CN109096474A - A kind of device and technique of aromatic polyester polyol synthesis - Google Patents
A kind of device and technique of aromatic polyester polyol synthesis Download PDFInfo
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- CN109096474A CN109096474A CN201811347591.4A CN201811347591A CN109096474A CN 109096474 A CN109096474 A CN 109096474A CN 201811347591 A CN201811347591 A CN 201811347591A CN 109096474 A CN109096474 A CN 109096474A
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- polyalcohol
- reaction kettle
- esterification
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/785—Preparation processes characterised by the apparatus used
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention discloses the device and technique of a kind of aromatic polyester polyol synthesis, including mixer, polyalcohol pans, reaction kettle of the esterification, batch condensation polymerization reactor, reconciliation reaction kettle and polyalcohol recovery tower etc.；Organic polycarboxylic acid is preheating to after certain temperature successively passes through reaction kettle of the esterification with the polyalcohol of certain temperature after mixer mixes, and batch condensation polymerization reactor, the reaction kettle that reconciles react to obtain the polyester polyol product of different size；Gas phase in reaction kettle of the esterification and batch condensation polymerization reactor enters polyalcohol recovery tower, and the polyalcohol of extraction enters the recycling of polyalcohol pans.The method of the present invention is compared with the more still reaction techniques of traditional batch, by rationally controlling esterification, polycondensation and reconciliation three phases technical data, so that properties of product specification adjustable extent wide (average molecular weight, carboxylic value and hydroxyl value etc.), polyalcohol recovery efficiency are high, loss is few, esterification and polycondensation process reaction efficiency are effectively promoted, external same performance index is reached while reducing products material consumption.
Description
Technical field
The present invention relates to the devices and technique of a kind of synthesis of polyester polyol, and in particular to the conjunction of aromatic polyester polyol
At technology, belong to polyester polyol technical field.
Background technique
Polyester polyol is usually by polyalcohol and Dicarboxylic Acids (acid anhydrides) through esterification and polycondensation or by polyalcohol
With lactones be polymerized with a hydroxy-end capped kind polyester, average molecular weight is no more than in 1000-4000, carboxyl concentration
0.02mol•kg.Polyester polyol is mainly used to the raw material synthesized as polyurethane, wear-resisting, resistance to compared with polyether polyol
Oil and heat resistance are preferable, high mechanical strength.According to the difference for using dicarboxylic acids, it is polynary to can be generally divided into aliphatic polyester
Alcohol, aromatic polyester polyol and mixing polyester polyols.Aromatic polyester polyol is due to introducing benzene in molecular structure
Ring structure improves the phenyl ring content in polyurethane chain, so that being enbrittled by the rigid polyurethane foam that it is prepared
Low, good toughness, intensity are high, thermal coefficient is low, flame retardant property is good and the advantages such as price is low, in insulation, shockproof, sound insulation, packaging
Material Field is widely used.
Polyester polyol mostly uses batch stirred tank reactor to produce at present, and one-pot production capacity has reached ten thousand tons of rule
Mould, the companies such as Du Pont, Bayer, BASF have applied for related patents in the batch production process of polyester polyol and formula.State
It is interior also to have gone out continuous production technology route at present, but above-mentioned continuous process technology all rests on lab scale and pilot scale rank at present
Section, apart from commercial applications, there are also huge distances.The synthesis of polyester polyol is generally divided into two stages, and the first stage is normal
Esterification Stage is pressed, this stage since polyalcohol and dicarboxylic acids concentration are high, do not need catalyst energy fast reaction and generates largely
Water；Second stage is polycondensation phase, needs additionally to add catalyst to promote the further polycondensation of polyester polyols alcohol monomer for big point
The polymer of son, the stage usually use vacuumizing, promote water and small-molecule substance that can leave system in time, improve reaction
Efficiency reduces the generation of side reaction.However batch stirred tank reaction process technology does not consider the spy in differential responses stage at present
Point, two stages reaction usually occur in one or more reaction kettle simultaneously, and polyalcohol is caused to lose, and process energy consumption is high,
The problems such as polyester polyol product specification is poor.
Summary of the invention
Goal of the invention: it is an object of the invention to for technology existing for traditional batch stirred-tank reactor production technology
Problem, the characteristics of device and technique, Dicarboxylic Acids and diol reaction of a kind of aromatic polyester polyol synthesis are provided,
Whole flow process is divided into three phases, it is excellent to entire reaction process and device structure progress for the reaction characteristics of different phase
Change.
Technical solution: a kind of device of aromatic polyester polyol synthesis of the present invention, including in mixer, polyalcohol
Between tank, reaction kettle of the esterification, batch condensation polymerization reactor, Intermediate Heat Exchanger, reconcile reaction kettle, polyalcohol recovery tower, overhead condenser, tower top
Return tank, control valve group and delivery pump；
The mixer is equipped with organic carboxyl acid feed inlet, mixer polyalcohol feed inlet and mixer discharge port, the polyalcohol
Pans are equipped with polyalcohol feed inlet and pans polyalcohol discharge port after fresh polyalcohol feed inlet, recycling, the pans
Polyalcohol discharge port is connect with mixer polyalcohol feed inlet, and connecting tube is equipped with the first control valve group；
Reaction kettle of the esterification gaseous phase outlet, reaction kettle of the esterification inert gas import are equipped at the top of the reaction kettle of the esterification, side is equipped with
Reaction kettle of the esterification feed inlet, the reaction kettle of the esterification feed inlet are connect with mixer discharge port, and bottom portion is equipped with material after esterification
Discharge port, which connect with the first conveying pump inlet, and discharge port is equipped with the second control valve group；Reaction kettle of the esterification is normal
Press operation, with agitating device and conduction oil heat tracing collet or steam tracing coil pipe；
It is more that batch condensation polymerization reactor gaseous phase outlet, batch condensation polymerization reactor vacuum system interface and supplement are equipped at the top of the batch condensation polymerization reactor
First alcohol feed inlet, side are equipped with batch condensation polymerization reactor mixed material feed inlet, which connect with the outlet of the first delivery pump；Kettle
Bottom is equipped with material discharge port after polycondensation, which connect with the second conveying pump inlet, and discharge port is equipped with the 4th control
Valve group, while the import of the second delivery pump is also connected with catalyst charge pipe；The Intermediate Heat Exchanger is set to the second delivery pump
On efferent duct；The supplement polyalcohol feed inlet is connect with pans polyalcohol discharge port, and connecting tube is controlled equipped with third
Valve group；Batch condensation polymerization reactor is vacuumizing, with agitating device and conduction oil heat tracing collet or steam tracing coil pipe；
Additive inlet port, reconciliation reaction kettle inert gas import and reconciliation reaction kettle vacuum system are equipped at the top of the reconciliation reaction kettle
System interface, side are equipped with batch condensation polymerization reactor and are mixed into material mouth, and the feed inlet and the second conveying pump main outlet connect, and reconciliation is anti-
Bottom portion is answered to be equipped with polyester polyol outlet for product；The reaction kettle that reconciles is normal pressure or vacuumizing, has agitating device；
The polyalcohol recovery tower tower bottom has recovery tower polyalcohol discharge port, and the discharge port and polyalcohol intermediate storage tank feed inlet connect
It connects, the polyalcohol recovery tower lower side is equipped with gas-phase feed mouth at two, is connected at one with reaction kettle of the esterification gaseous phase outlet, separately
It is connected at one with batch condensation polymerization reactor gaseous phase outlet, recovery tower gaseous phase outlet is equipped at the top of the polyalcohol recovery tower, which goes out
Mouth is connected with overhead condenser import；The overhead condenser outlet is connect with return tank of top of the tower feed inlet, the overhead reflux
The material refluxing opening of tank is connect with the refluxing opening of polyalcohol recovery tower top-side, and the overhead reflux tank top is equipped with fixed gas
Outlet, bottom are equipped with material and produce mouth.
The technique that aromatic polyester polyol synthesis is carried out using the device of above-mentioned aromatic polyester polyol synthesis, including
Following steps:
1.1, be preheating to certain temperature organic polycarboxylic acid and polyalcohol difference slave carboxylic acid feed mouth, mixer polyalcohol into
Material mouth enters mixer, is sent into reaction kettle of the esterification after mixing in mixer, carries out the first step under inert gas protection
Esterification, reaction generates a large amount of water, polyester polyols alcohol monomer, remaining polyalcohol and other by-products, wherein whole water
Polyalcohol recovery tower is entered through gaseous phase outlet with gas phase with excessive polyalcohol and by-product, carries out returning for polyalcohol
It receives, wherein organic polycarboxylic acid is preheating to 100-200 DEG C, and dihydric alcohol is preheating to 70-150 DEG C；Reaction time is 0.5-6h, preferably
For 2-3.5h, reaction kettle of the esterification bottom discharge port control valve is opened, and polyester polyols alcohol monomer is adopted from reactor bottom material outlet
Out, batch condensation polymerization reactor is pumped into through delivery pump together with catalyst；
1.2, polyester polyols alcohol monomer and catalyst that step 1.1 produces are pumped into batch condensation polymerization reactor through delivery pump, polycondensation is anti-
Answer kettle using vacuumizing, under inert gas protection, polyester polyols alcohol monomer is under the action of catalyst in batch condensation polymerization reactor
Polycondensation dehydration is carried out, to supplement certain weight polyalcohol in reaction process, organic multicomponent carboxylic in the polyalcohol of supplement and charging
The molar ratio of acid is 0.1-1, preferably 0.1-0.5；Polycondensation reaction is promoted to carry out thoroughly, polycondensation reaction time 0.5-8h is excellent
It is selected as 2-4h, the reaction time is determined by the carboxylic value and hydroxyl value of periodic measurement material, when hydroxyl value concentration is less than 500mgKOH/
G, when carboxylic value is less than 5mgKOH/g, polycondensation reaction can terminate, and material discharge port produces after the polycondensation of batch condensation polymerization reactor bottom
Polyester polyol polymer；The water and a small amount of polyalcohol that polycondensation reaction generates enter in polyalcohol recovery tower through gaseous phase outlet, into
The recycling of row polyalcohol；
1.3, the polyester polyol polymer that step 1.2 produces is pumped into Intermediate Heat Exchanger, through Intermediate Heat Exchanger by polyester polyol
Polymer is cooled to 30-100 DEG C, preferably 40-80 DEG C, rear to be sent into reconciliation reaction kettle, under inert gas protection, by adding not
With additive component adjust average molecular weight, the degree of polymerization, carboxylic value and the hydroxyl value index of polyester polyol polymer, reconcile anti-
Answer kettle can be using vacuum or atmospheric operation, the reaction kettle that reconciles is needed using inert gas seal, by discharge in kettle into
Row detection and analysis produces qualified products wait reconcile when material in reactor reaches desired value, which includes mean molecule
Amount, carboxylic value and hydroxyl value index, average molecular weight 2000-5000, hydroxyl value are not more than 100mgKOH/g, carboxylic value be no more than
1mgKOH/g；
1.4, step 1.1 and the gas phase of 1.2 extraction are entered in polyalcohol recovery tower by two gas-phase feed mouth of polyalcohol recovery tower,
After rectifying separates, polyalcohol feed inlet enters polyalcohol intermediate storage tank after tower bottom extraction polyalcohol is recovered, water and a small amount of
Polyalcohol and other by-products enter return tank of top of the tower from tower top after overhead condenser condenses, and return tank Partial Liquid Phase is through more
First alcohol recovery tower refluxing opening enters polyalcohol recovery tower, Partial Liquid Phase extraction, and fixed gas is produced from overhead reflux tank top；
Preferably, the Dicarboxylic Acids are by phthalic acid, M-phthalic acid, terephthalic acid (TPA), 1,2,4- benzene front threes
It is one or more kinds of in acid, 1,3,5- benzenetricarboxylic acids and 2,6-naphthalenedicarboxylic acid to constitute, the polyalcohol by ethylene glycol, diethylene glycol (DEG),
One of polyethylene glycol, 1,2-PD, 1,3-PD, dipropylene glycol, 1,4-butanediol and neopentyl glycol or
A variety of compositions.
Preferably, the catalyst is selected from following compounds: isopropyl titanate, tetrabutyl titanate, titanium ethylene glycolate, novel
Resistant to hydrolysis titanium catalyst, antimony oxide, antimony acetate, antimony glycol, germanium dioxide, dibutyl tin laurate, in phosphotungstic acid
It is one or more.
Preferably, the preferred isopropyl titanate of the catalyst or tetrabutyl titanate.
Further, the catalyst concn is 10-100ppm.
The preferred 20-50ppm of catalyst concn.
Further, the operating temperature of the mixer is 80-200 DEG C；Reaction kettle of the esterification operating pressure is -0.1Mpa-
0.1Mpa(absolute pressure), reaction temperature is 150-280 DEG C, and alcohol/acid molar ratio into reaction kettle of the esterification is 1.05-1.35；Polycondensation
Reaction kettle operating pressure is 0-0.1Mpa(absolute pressure), reaction temperature is 150-280 DEG C, supplement polyalcohol and more in batch condensation polymerization reactor
First carboxylic acid molar ratio is 0.05-0.30；The reaction kettle reaction temperature that reconciles is 30-150 DEG C, and operating pressure is -0.1Mpa-0.1Mpa
(absolute pressure)；
The additive includes antioxidant, acid value and hydroxyl value regulator；The antioxidant is acidic antioxidant or phosphite ester
Kind antioxidant；Acidic antioxidant mainly has boric acid, hypophosphorous acid etc., and phosphite ester antioxidant mainly has triphenyl phosphite, three
Nonyl phosphite ester etc..
The acid value and hydroxyl value regulator are the acid rich in hydroxyl value or carboxylic value, the alcohol rich in hydroxyl value or carboxylic value
Substance.Subsequent the reason of acids and alcohols material is added is the requirement according to different clients to the hydroxyl value and carboxylic value of product, is led to
Cross what addition acids or alcohols material in reconciliation reaction kettle were finally reached.
The theoretical cam curve of the polyalcohol recovery tower is 10-30 block, and operating pressure 0.01-0.4Mpa, reflux ratio is
1.2-5。
The utility model has the advantages that (1)
(1) production procedure is divided into esterification, polycondensation and reconciles three phases, for different phase material physical property and response characteristic,
Different phase technological parameter and device parameter are optimized, norm controlling range of enhancing product performance, promotes esterification and polycondensation
Reaction efficiency.
(2) esterification and polycondensation phase gas phase are taken out of to the polyalcohol and water and other by-products of reactor by setting rectifying column
Object is efficiently separated, and the system circulation of dihydric alcohol is realized, and is lost in the process less.
(3) a process route is realized by setting reconciliation reaction kettle, the polyester polyol of the production multiple performance trade mark produces
Product.
(4) the method for the present invention is simple, effect is good, high conversion rate, and being conducive to reduce in product in polyester polyol field has
The content of the unfavorable impurity of evil, index of enhancing product performance reduce the consumption of ton products material, meet industry development relevant policies.
Detailed description of the invention
Fig. 1 is the device and flow diagram of the synthesis of aromatic polyester polyol described in embodiment 1.
Wherein, V1- polyalcohol intermediate storage tank, M1- mixer, R1- reaction kettle of the esterification, R2- batch condensation polymerization reactor, R3- reconcile
Reaction kettle, T1- polyalcohol recovery tower, V2- return tank of top of the tower, E1- overhead condenser, E2- Intermediate Heat Exchanger, ZV1 ~ 4- first to
Five control valve groups, the first and second delivery pump of P1, P2-, 1- organic polycarboxylic acid, the charging of 2- polyalcohol, 3- enter the polynary of mixer
Alcohol, 4- polyester polyols alcohol monomer, 6- polyester polyol polymer, 8- catalyst, 9- polyester polyol product, 14- on-condensible gas,
17- vacuum system interface, 18- inert gas, 19- additive, 21- waste water.
Specific embodiment
Technical solution of the present invention is described in detail below by attached drawing, but protection scope of the present invention is not limited to
The embodiment.
Embodiment 1: as shown in Figure 1, a kind of device of aromatic polyester polyol synthesis, including in mixer, polyalcohol
Between tank, reaction kettle of the esterification, batch condensation polymerization reactor, Intermediate Heat Exchanger, reconcile reaction kettle, polyalcohol recovery tower, overhead condenser, tower top
Return tank, control valve group and delivery pump；
The mixer is equipped with organic carboxyl acid feed inlet, mixer polyalcohol feed inlet and mixer discharge port, the polyalcohol
Pans are equipped with polyalcohol feed inlet and pans polyalcohol discharge port after fresh polyalcohol feed inlet, recycling, the pans
Polyalcohol discharge port is connect with mixer polyalcohol feed inlet, and connecting tube is equipped with the first control valve group；
Reaction kettle of the esterification gaseous phase outlet, reaction kettle of the esterification inert gas import are equipped at the top of the reaction kettle of the esterification, side is equipped with
Reaction kettle of the esterification feed inlet, the reaction kettle of the esterification feed inlet are connect with mixer discharge port, and bottom portion is equipped with material after esterification
Discharge port, which connect with the first conveying pump inlet, and discharge port is equipped with the second control valve group；Reaction kettle of the esterification is normal
Press operation, with agitating device and conduction oil heat tracing collet or steam tracing coil pipe；
It is more that batch condensation polymerization reactor gaseous phase outlet, batch condensation polymerization reactor vacuum system interface and supplement are equipped at the top of the batch condensation polymerization reactor
First alcohol feed inlet, side are equipped with batch condensation polymerization reactor mixed material feed inlet, which connect with the outlet of the first delivery pump；Kettle
Bottom is equipped with material discharge port after polycondensation, which connect with the second conveying pump inlet, and discharge port is equipped with the 4th control
Valve group, while the import of the second delivery pump is also connected with catalyst charge pipe；The Intermediate Heat Exchanger is set to the second delivery pump
On efferent duct；The supplement polyalcohol feed inlet is connect with pans polyalcohol discharge port, and connecting tube is controlled equipped with third
Valve group；Batch condensation polymerization reactor is vacuumizing, with agitating device and conduction oil heat tracing collet or steam tracing coil pipe；Polycondensation is anti-
Kettle top portion vacuum system interface is answered to be equipped with the 5th control valve group；
Additive inlet port, reconciliation reaction kettle inert gas import and reconciliation reaction kettle vacuum system are equipped at the top of the reconciliation reaction kettle
System interface, side are equipped with batch condensation polymerization reactor and are mixed into material mouth, and the feed inlet and the second conveying pump main outlet connect, and reconciliation is anti-
Bottom portion is answered to be equipped with polyester polyol outlet for product；The reaction kettle that reconciles is normal pressure or vacuumizing, has agitating device；
The polyalcohol recovery tower tower bottom has recovery tower polyalcohol discharge port, and the discharge port and polyalcohol intermediate storage tank feed inlet connect
It connects, the polyalcohol recovery tower lower side is equipped with gas-phase feed mouth at two, is connected at one with reaction kettle of the esterification gaseous phase outlet, separately
It is connected at one with batch condensation polymerization reactor gaseous phase outlet, recovery tower gaseous phase outlet is equipped at the top of the polyalcohol recovery tower, which goes out
Mouth is connected with overhead condenser import；The overhead condenser outlet is connect with return tank of top of the tower feed inlet, the overhead reflux
The material refluxing opening of tank is connect with the refluxing opening of polyalcohol recovery tower top-side, and the overhead reflux tank top is equipped with fixed gas
Outlet, bottom are equipped with material and produce mouth.
In the present embodiment, the processing step of aromatic polyester polyol synthesis is carried out using above-mentioned apparatus are as follows:
1.1, it is preheating to 140 DEG C of 16.6kg phthalic acid and enters with the diethylene glycol (DEG) for the 11.67kg for being preheating to 100 DEG C and mix
Device, mixer temperature are 140 DEG C, are sent into reaction kettle of the esterification after mixing in mixer, reaction kettle of the esterification operating pressure is
0.1Mpa(absolute pressure), temperature is 180 DEG C, carries out the esterification of the first step under nitrogen protection and generates after reaction 2.5h reaction
A large amount of water and polyester polyols alcohol monomer, remaining diethylene glycol (DEG) and other by-products, wherein water and excessive polyalcohol and by-product
Object enters polyalcohol recovery tower through gaseous phase outlet with gas phase, carries out the recycling of polyalcohol.Reaction kettle of the esterification bottom discharge port
Control valve is opened, and polyester polyols alcohol monomer is produced from reactor bottom material outlet, through defeated together with catalyst tetrabutyl titanate
Pump is sent to be pumped into batch condensation polymerization reactor；
1.2, polyester polyols alcohol monomer and catalyst tetrabutyl titanate that step 1.1 produces are pumped into batch condensation polymerization reactor through delivery pump
In, tetrabutyl titanate concentration is 50ppm, and batch condensation polymerization reactor uses vacuumizing, vacuum degree 5Kpa, and temperature is 225 DEG C.In nitrogen
Under gas shielded, polyester polyols alcohol monomer carries out polycondensation dehydration in batch condensation polymerization reactor under the action of catalyst, mends in reaction
The diethylene glycol (DEG) of 1.6Kg is filled, 2.5h is reacted, the water and a small amount of polyalcohol that polycondensation reaction generates enter polyalcohol through gaseous phase outlet and recycles
In tower, the recycling of polyalcohol is carried out；Material discharge port produces polyester polyol polymer after the polycondensation of batch condensation polymerization reactor bottom；
1.3, the polyester polyol polymer that step 1.2 produces is pumped into Intermediate Heat Exchanger, through Intermediate Heat Exchanger by polyester polyol
Polymer is sent into reconciliation reaction kettle, reconciliation reaction kettle operating pressure 20Kpa after being cooled to 70 DEG C, temperature is 70 DEG C.It is protected in nitrogen
Under shield, the modifying agent isophthalic anhydride of antioxidant triphenyl phosphite and 0.05wt% that 0.1wt% is added is more to adjust polyester
The indexs such as average molecular weight, hydroxyl value and the carboxylic value of first alcohol polymer, final products average molecular weight are 2000, and water content is
0.03wt%, acid value 0.5mgKOH/g, hydroxyl value 80mgKOH/g.
1.4, step 1.1 and the gas phase of 1.2 extraction enter polyalcohol by two gas-phase feed mouth of polyalcohol recovery tower and recycle
In tower, the theoretical cam curve of polyalcohol recovery tower is 15 pieces, operating pressure 0.1Mpa, reflux ratio 1.5, tower top temperature 100
℃.After rectifying separates, tower bottom produces polyalcohol and enters polyalcohol intermediate storage tank through polyalcohol feed inlet, water and a small amount of polynary
Alcohol and other by-products enter return tank of top of the tower from tower top after overhead condenser condenses, and return tank Partial Liquid Phase is through polyalcohol
Recovery tower refluxing opening enters polyalcohol recovery tower, Partial Liquid Phase extraction, and fixed gas is produced from overhead reflux tank top.
As described above, must not be explained although the present invention has been indicated and described referring to specific preferred embodiment
For the limitation to invention itself.It without prejudice to the spirit and scope of the invention as defined in the appended claims, can be right
Various changes can be made in the form and details for it.
Claims (10)
1. a kind of device of aromatic polyester polyol synthesis, it is characterised in that: including mixer, polyalcohol pans, esterification
Reaction kettle, batch condensation polymerization reactor, Intermediate Heat Exchanger, reconciliation reaction kettle, polyalcohol recovery tower, overhead condenser, return tank of top of the tower, control
Valve group processed and delivery pump；
The mixer is equipped with organic carboxyl acid feed inlet, mixer polyalcohol feed inlet and mixer discharge port, the polyalcohol
Pans are equipped with polyalcohol feed inlet and pans polyalcohol discharge port after fresh polyalcohol feed inlet, recycling, the pans
Polyalcohol discharge port is connect with mixer polyalcohol feed inlet, and connecting tube is equipped with the first control valve group；
Reaction kettle of the esterification gaseous phase outlet, reaction kettle of the esterification inert gas import are equipped at the top of the reaction kettle of the esterification, side is equipped with
Reaction kettle of the esterification feed inlet, the reaction kettle of the esterification feed inlet are connect with mixer discharge port, and bottom portion is equipped with material after esterification
Discharge port, which connect with the first conveying pump inlet, and discharge port is equipped with the second control valve group；
It is more that batch condensation polymerization reactor gaseous phase outlet, batch condensation polymerization reactor vacuum system interface and supplement are equipped at the top of the batch condensation polymerization reactor
First alcohol feed inlet, side are equipped with batch condensation polymerization reactor mixed material feed inlet, which connect with the outlet of the first delivery pump；Kettle
Bottom is equipped with material discharge port after polycondensation, which connect with the second conveying pump inlet, and discharge port is equipped with the 4th control
Valve group, while the import of the second delivery pump is also connected with catalyst charge pipe；The Intermediate Heat Exchanger is set to the second delivery pump
On efferent duct；The supplement polyalcohol feed inlet is connect with pans polyalcohol discharge port, and connecting tube is controlled equipped with third
Valve group；
Additive inlet port, reconciliation reaction kettle inert gas import and reconciliation reaction kettle vacuum system are equipped at the top of the reconciliation reaction kettle
System interface, side are equipped with batch condensation polymerization reactor and are mixed into material mouth, and the feed inlet and the second conveying pump main outlet connect, and reconciliation is anti-
Bottom portion is answered to be equipped with polyester polyol outlet for product；
The polyalcohol recovery tower tower bottom has recovery tower polyalcohol discharge port, and the discharge port and polyalcohol intermediate storage tank feed inlet connect
It connects, the polyalcohol recovery tower lower side is equipped with gas-phase feed mouth at two, is connected at one with reaction kettle of the esterification gaseous phase outlet, separately
It is connected at one with batch condensation polymerization reactor gaseous phase outlet, recovery tower gaseous phase outlet is equipped at the top of the polyalcohol recovery tower, which goes out
Mouth is connected with overhead condenser import；The overhead condenser outlet is connect with return tank of top of the tower feed inlet, the overhead reflux
The material refluxing opening of tank is connect with the refluxing opening of polyalcohol recovery tower top-side, and the overhead reflux tank top is equipped with fixed gas
Outlet, bottom are equipped with material and produce mouth.
2. carrying out the work of aromatic polyester polyol synthesis using the device that the aromatic polyester polyol of claim 1 synthesizes
Skill, which comprises the steps of:
1.1, be preheating to certain temperature organic polycarboxylic acid and polyalcohol difference slave carboxylic acid feed mouth, mixer polyalcohol into
Material mouth enters mixer, is sent into reaction kettle of the esterification after mixing in mixer, carries out the first step under inert gas protection
Esterification, reaction generates a large amount of water, polyester polyols alcohol monomer, remaining polyalcohol and other by-products, wherein whole water
Polyalcohol recovery tower is entered through gaseous phase outlet with gas phase with excessive polyalcohol and by-product, carries out returning for polyalcohol
It receives, wherein organic polycarboxylic acid is preheating to 100-200 DEG C, and polyalcohol is preheating to 70-150 DEG C；Reaction time is 0.5-6h, esterification
Reactor bottom discharge port control valve is opened, and polyester polyols alcohol monomer is produced from reactor bottom material outlet, with catalyst one
It rises and is pumped into batch condensation polymerization reactor through delivery pump；
1.2, polyester polyols alcohol monomer and catalyst that step 1.1 produces are pumped into batch condensation polymerization reactor through delivery pump, polycondensation is anti-
Answer kettle using vacuumizing, under inert gas protection, polyester polyols alcohol monomer is under the action of catalyst in batch condensation polymerization reactor
Polycondensation dehydration is carried out, to supplement certain weight polyalcohol in reaction process, organic multicomponent carboxylic in the polyalcohol of supplement and charging
The molar ratio of acid is 0.1-1；Polycondensation reaction is promoted to carry out thoroughly, polycondensation reaction time 0.5-8h, the reaction time is by fixed
Phase measures carboxylic value and the hydroxyl value of material to determine, when hydroxyl value concentration is less than 500mgKOH/g, and carboxylic value is less than 5mgKOH/g, contracts
Poly- reaction can terminate, and material discharge port produces polyester polyol polymer after the polycondensation of batch condensation polymerization reactor bottom；Polycondensation reaction
The water of generation and a small amount of polyalcohol enter in polyalcohol recovery tower through gaseous phase outlet, carry out the recycling of polyalcohol；
1.3, the polyester polyol polymer that step 1.2 produces is pumped into Intermediate Heat Exchanger, through Intermediate Heat Exchanger by polyester polyol
Polymer is sent into reconciliation reaction kettle after being cooled to 30-100 DEG C, under inert gas protection, pass through and add different additive groups
Divide to adjust average molecular weight, the degree of polymerization, carboxylic value and the hydroxyl value index of polyester polyol polymer, the reaction kettle that reconciles can use
Vacuum or atmospheric operation, the reaction kettle that reconciles is needed using inert gas seal, by being detected and analyzed to discharging in kettle,
Qualified products are produced wait reconcile when material in reactor reaches desired value, which includes average molecular weight, carboxylic value and hydroxyl
It is worth index, average molecular weight 2000-5000, hydroxyl value is not more than 100mgKOH/g, and carboxylic value is no more than 1mgKOH/g；
1.4, step 1.1 and the gas phase of 1.2 extraction are entered in polyalcohol recovery tower by two gas-phase feed mouth of polyalcohol recovery tower,
After rectifying separates, polyalcohol feed inlet enters polyalcohol intermediate storage tank after tower bottom extraction polyalcohol is recovered, water and a small amount of
Polyalcohol and other by-products enter return tank of top of the tower from tower top after overhead condenser condenses, and return tank Partial Liquid Phase is through more
First alcohol recovery tower refluxing opening enters polyalcohol recovery tower, Partial Liquid Phase extraction, and fixed gas is produced from overhead reflux tank top.
3. the technique of aromatic polyester polyol synthesis according to claim 2, which is characterized in that the organic multicomponent carboxylic
Acid is by phthalic acid, M-phthalic acid, terephthalic acid (TPA), 1,2,4- benzenetricarboxylic acids, 1,3,5- benzenetricarboxylic acids and 2,6- naphthalene two
It is one or more kinds of in formic acid to constitute；The polyalcohol is by ethylene glycol, diethylene glycol (DEG), polyethylene glycol, 1,2-PD, 1,3- the third two
One or more of alcohol, dipropylene glycol, 1,4-butanediol and neopentyl glycol are constituted.
4. the technique of aromatic polyester polyol synthesis according to claim 2, which is characterized in that the catalyst is selected from
Following compounds: isopropyl titanate, tetrabutyl titanate, titanium ethylene glycolate, water-resistant solution titanium catalyst, antimony oxide, acetic acid
One of antimony, antimony glycol, germanium dioxide, dibutyl tin laurate, phosphotungstic acid are a variety of.
5. the technique of aromatic polyester polyol synthesis according to claim 4, which is characterized in that the catalyst is preferred
Isopropyl titanate or tetrabutyl titanate.
6. the technique of aromatic polyester polyol synthesis according to claim 5, which is characterized in that the catalyst concn
For 10-100ppm.
7. the technique of aromatic polyester polyol synthesis according to claim 6, which is characterized in that the catalyst concn
It is preferred that 20-50ppm.
8. the technique of aromatic polyester polyol synthesis according to claim 2, which is characterized in that the work of the mixer
Making temperature is 80-200 DEG C；Reaction kettle of the esterification operating pressure is -0.1Mpa-0.1Mpa, and reaction temperature is 150-280 DEG C, is entered
The alcohol of reaction kettle of the esterification/acid molar ratio is 1.05-1.35；Batch condensation polymerization reactor operating pressure is 0-0.1Mpa, and reaction temperature is
150-280 DEG C, supplement polyalcohol and polybasic carboxylic acid molar ratio are 0.05-0.30 in batch condensation polymerization reactor；The reaction kettle reaction that reconciles is warm
Degree is 30-150 DEG C, and operating pressure is -0.1Mpa-0.1Mpa.
9. the technique of aromatic polyester polyol according to claim 2 synthesis, which is characterized in that the additive includes
Antioxidant, acid value and hydroxyl value regulator；The antioxidant is acidic antioxidant or phosphite ester antioxidant；The acid value and
Hydroxyl value regulator is the acid rich in hydroxyl value or carboxylic value, the alcohols material rich in hydroxyl value or carboxylic value.
10. the technique of aromatic polyester polyol synthesis according to claim 2, which is characterized in that the polyalcohol returns
The theoretical cam curve for receiving tower is 10-30 block, operating pressure 0.01-0.4Mpa, reflux ratio 1.2-5.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110183638A (en) * | 2019-05-21 | 2019-08-30 | 中建安装集团有限公司 | A kind of device and technique of the synthesis of polyester polyol series of products |
| CN116440803A (en) * | 2023-06-16 | 2023-07-18 | 北京湃普莱恩尼龙新材料技术有限公司 | Preparation process and preparation device of polyamide |
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| JP2009114234A (en) * | 2007-11-01 | 2009-05-28 | Mitsubishi Chemicals Corp | Method for producing polyester |
| CN206337204U (en) * | 2016-12-30 | 2017-07-18 | 上海聚友化工有限公司 | A kind of PEPA continuous production device |
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| CN110183638A (en) * | 2019-05-21 | 2019-08-30 | 中建安装集团有限公司 | A kind of device and technique of the synthesis of polyester polyol series of products |
| CN116440803A (en) * | 2023-06-16 | 2023-07-18 | 北京湃普莱恩尼龙新材料技术有限公司 | Preparation process and preparation device of polyamide |
| CN116440803B (en) * | 2023-06-16 | 2023-09-05 | 北京湃普莱恩尼龙新材料技术有限公司 | Preparation process and preparation device of polyamide |
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