CN1444504A - Process and unit for continuous preparation of isocyanate-containing polyurethane prepolymers - Google Patents
Process and unit for continuous preparation of isocyanate-containing polyurethane prepolymers Download PDFInfo
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- CN1444504A CN1444504A CN 01813376 CN01813376A CN1444504A CN 1444504 A CN1444504 A CN 1444504A CN 01813376 CN01813376 CN 01813376 CN 01813376 A CN01813376 A CN 01813376A CN 1444504 A CN1444504 A CN 1444504A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- 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
- B01J19/0053—Details of the reactor
- B01J19/006—Baffles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/185—Stationary reactors having moving elements inside of the pulsating type
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- 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
- B01J19/28—Moving reactors, e.g. rotary drums
- B01J19/285—Shaking or vibrating reactors; reactions under the influence of low-frequency vibrations or pulsations
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0895—Manufacture of polymers by continuous processes
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00105—Controlling the temperature by indirect heating or cooling employing heat exchange fluids part or all of the reactants being heated or cooled outside the reactor while recycling
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00159—Controlling the temperature controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00761—Details of the reactor
- B01J2219/00763—Baffles
- B01J2219/00765—Baffles attached to the reactor wall
- B01J2219/00777—Baffles attached to the reactor wall horizontal
Abstract
This invention relates to a process for the continuous preparation of moderate to high viscosity reaction products requiring moderate to long reaction times (e.g. a polymer(s) including prepolymer(s)), specifically relates to the continuous preparation of an isocyanate-containing polyurethane prepolymer(s) useful in the production of polyurethane articles.
Description
Invention field
The present invention relates to continuously, preparation needs the medium to the high viscosity reaction product method of (as polymkeric substance, comprising prepolymer) of medium extremely long reaction times.
The present invention is specifically related to method and the unit that preparation continuously is used for the polyurethane prepolymer that contains isocyanic ester of polyurethane product production.
Background of invention
The traditional method that preparation contains the polyurethane prepolymer of isocyanic ester is to make polyol and polymeric polyisocyanate rhythmic reaction under hot conditions.
The interrupter method of producing polyisocyanate prepolymer is known, and has obtained widespread use.Yet they have several shortcomings.Because whole process need is filled in first reactant (being generally isocyanic ester) in the reactor for a long time, need long-time preheating, need for a long time to add other reactant (polyol) and they are reacted, and need be cooled to storage temperature for a long time, so need long period.In addition, they need be difficult to the complicated and huge device of operation and maintenance.Simultaneously, also be difficult to produce a spot of given product, because this method only is only economy usually under bigger plant size.
Therefore, need a kind of method for preparing polyisocyanate prepolymer that reduces these problems of part.This method can be a continuous processing.
Disclose the continuous processing that a kind of NCO of preparation content is the isocyanate-terminated prepolymer of 2-15% weight in No. 480588, the european patent application, described method comprises the steps:
(i) continuously supply with organic polyisocyanate composition and molecular-weight average to reaction zone and be at least 1000 isocyanate-reactive compound, the relative proportion of isocyanate composition and isocyanate-reactive compound is suitable for forming the prepolymer of NCO content in given range;
(ii) make isocyanate composition and isocyanate-reactive compound in reaction zone, react with form isocyanate-terminated prepolymer and
(iii) shift out prepolymer from reaction zone continuously.
Disclose a kind of continuous processing for preparing isocyanate-terminated prepolymer in No. 598283, the european patent application, described method comprises makes at least a vulcabond and one or more be essentially the step of linear polyol by 1.3: 1.0 to 15.1: 1.0 molar ratio reaction.The described length-to-diameter ratio that is reflected at is carried out at least 2 the tubular reactor, and this reactor is essentially continuous stirred tank reactor, and a part of recirculation of products therefrom is returned in the fresh monomer charging, takes this products therefrom is thoroughly mixed.By using suitable agitator, under suitable rotating speed, operate in inside reactor and realize recirculation loop.
Disclose a kind of method for preparing polyether polyols with reduced unsaturation among the EP-A-0087817, this method comprises makes isocyanic ester and polyol combination in the jacket layer conduit.Contain in the sleeve pipe and maintain the homothermic heat-transfer medium, it is used for controlling the peak value of maximum temperature.Comprise the mixing device that produces piston shape velocity distribution in the conduit.For example, this device can be the volution reactor.
Brief summary of the invention
Therefore, general objects of the present invention provides and a kind ofly can prepare the medium medium continuous processing to high viscosity compound or polymkeric substance to the long reaction times of needs.
Further aim of the present invention provides the unit of a kind of continuous preparation compound or polymkeric substance, this unit compactness, realize and safeguard simple, useful and can be incorporated in the standard design to environment.
Therefore, specific purposes of the present invention provide a kind of continuous processing that can prepare the high-quality prepolymer.
Another object of the present invention provides the unit of a kind of continuous preparation and the similar prepolymer of prepolymer that is obtained by traditional batch production device, this unit can be enough to realize required transformation efficiency medium to the long reaction times medium to the high viscosity work of finishing drilling.
A further object of the present invention provides the unit of this prepolymer of a kind of continuous preparation, and this unit compactness realizes, operation and maintenance is simple, is easy to transportation.
Also purpose of the present invention provides the unit of the prepolymer of the useful environment of a kind of continuous preparation.
Therefore the present invention relates to a kind of method of in being connected with the plug flow reactor of surge tank, carrying out (preferred adiabatic).
According to another embodiment, the present invention relates to a kind of method of in the pulse porous plate reactor of under impulsive condition, operating, carrying out (preferred adiabatic).
The present invention describes in detail
A kind of continuous method for preparing compound or polymkeric substance, it comprises the steps:
A) reactant is incorporated in the plug flow reactor into the porous plate reactor;
B) under required pressure and temperature condition, reactant is reacted in above-mentioned reactor;
C) from above-mentioned reactor, shift out reaction product.
A kind of continuous preparation contains the method for the polyurethane prepolymer of isocyanic ester, and it comprises the steps:
(a) reactant is incorporated in the plug flow reactor (10), described reactant is at least a isocyanate-reactive compound and at least a isocyanic ester;
(b) under required pressure and temperature condition, reactant is reacted in described reactor;
(c) from above-mentioned reactor, shift out reaction product.
Preferred plug flow reactor is the porous plate reactor in the aforesaid method, and most preferred process is adiabatic process.
According to a specific embodiments, the invention provides the continuous processing (preferred adiabatic) that a kind of preparation contains the polyurethane prepolymer of isocyanic ester, this method comprises the steps:
(a) at least a isocyanate-reactive compound of heating and at least a isocyanic ester;
(b) blended thermal response thing is incorporated in the plug flow reactor;
(c) reactant of heating is reacted in described reactor;
(d) reaction product is moved to from described reactor in the snubber assembly (as container).
The continuous processing (preferred adiabatic) that the present invention also provides a kind of preparation to contain the polyurethane prepolymer of isocyanic ester, this method comprises the steps:
(a) at least a isocyanate-reactive compound of heating and at least a isocyanic ester;
(b) blended thermal response thing is incorporated in the porous plate reactor;
(c) the thermal response thing is reacted in described reactor; With
(d) from described reactor, shift out reaction product.
In one embodiment of the invention, plug flow reactor is the porous plate reactor.In this embodiment, the porous plate reactor is the vertical vessel that for example extends, and introduces hot mixt in the bottom of described lengthening vertical vessel, shifts out reaction product at the top of described lengthening vertical vessel, is preferably overflow.Plug flow reactor can be the piston reactor of any kind, comprises baffled reactor.Therefore term " plug flow reactor " has comprised that the residence time distributes in fact near the reactor of piston reactor (the single discrete distribution as near the residence time intermediate value is 25%, preferred 20%).
Term " thermal insulation " is meant does not have heat automatic and the reactor exchange; In reaction process, do not heat or cooling reactor.Yet this can not hinder before reaction zone solid is heated into liquid.This can not hinder when beginning reaction the reacting by heating mixture to set initial reaction temperature.In other words, term " thermal insulation " is meant and does not attempt to be undertaken by isothermal reaction.
In another embodiment, described porous plate reactor comprises a series of porous plates that are positioned at reactor regularly.
In an embodiment again, the part free area of each porous plate of described reactor is 5-70%, preferred 15-35%, most preferably from about 25%.
According to an embodiment, described being reflected under the impulsive condition carried out.According to this embodiment, the pulse-repetition that puts on the thermal reaction mixture is 0.1-10, preferred 0.5-2Hz.
According to another embodiment, the surperficial amplitude of pulse on the reactor body cross section that puts on the thermal reaction mixture is 0.5-50, preferred 1-15mm, most preferably 2-10mm.
In one embodiment, when described thermal reaction mixture being introduced described porous plate reactor, on it, apply pulse.
In another embodiment, the porous plate by moving described reactor and or liquid, pulse is put on the described thermal reaction mixture.
According to an aspect of the present invention, in step a), by mixing first reactant and second reactant, heated mixt and obtain hot mixt then.
Reach temperature in by online or off-line as heating in feed storage tank or cooling.
On the other hand, in step a), obtain hot mixt by second reactant that mixes first reactant and preheating.
Also on the one hand, in step a), by mixing second reactant of first reactant and preheating, the mixture that obtains of heating and obtain hot mixt then.
On the one hand, in step a), heat the mixture that obtains then by second reactant that mixes the first preheating reactant and preheating and obtain hot mixt again.
In another embodiment, described method also comprises the step of cooling off reaction product.
In going back an embodiment, described method also comprises the step of filtration (refrigerative) reaction product.
According to an aspect of the present invention, the hot mixt that enters reactor has 0.15cP-2000cP usually, the viscosity of preferred 2cP-1000cP, and the mixture that leaves reactor has 0.2cP-10,000cP, preferred 0.8cP-2000cP, the viscosity of preferred especially 0.8cP-400cP (cP is mPa.s).
In another embodiment, described method comprises that also the product that will obtain is recycled to the step that is fed into oral region.
The invention still further relates to a unit of preparation polymer product continuously, described unit comprises:
(a) inlet device of reactant;
(b) heating unit of at least a reactant of heating;
(c) mixing device of mixed reactant;
(d) normal pressure plug flow reactor; With
(e) surge tank.
The present invention also relates to a preferred adiabatic unit for preparing compound or polymkeric substance down continuously at last, and described unit comprises:
(a) inlet device of reactant (1,2,2a, 5);
(b) heating unit (6,9) of at least a reactant of heating;
(c) mixing device of mixed reactant (4);
(d) porous plate reactor (10); With
(e) material in porous plate reactor (10) applies the pulse generating unit (11) of pulse.
The present invention also relates to a unit for preparing the polyurethane prepolymer that contains isocyanic ester continuously, described unit comprises:
(a) inlet device of at least a isocyanate-reactive compound and at least a isocyanic ester;
(b) heating unit of at least a reactant of heating;
(c) mixing device of mixed reactant;
(d) normal pressure plug flow reactor; With
(e) surge tank.
The present invention also relates to a preferred adiabatic unit for preparing the polyurethane prepolymer that contains isocyanic ester down continuously at last, and described unit comprises:
(a) inlet device of at least a isocyanate-reactive compound and at least a isocyanic ester (1,2,2a, 5);
(b) heating unit (6,9) of at least a reactant of heating;
(c) mixing device of mixed reactant (4);
(d) porous plate reactor (10); With
(e) material in porous plate reactor (10) applies the pulse generating unit (11) of pulse.
In one embodiment of the invention, plug flow reactor is the porous plate reactor.
In another embodiment of the invention, described unit also comprises heating or refrigerating unit in heating or the cooling reactor or that leave the reaction product behind the surge tank.
In also embodiment of the present invention, described unit also comprise be positioned at reactor after, the filtration unit of filtration (refrigerative) reaction product behind the particularly described refrigerating unit.
According to an embodiment, described unit also is included in the last with the shut-down recirculation unit of (refrigerative) reaction product (fully) recirculation by heating, mixing (and pulse) generation device, (porous plate) reactor, optional surge tank and optional refrigerating unit of production run.
With reference to following detailed description and accompanying drawing, other purpose of the present invention, feature and advantage will be more apparent.
Fig. 1 is the FB(flow block) of the inventive method;
Fig. 2 is the vertical cross-section synoptic diagram of the unitary porous plate reactor of the present invention along B-B;
Fig. 3 is the horizontal section synoptic diagram of the unitary porous plate reactor of the present invention along A-A.
Method of the present invention and unit are particularly suitable for heat release leniently, the medium or addition reaction of absorbing heat as mild as a dove, and these reactions have the high viscosity reactant and the reaction product of appropriateness.
Here " heat release leniently " be meant that the heat of those generations is up to one and is lower than the reaction of temperature spot that some products begin degraded (as atomizing, yellowing etc.) temperature.Usually, temperature raises and reaches as high as 50 ℃ (or higher), and generally is up to 20 ℃.
Here " leniently heat absorption " is meant the reaction that the heat of those consumption can not hinder these reactions to carry out.Typical temperature descends the highest 20 ℃, preferably the highest 10 ℃.
Here " high viscosity of appropriateness " typically refers to 20-2000cP (mPa.s).
Hereinafter be the example of the medium method to the high viscosity reaction product of continuously preparation, use organic polymeric polyisocyanate.
With reference to Fig. 1, will introduce in the entry mixers 4 by pipeline 1, pump 2 and pipeline 3 for first reactant of organic polyisocyanate composition, it mixes with isocyanate-reactive compound by pipeline 5, pump 2a introducing and passes through preheater 6 preheatings there.Entry mixers can be for example simple mixing valve or dynamic mixer or static mixer, the preferred latter.
The pump of preferred maneuvering system is a surge pump.This pump can be handled the composition that contains little solid of part such as MDI at low temperatures; This is the superior part that surpasses the conventional tooth wheel pump.Therefore surge pump is durable.They also are suitable for transportation.Also preferred described pump is coaxial pump, and promptly a drive shaft (motor) drives several pumps.
Also preferred described pump is connected directly to charging.This can be avoided relying on traditional heavy circulation loop.
Preference is as heating pipeline, the especially pipeline of isocyanic ester one side by the electrical tracing on the feeding line.
The well heater that is used in instantaneous (instant) unit can be a random conventional type.Be preferably fin-type, promptly have the cylinder shape well heater of side direction fin on the center part of pipeline.
Preferably described mixing tank is placed on the place that is right after after incoming flow converges, as in front of at well heater.Described mixing tank can be (when particularly not heating before reactor) before the inlet of reactor yet.This mixing tank can be an any type.The static mixer-type of filling material in being preferably.
Organic polyisocyanate composition can be selected from aliphatic series, alicyclic and araliphatic (araliphatic) polymeric polyisocyanate, vulcabond particularly, as 1, hexamethylene-diisocyanate, isophorone diisocyanate, hexanaphthene-1,4-vulcabond, 4,4 '-dicyclohexyl methane diisocyanate and-and right-tetramethyl xylylene diisocyanate, aromatic polyisocyanate particularly, as tolylene diisocyanate (TDI), phenylene diisocyanate, most preferably has the methylene diphenyl isocyanate of at least two isocyanate functionalities.Preferred methylene diphenyl isocyanate (MDI).It is pure 4 that methylene diphenyl isocyanate (MDI) can be selected from, 4 '-MDI; 4,4 '-MDI and 2,4 '-MDI and be lower than 2 of 10% weight, the isomeric mixtures of 2 '-MDI; Isocyanate functionality surpasses 2 rough and polymeric MDI; The modification variant of their carbodiimide, uretonimine, isocyanuric acid ester, urethane, aliphanate, urea or biuret group.Most preferred methylene diphenyl isocyanate is pure 4,4 '-MDI, 2,4 '-MDI and the optional MDI that contains isomeric mixtures and the uretonimine and/or the carbodiimide modified of the polymeric MDI that is up to 50% weight.If desired, can use methylene diphenyl isocyanate and particularly be up to the mixture of other above-mentioned polymeric polyisocyanate of 25% weight.
Isocyanate-reactive compound is a kind of compound that comprises the hydrogen atom (as hydroxyl or amine hydrogen atom) of energy and isocyanate reaction.
The preferred isocyanate reactive compounds is a polyol, and it can be selected from polyether polyhydroxy-compound, polyester polyol, polyesteramide polyol, polythioether polyol, polycarbonate polyhydroxylated compound, polyacetal polyol, polyolefin polyol etc.Preferred polyol is a polyether polyhydroxy-compound, particularly those polyols of being made up of propylene oxide PO and/or oxyethane EO (end capped or random).
Other extensively uses component in the art also can join in the reactor.The technician can know the characteristic and the quantity of isocyanic ester and isocyanate-reactive compound and these traditional components.EP-A-480588 (its content is combined in herein as a reference) comprises many descriptions to these components.
If desired, preferably additive is introduced in the entry mixers 4 through pipeline 7 and pump 8.
Then, in reactant well heater 9, will leave the mixture heating up to 45 ℃ of entry mixers 4 to being higher than 200 ℃, preferred 60-130 ℃ temperature.
11 (pulsating elements) flow into plug flow reactor 10 to hot mixt through the unit, react there.
The technician who knows isocyanate content and functional group and isocyanate-reactive compound molecular weight will be easy to determine to deliver to the relative quantity of each component in the reactor in view of the required NCO content of prepolymer.NCO content is generally for example 2-31% weight, preferred 5-25% weight.
The residence time generally between 5 minutes-5 hours, preferred 10-90 minute, most preferably 15-45 minute.
Time decreased is the huge advantage with respect to the traditional batch reactor.By embodiment, following table is contrast (value of the present invention that provides is only as illustration) side by side.Time unit is minute.
| Step | Prior art | The present invention |
| With isocyanic ester filling reactor | ????＞200 | ????- |
| Be warmed to temperature of reaction | ????30 | ????2 |
| Add polyol | ????＞100 | ????- |
| Finish reaction | ????90 | ????15-45 |
| Be cooled to storage temperature | ????＞150 | ????10 |
The time of comparing with prior art was saved above 8 hours.
The plug flow reactor that this paper gives an example is a porous plate reactor 10.The porous plate reactor is made following description.
Reactor also preferred fit has pulse unit 11, and it can make the reaction mixture vibration and stably move upward.This pulse unit can comprise as diaphragm type pump (but not having non-return valve).
The pulse-repetition that puts on the thermal reaction mixture is 0.1-10Hz, preferred 0.5-2Hz.
The amplitude range of pulse is 0.5-50mm, preferred 1-15mm, more preferably 2-10mm.Amplitude is given peak-to-peak value.
The reaction product of leaving porous plate reactor 10 tops flows into surge tank 12 then.The effect of surge tank 12 is to provide high flexibility to unit of the present invention.At first, it guarantees that the product rate of discharge is more steady.Secondly, it makes reactor 10 overflows, rather than is connected to out port system with the hard tube line; Therefore, reactor can be non-pressure vessel rather than pressurized vessel.(normal pressure also refers to exist nitrogen blanket on reactor; But relevant pressure can be ignored).Owing to do not need to assemble complicated overvoltage protective system, therefore reduced unitary weight, cost and complicacy.The 3rd, surge tank is as the buffering when disturbing the technological process in downstream, described unit, and it can give operator's time to deal with problems before having to stop in described unit.This has reduced the quality product risk that causes owing to these interference.
When using the porous plate reactor,, can cancel surge tank (but preferably have surge tank, particularly under condition of normal pressure) particularly in impulsive condition following time.Also can carry out under the condition of surge tank not having being higher than under the non-pressurized pressure method of operating, even can not have to carry out (although preferred pulse mode) under the impulsive condition.
Leave the product of surge tank 12 by product water cooler 13 (as coil heat exchanger) cooling, and pass through product strainer 14 and filter.
Provide shut-down re-circulation line 15 at product water cooler 13 and 14 of product strainers.It is connected to the outlet of product water cooler 13 inlet of entry mixers 4.This feature makes owing to the waste material amount that forms at the last generation of production run so-called " substandard " material (promptly at the extraneous material of desired parameters) is minimum, and this is because the content recirculation of device is finished by equipment to reaction.This recirculation also can make device cool down before emptier, had reduced the risk that remaining prepolymer stops up in equipment, and the obstruction of prepolymer in equipment will increase the risk of maintenance or crossed contamination.
When the last recirculation unit in production run, surge tank 12 is as storage tank.Because cooling back fluid contraction, this fluidic surge capability helps recirculation and cooling fluid.
Referring now to Fig. 2, can see the vertical vessel of porous plate reactor 10 for lengthening, it is a cylinder shape.It is equipped with a series of fixedly porous plates, and these plates are arranged with parallel in fact mode and regular in fact interval along the longitudinal axis X of post.
Spacing between two successive plates is 10-500mm, preferred 50-200mm, most preferably 100-150mm.The size of reactor can be as follows: internal diameter is 50-2000mm, preferred 100-500mm, high 0.5-10m, preferred 2-6m.Therefore the number of plate can be determined divided by the spacing of plate by height.The diameter in hole can change on the porous plate, for example is 4-12mm, preferred 6-10mm.
In a selective embodiment (describe), porous plate can be installed on the axle in the reactor 10, makes shaft vibration by pulse unit 11.Therefore the material in the reactor 10 is except stably moving upward, and also has effective vibration that the motion by plate 16 causes.
In another selective embodiment, with being with slotted plate, wire netting, other baffle arrangements (arrange free area very close to each other, mix or jet) to replace porous plate 16 thereby when applying pulse, produce to intersect.Plate perpendicular to the axis of reactor, has also been imagined tilted plate usually, for example is used for improving the free-draining characteristic.
Plug flow reactor 10 (preferred porous plate reactor), the reactor that has particularly added pulse unit 11 has several advantages: it can make the long reaction times have narrow residence time distribution, therefore passes through the behavior at intermittence of reactor near the composition of reaction mixture.Flowing of reaction mixture almost reaches the behavior of piston flow.In addition, this is to realize under the situation of the tumbler that does not contact with process fluid, has therefore simplified design, has improved reliability, has alleviated weight, has reduced the maintenance cost of reactor.And the water vent of reactor is good, therefore makes the central refuse of product minimum.
Pulse unit has relaxed the temperature that goes into operation, because the material of the pulse generation unit of reactor inlet is as heat sink, and helps to realize correct temperature control when going into operation.This also makes generation " substandard " material minimum.
Use another advantage of plug flow reactor (preferred porous plate reactor) to be that it can make and be reflected near carrying out under the adiabatic condition, this has simplified unit design, the accurate temperature of controlling reactor, and this allows to change the diameter of reactor.
Unitary another peculiar property of the present invention is that it can be used as packaged unit and builds.Described unit can transport in the standard delivery container, its very firm any position that produces that is transported to.Do not need complex system to support its operation in the production place.For example, it can be from chargings such as jar, charging stock tank, feed containers.Minority personnel just can operate, because common maintenance obtains simplifying, operator also can bear this unitary common maintenance task.
Can be separately or in conjunction with given unit (as conventional unit, as the unit at intermittence) use durable compact type pump, preheater, the plug flow reactor of under normal pressure, operating, porous plate reactor, surge tank, static mixer, fast reaction times and above-mentioned all other.These parts can be separately and are obtained this mobile unit together.
Described unit only needs to supply with the on-the-spot service of standard at scene, many warehouses, i.e. electricity, the water coolant of choosing wantonly, pressurized air (suitable is the bottled nitrogen of supply).Reaction product can be loaded into a jar charging system, tank wagon or storage tank in bulk.
Therefore, the invention provides the running gear unit that to operate in fact anywhere.
Therefore, be outside the described unitary uniqueness that it can easily transport, can provide range of viscosities wide quality products simultaneously.
And, because this reactor stablize the liquid level work of finishing drilling, comparing with periodical operation that the metathetical quantity of steam significantly reduces in operating process, in the periodical operation process, must empty regularly and the described device of filling, operate each time and all will replace steam.Another advantage is that equipment is also less, therefore contains steam still less, and metathetical steam can be handled (for example by being adsorbed onto on the gac) very up hill and dale to remove unwanted steam.Actual measurement shows that quantity discharged is very low.But this has strengthened described unitary transportcapacity, because it makes environmental impact minimization thereby can use in the whole world.
Preferred unit of the present invention is a mobile unit.It is designed to separate unit up to now, but it also can be connected with more complicated production chain.
Although disclose the specific embodiment of a relevant polyurethane prepolymer, the present invention also can be applied to be characterized as in have other reaction of medium-viscosity fluidic under the isometric reaction times.Preferred those need the reaction of high conversion especially, i.e. polyreaction and/or biological respinse.
Claims (31)
1. method for preparing continuously compound or polymkeric substance, it comprises the steps:
A) reactant is incorporated in the plug flow reactor into the porous plate reactor;
B) under required pressure and temperature condition, reactant is reacted in described reactor;
C) from described reactor, shift out reaction product.
One kind continuously preparation contain the method for the polyurethane prepolymer of isocyanic ester, it comprises the steps:
(a) reactant is incorporated in the plug flow reactor (10), described reactant is at least a isocyanate-reactive compound and at least a isocyanic ester;
(b) under required pressure and temperature condition, reactant is reacted in described reactor;
(c) from described reactor, shift out reaction product.
3. the method for a claim 2, wherein said plug flow reactor is the porous plate reactor.
4. the method for a claim 2, it comprises the steps:
(a) at least a isocyanate-reactive compound of heating and at least a isocyanic ester;
(b) blended thermal response thing is incorporated in the plug flow reactor;
(c) the thermal response thing is reacted in described reactor;
(d) from described reactor, shift out reaction product.
5. the method for a claim 1-4, it is adiabatic process.
6. claim 1 or 2 method, wherein said reactant is upwards introduced at end of described reactor (10) or near terminal, and described reaction product preferably shifts out as overflow in the optional position along reactor (10).
7. claim 1 or 3 method, wherein said porous plate reactor comprises a series of porous plates (16) that are positioned at described reactor (10).
8. the method for a claim 7, wherein the part free area of each described porous plate (16) is at 5-70%, and preferred 15-35% is most preferably from about in 25% the scope.
9. each method in the claim 8, wherein said being reflected under the impulsive condition that puts on the described thermal response thing carried out.
10. the method for a claim 9, the wherein said pulse-repetition that puts on the described thermal reaction mixture is 0.1-10Hz, preferred 0.5-2Hz.
11. the method for a claim 9 or 10, the wherein said pulse-response amplitude that puts on the described thermal reaction mixture is 0.5-50mm, preferred 1-15mm, most preferably 2-10mm.
12. the method for a claim 4, wherein said pulse put on the described reaction mixture, this mixture is introduced in the described porous plate reactor (10) simultaneously.
13. the method for a claim 12 wherein puts on described pulse on the described reaction mixture by the porous plate (16) that moves described reactor (10).
14. the method for a claim 4, wherein in step (a), heated mixt obtains hot mixt by mixing first reactant and second reactant then.
15. the method for a claim 4 wherein in step (a), obtains hot mixt by second reactant mixing with first reactant and preheating.
16. the method for a claim 4 wherein in step (a), obtains hot mixt by the mixture that obtains is heated in second reactant mixing of first reactant and preheating then.
17. each method among the claim 1-16, it also comprises the step of cooling off described reaction product.
18. each method among the claim 1-16, the range of viscosities of wherein said hot mixt is 0.15cP-2000cP, preferred 2cP-1000cP (mPa.s).
19. each method among the claim 2-18, wherein said organic polyisocyanate composition is the aromatic polyisocyanate that is selected from MDI, polymeric MDI and their modification variant.
20. each method among the claim 2-19, wherein said isocyanate-reactive compound is a polyol.
21. a unit for preparing the polyurethane prepolymer that contains isocyanic ester continuously, it comprises:
(a) inlet device of at least a isocyanate-reactive compound and at least a isocyanic ester (1,2,2a, 5);
(b) heating unit (6,9) of at least a reactant of heating;
(c) mixing device of mixed reactant (4);
(d) normal pressure plug flow reactor (10); With
(e) surge tank (12).
The porous plate reactor (10) that the vertical vessel of lengthening is formed 21. serve as reasons in the unit of a claim 21, wherein said plug flow reactor.
22. the unit of a claim 21 or 22, wherein said hot mixt is introduced in the bottom of described reactor, and described reaction product is discharged as overflow at the top.
23. the unit of a claim 22, wherein said porous plate reactor (10) comprise that series of rules ground is positioned at the porous plate (17) of reactor (10).
24. the unit of a claim 22, wherein the part free area of each described porous plate (17) is at 10-50%, and preferred 15-35% is most preferably from about in 25% the scope.
25. each unit in the claim 21, it also comprises:
On the content of described porous plate reactor (10), apply the pulse generating device (11) of pulse.
26. each unit among the claim 21-26, it also comprises:
The refrigerating unit (13) of the reaction product of surge tank (12) is left in cooling.
27. the unit of a claim 21, it also comprises:
Be positioned at described refrigerating unit (13) filtration unit that is used to filter described cooling reaction product (14) afterwards.
28. the unit of a claim 21, it also comprises:
Be used for making the shut-down recirculation unit (15) of reaction product recirculation at last by described mixing tank (4) and well heater (9), described reactor (10), described surge tank (12) and optional described refrigerating unit (13) in production process.
29. the unit of a claim 21, this unit are packaged unit.
30. the unit of a claim 21, this unit are mobile unit.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0013066.6 | 2000-05-31 | ||
| GB0013068A GB0013068D0 (en) | 2000-05-31 | 2000-05-31 | Process and unit for continuous preparation of isocyanate-containing polyurethane prepolymers |
| GB0013068.2 | 2000-05-31 | ||
| GB0013066A GB0013066D0 (en) | 2000-05-31 | 2000-05-31 | Process and unit for continuous preparation of isocyanate-containing polyurethane prepolymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1444504A true CN1444504A (en) | 2003-09-24 |
Family
ID=26244379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01813376 Pending CN1444504A (en) | 2000-05-31 | 2001-04-10 | Process and unit for continuous preparation of isocyanate-containing polyurethane prepolymers |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1292389A1 (en) |
| JP (1) | JP2003535166A (en) |
| CN (1) | CN1444504A (en) |
| AU (1) | AU2001273936A1 (en) |
| WO (1) | WO2001091897A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102029137A (en) * | 2009-10-07 | 2011-04-27 | 林德股份公司 | Method for reaction control of exothermic reaction and apparatus therefore |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1609525A1 (en) * | 2004-06-14 | 2005-12-28 | Tema Technopolymers S.r.l. | Plant for manufacturing polyurethane goods. |
| US20100216631A1 (en) * | 2005-06-23 | 2010-08-26 | Ni Xiong-Wei | Method and apparatus for fluid-liquid reactions |
| US7435787B2 (en) | 2005-09-14 | 2008-10-14 | Momentive Performance Materials Inc. | Process for the continuous production of silylated resin |
| KR101502647B1 (en) | 2008-03-14 | 2015-03-13 | 디아이씨 가부시끼가이샤 | Process for producing urethane (meth)acrylate |
| DE102010027052A1 (en) | 2010-07-13 | 2012-01-19 | Bayer Materialscience Ag | Process for the preparation of isocyanate group-containing polyurethane prepolymers |
| JP2017516905A (en) * | 2014-06-06 | 2017-06-22 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ | Method for continuous production of stable prepolymers |
| CN106660934B (en) | 2014-06-24 | 2020-03-03 | 科思创德国股份有限公司 | Process for preparing nitrobenzene |
| US20220185938A1 (en) | 2019-04-01 | 2022-06-16 | Basf Se | Continuous production of polyurethane prepolymers |
| KR102362979B1 (en) * | 2019-12-26 | 2022-02-16 | 주식회사 삼양사 | Isocyanate prepolymer product with improved storage stability and method for preparing the same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI830714A (en) * | 1982-03-03 | 1983-09-04 | Castle & Cooke Techniculture | APPARATUS, PROCESS OCH FOERFARANDE FOER KONTINUERLIG POLYMERISATION |
| JPS60244280A (en) * | 1984-05-18 | 1985-12-04 | Mitsubishi Heavy Ind Ltd | Aeration and agitation tank |
| US5200075A (en) * | 1991-03-08 | 1993-04-06 | Nkk Corporation | Separator |
| US5471037A (en) * | 1992-08-18 | 1995-11-28 | E. I. Du Pont De Nemours And Company | Process for preparing polymeric material with microwave |
| IL115063A0 (en) * | 1994-09-09 | 1995-12-08 | Urea Casale Sa | Method for in-situ modernization of a urea synthesis reactor |
-
2001
- 2001-04-10 AU AU2001273936A patent/AU2001273936A1/en not_active Abandoned
- 2001-04-10 WO PCT/EP2001/004089 patent/WO2001091897A1/en not_active Application Discontinuation
- 2001-04-10 EP EP01940315A patent/EP1292389A1/en not_active Withdrawn
- 2001-04-10 CN CN 01813376 patent/CN1444504A/en active Pending
- 2001-04-10 JP JP2001587902A patent/JP2003535166A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102029137A (en) * | 2009-10-07 | 2011-04-27 | 林德股份公司 | Method for reaction control of exothermic reaction and apparatus therefore |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001091897A1 (en) | 2001-12-06 |
| EP1292389A1 (en) | 2003-03-19 |
| AU2001273936A1 (en) | 2001-12-11 |
| JP2003535166A (en) | 2003-11-25 |
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