintains reaction 4 hours；After completion of the reaction, it is cooled to
60 DEG C, stops stirring stratification, upper water is discharged；Start water washing operations again, maintain 60 DEG C of temperature in the kettle, opens stirring,
And the pure water of 2 times of phenol quality is added, after twenty minutes, stratification is then exhausted from upper water for stirring；Finally reaction kettle is changed to take off
Water state starts to warm up dehydration, falls toluene and remaining water evaporation just to obtain pure benzoxazine.
Embodiment 5
The device that benzoxazine is prepared using serialization prepares the method for benzoxazine, includes the following steps：
Step S1, prepare raw material：Add respectively into two material blending tanks (material blending tank A and material blending tank B)
Enter toluene as solvent；Sequentially add phenol, paraformaldehyde, diaminodiphenylmethane and catalyst sodium hydroxide；The object
Toluene dosage accounts for 30% of all reaction mass gross masses in tank in material blending tank, phenol, paraformaldehyde, diamino hexichol first
The mass ratio 188 of alkane, agent sodium hydroxide:120:198:3.76, stirring is opened, raw material is sufficiently mixed and is dissolved in toluene solvant
In.
Step S2, microwave heating equipment is opened, makes the control of heating chamber indoor temperature at 80 DEG C, the material that step S1 is obtained
Mixed reaction solution is continuously squeezed into tubular reactor by infusion pump A after blending tank A adjustment flows；Due at such a temperature,
Mancini polycondensation reaction can occur for phenol, aldehyde, amine three, and the benzoxazine of generation is dissolved in toluene solvant, while generating water.Material
The buzzer of setting lowest order in blending tank closes infusion pump A, and unlatching infusion pump B makes material immediately after buzzer A is rung
Mixed reaction solution in blending tank B is continual to pass through tubular reactor.It prepares to material and mixes according still further to step 1 operating method
Reaction mass is added in tank A, prepares mixed reaction solution.After buzzer B is rung, infusion pump B is closed, opens infusion pump A.According still further to
Prepared by step 1 operating method is added reaction mass into material blending tank A, prepares mixed reaction solution.And so on, it can realize
Continual that reaction solution is inputted into tubular reactor, reaction solution, which reacts to each other, generates benzoxazine.
Step S3, by containing benzoxazine, water, the hydroxide being dissolved in toluene in the mixed liquor of tubular reactor discharge
The mixed liquor is pumped into vertical pipe by sodium and unreacted phenol, paraformaldehyde, diaminodiphenylmethane by transfer tube
In formula ceramic membrane separation device.By Ceramics membrane aperture can by maximum molecular weight Mn be no more than 400 ceramic membrane.Not
The small molecules such as phenol, paraformaldehyde, diaminodiphenylmethane and the toluene of reaction and the water of generation under pressure will
Permeation ceramic membrane enters oil water separator；Macromolecular benzoxazine cannot then pass through ceramic membrane.It thus can be by macromolecular benzene
Bing oxazines and small molecule toluene, water, sodium hydroxide and unreacted phenol, paraformaldehyde, diaminodiphenylmethane separate,
Obtain benzoxazine head product.Also it is mingled with a small amount of toluene, water, sodium hydroxide in the benzoxazine head product and dissociates
The small molecules such as phenol, paraformaldehyde, diaminodiphenylmethane.
S4, the benzoxazine head product that step S3 is obtained is pumped into scraper film evaporator, by negative-pressure vacuum and
Heating makes remaining a small amount of toluene, water and free phenol, paraformaldehyde, diaminodiphenylmethane and benzoxazine into one
Step separation obtains the refined benzoxazine of purifying.
S5, step S3 isolated small molecule toluene, water and unreacted phenol, paraformaldehyde, diamino hexichol
The mixed liquor of methane enters in oil water separator, stratification, the toluene on upper layer and unreacted phenol, paraformaldehyde, diamino
The mixing oil phase of base diphenyl-methane, which is pumped by oil outlet in material blending tank, to recycle, and the water phase of lower layer enters waste water tank.It is useless
Water phase in water pot contains a small amount of unreacted phenol, paraformaldehyde, diaminodiphenylmethane, which passes through biochemical treatment
Discharge after COD is up to standard.
Comparative example 4
First, toluene solvant is added into individual reaction kettle, adds phenol, maintain reaction kettle at 40 DEG C, the object
Toluene dosage accounts for 30% of all reaction mass gross masses in tank in material blending tank；It is then turned on stirring, paraformaldehyde, two are added
Diaminodiphenylmethane and sodium hydroxide, phenol, paraformaldehyde, diaminodiphenylmethane, sodium hydroxide mass ratio 188:120:
198:3.76, it starts to warm up, is warming up within 30 minutes 80 DEG C, stop heating, it is 80 DEG C to maintain reacting liquid temperature, and maintains reaction 4
Hour；After completion of the reaction, 60 DEG C are cooled to, stops stirring stratification, upper water is discharged；Start water washing operations again, maintains
60 DEG C of temperature in the kettle opens stirring, and the pure water of 2 times of phenol quality is added, and after twenty minutes, stratification is then exhausted from for stirring
Layer water；Reaction kettle is finally changed to dewatering state, starts to warm up dehydration, falls toluene and remaining water evaporation just to obtain pure benzene
Bing oxazines.
Detection method：Molecular weight detection equipment is waters companies.1515 chromatogram pumps, 2414 differential refraction detectors, six
Port valve injector, column oven.Chromatographic column is HR1, tri- toluene solvant gel columns of HR2, HR4E.Software is Breeze2.Embodiment
2-5, benzoxazine index prepared by comparative example 1-4 are shown in Table 1.
Table 1, embodiment 2-5, the molecular weight determination of benzoxazine prepared by comparative example 1-4
| Sample | Molecular weight Mn | Molecular weight distribution | Yield (according to phenol meter %) |
| Embodiment 2 | 220 | 1.102 | 2.32 |
| Comparative example 1 | 206 | 1.677 | 2.21 |
| Embodiment 3 | 461 | 1.128 | 2.01 |
| Comparative example 2 | 451 | 1.712 | 1.9 |
| Embodiment 4 | 435 | 1.115 | 2.3 |
| Comparative example 3 | 429 | 1.832 | 2.22 |
| Embodiment 5 | 436 | 1.119 | 2.38 |
| Comparative example 4 | 422 | 1.912 | 2.25 |
Pass through the comparison to embodiment 2-5 and comparative example 1-4, it can be seen that point of the benzoxazine synthesized in the present invention
Son amount distribution is narrower, and yield is more increased.The purpose of the continuous production of benzoxazine is realized, while having saved the manufacturing
Time improves the conversion ratio of raw material, reduces wastewater flow rate, reduces manufacturing cost, has reached the effect of energy-saving and emission-reduction
Fruit.
In conclusion the present invention provides the preparation facilities that a kind of serialization prepares the method for benzoxazine and uses.Even
The production technology of continuousization, each link of production operation is continuous, is carried out at the same time, continual production output products.With intermittent system
Preparation Method is compared, and continuous preparation method substantially increases production efficiency, and manual operation is simple, saves manpower and time, favorably
In industrialization large-scale production.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, though
So the present invention has been disclosed as a preferred embodiment, and however, it is not intended to limit the invention, any technology people for being familiar with this profession
Member, without departing from the scope of the present invention, when the technology contents using the disclosure above make a little change or modification
For the equivalent embodiment of equivalent variations, as long as being the content without departing from technical solution of the present invention, according to the technical essence of the invention
To any simple modification, equivalent change and modification made by above example, in the range of still falling within technical solution of the present invention.
Claims (10)
1. a kind of serialization prepares the device of benzoxazine, which is characterized in that including：At least two material blending tanks, microwave add
Thermal, tubular reactor, ceramic membrane separation device, oil water separator, scraper film evaporator, waste water tank and controller；
Liquid level gauge is set on the material blending tank and buzzer, controller are connect with liquid level gauge and buzzer respectively, controller
Being turned on and off for buzzer is controlled based on the liquid level information that liquid level gauge detects；Each material blending tank is and tubular reactor
Feed inlet connection, the microwave heating equipment carry heating chamber, tubular reactor be arranged in heating chamber；Pipe reaction
The discharge port of device connects ceramic membrane separation device, and ceramic membrane separation device bottom liquid outlet connects oil water separator, and product is arranged in top
Benzoxazine exports, and connection scraper film evaporator in benzoxazine outlet is obtained refined by scraper film evaporator
Benzoxazine；The side surface upper part of oil water separator, lower part are equipped with oil outlet, and bottom is equipped with water outlet, and two oil outlets pass through
Woven hose is connect with a material blending tank, and water outlet connects waste water tank.
2. serialization as described in claim 1 prepares the device of benzoxazine, which is characterized in that each material reaction tank and pipe
It is equipped with infusion pump and flowmeter on connecting line between formula reactor.
3. serialization as claimed in claim 2 prepares the device of benzoxazine, which is characterized in that the controller also with it is each
Infusion pump connects, and being turned on and off for infusion pump is controlled based on the liquid level information that liquid level gauge detects.
4. serialization as described in claim 1 prepares the device of benzoxazine, which is characterized in that the tubular reactor is by more
Root reaction tube is connected in series.
5. serialization as described in claim 1 prepares the device of benzoxazine, which is characterized in that the ceramic membrane separation device is
Vertical tubular ceramic membrane separator, ceramic membrane aperture can by maximum molecular weight Mn be no more than 200 or 400.
6. serialization as described in claim 1 prepares the device of benzoxazine, which is characterized in that the wipe film evaporation
Device carries vacuum equipment and heat-conducting oil heating.
7. a kind of method preparing benzoxazine using claim 1-6 any one described device serializations, which is characterized in that
Include the following steps：
S1, toluene is added into each material blending tank as solvent, sequentially adds reactant phenol, aldehyde, amine, phenol：Aldehyde：Amine rubs
You are than being 1:2:1, stirring is opened, so that each component is uniformly mixed and is dissolved in toluene solvant, obtains mixed reaction solution；
S2, microwave heating equipment is opened, makes the control of heating chamber indoor temperature at 70-80 DEG C, then mixes one of material
Mixed reaction solution in tank is pumped into tubular reactor, and Mancini polycondensation reaction occurs in tubular reactor and generates benzo for reaction solution
Oxazine and water, benzoxazine are dissolved in toluene solvant；When liquid level reaches the unlatching alarm of minimum buzzer in material blending tank,
The infusion pump in work is closed, and the infusion pump for opening another material blending tank continues to convey hybrid reaction to tubular reactor
Liquid makes mixed reaction solution is continual to enter pipeline reactor；During this, according to the operating method of step S1 to empty object
Mixed reaction solution is supplemented in material blending tank；When buzzer sounds again, then replace another material blending tank；And so on,
Realize that serialization inputs mixed reaction solution into tubular reactor；
S3, the material after tubular reactor reacts is pumped into ceramic membrane separation device, by UF membrane by macromolecular benzo
Oxazine is detached with small molecule toluene, water and unreacted phenol, aldehyde, amine, obtains benzoxazine head product；
S4, the benzoxazine head product that step S3 is obtained is pumped into scraper film evaporator, by negative-pressure vacuum and heating,
So that remaining a small amount of small molecule toluene, water and free phenol, aldehyde, amine is further detached with benzoxazine, it is refined to obtain purifying
Benzoxazine；
S5, step S3 isolated small molecule toluene, water and unreacted phenol, aldehyde, amine mixed liquor enter water-oil separating
In device, stratification, the toluene on upper layer and unreacted phenol, aldehyde, amine mixing oil phase be pumped into material blending tank by oil outlet
Recycling, the water phase of lower layer enter waste water tank.
8. the method that serialization as claimed in claim 7 prepares benzoxazine, which is characterized in that further include in the step S1
The operation of catalyst sodium hydroxide is added, catalyst is made to be sufficiently mixed with each raw material component.
9. the method that serialization as claimed in claim 8 prepares benzoxazine, which is characterized in that first in the material blending tank
Benzene dosage accounts for 30% of all reaction mass gross masses in tank.
10. the method that serialization as claimed in claim 9 prepares benzoxazine, which is characterized in that in the step S3, pass through
The tubular ceramic membrane of special pore size distribution size, unreacted small molecule phenol, aldehyde, amine and toluene and the water of generation is selected to make in pressure
With lower permeation ceramic membrane, oil water separator is entered by the liquid outlet of separator bottom, the benzoxazine of macromolecular is by separator top
The outlet in portion is discharged.
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| CN111569450A (en) * | 2020-05-22 | 2020-08-25 | 浙江省天正设计工程有限公司 | Methyl phosphine aldehyde reaction liquid continuous evaporation concentration device and concentration process |
| CN115703873A (en) * | 2021-08-04 | 2023-02-17 | 华东理工大学 | Method for continuously preparing main chain type benzoxazine derivatives |
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