CN112210076B - Method and device for continuously producing polyether amide elastomer - Google Patents
Method and device for continuously producing polyether amide elastomer Download PDFInfo
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- CN112210076B CN112210076B CN201910625077.0A CN201910625077A CN112210076B CN 112210076 B CN112210076 B CN 112210076B CN 201910625077 A CN201910625077 A CN 201910625077A CN 112210076 B CN112210076 B CN 112210076B
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
Abstract
The invention relates to a method and a device for continuously producing polyether amide elastomer. The continuous production method of the polyether amide elastomer comprises the following steps: a) Carrying out prepolymerization reaction on low molecular weight polyamide, polyether and a catalyst to obtain a prepolymerization reaction material; b) And d), feeding the prepolymerized reaction material obtained in the step a) into a tubular reactor for polymerization reaction to obtain a polymerization reaction material. The method has the advantages of simple process, easy operation of steps, high production efficiency, adjustable product types, stable quality and wide application range of the produced polyether amide elastomer by adopting a continuous process to produce the polyether amide elastomer.
Description
Technical Field
The invention belongs to the technical field of polymer preparation, and particularly relates to a method and a device for continuously producing polyether amide elastomer.
Background
Polyether amide thermoplastic elastomers refer to a class of block copolymers consisting of high melting crystalline polyamide hard segments and polyether or polyester soft segments. The polyether amide elastomer has the advantages of toughness, wear resistance, fatigue resistance, sound absorption, good thermal stability and cold resistance, easy processing and forming, and wide application in the fields of automobiles, machinery, electronic appliances, electrical precision instruments, sports goods, medical treatment and the like. The current production method of polyether amide elastomer mainly adopts batch reaction of a reaction kettle. Batch processes have low production efficiency and poor product quality batch stability. In order to obtain higher production efficiency and stable quality, it is important to develop a continuous production process.
Disclosure of Invention
In order to solve the problems of the prior art, the first aspect of the present invention provides a method for continuously producing polyether amide elastomer, which is beneficial to improving the efficiency and the quality of the product. In a second aspect, the invention provides an apparatus for use in a process for continuously producing polyether amide elastomers.
According to a first aspect, the present invention provides a process for the continuous production of polyether amide elastomers comprising the steps of:
a) Carrying out prepolymerization reaction on low molecular weight polyamide, polyether and a catalyst to obtain a prepolymerization reaction material;
b) And d), feeding the prepolymerized reaction material obtained in the step a) into a tubular reactor for polymerization reaction to obtain a polymerization reaction material.
According to some embodiments of the invention, the process further comprises step c) feeding the polymerization reaction mass obtained in step b) to an extruder, such as a twin screw extruder, for extrusion, to obtain the polyether amide elastomer.
According to some embodiments of the invention, the low molecular weight polyamide is selected from one or more of a carboxyl terminated AABB type or AB type polyamide, such as one or more of a carboxyl terminated polyamide PA6, a carboxyl terminated polyamide PA12, a carboxyl terminated polyamide PA610 and a carboxyl terminated polyamide PA 1010.
According to some embodiments of the invention, the low molecular weight polyamide has a molecular weight of 200 to 5000g/mol, preferably 500 to 1500g/mol, for example 1000g/mol.
According to some embodiments of the invention, the polyether is selected from one or more of hydroxyl-terminated and/or amino-terminated polyethers, preferably from one or more of hydroxyl-terminated polyethers, such as polytetrahydrofuran ether.
According to some embodiments of the invention, the polyethers have a molecular weight of 200 to 3000g/mol, preferably 600 to 2000g/mol, for example 600g/mol, 1000g/mol and 2000g/mol.
According to some embodiments of the invention, when hydroxyl-terminated polyethers are used, metal derivatives containing titanium, zirconium, hafnium are used, preferably of the general formula M (OR) 4 Metal derivatives of (2), whichWherein M represents a titanium, zirconium, hafnium metal atom, R, which may be the same or different, represents an alkyl group having 1 to 24 carbon atoms, which may be linear or branched. The catalyst described in the above formula comprises Ti (OC 2 H 5 ) 4 、Ti(OC 3 H 7 ) 4 、Ti(OC 4 H 9 ) 4 、Zr(OC 2 H 5 ) 4 、Zr(OC 4 H 9 ) 4 And Ti (OC) 6 H 13 ) 4 Is a kind of medium. Tetrabutyl titanate is preferred. When amine-terminated polyethers are used, compounds containing phosphorus atoms, such as phosphoric acid, phosphorous acid, hypophosphorous acid, triphenyl phosphite, are used. Phosphoric acid is preferred.
According to some embodiments of the invention, the mass ratio of the low molecular weight polyamide to the polyether is 100 (10-1000), preferably 100 (20-600).
According to some embodiments of the invention, the mass ratio of the low molecular weight polyamide to the catalyst is 100 (0.01 to 1.0), preferably 100 (0.1 to 0.5).
According to some embodiments of the invention, the mass ratio of the low molecular weight polyamide, polyether and catalyst is 100 (10-1000): (0.01-1.0), preferably 100 (20-600): (0.1-0.5).
According to some embodiments of the invention, the temperature of the reaction in step a) is 200-250 ℃, the pressure of the reaction is 0-0.09 MPa, and the time of the reaction is 0.5-2 h.
According to some embodiments of the invention, the reaction in step b) is carried out at 200 to 270 ℃, preferably at 230 to 250 ℃, the vacuum degree of the reaction is 100 to 10000Pa, preferably 200 to 6000Pa, and the reaction time is 0.5 to 3 hours, preferably 0.5 to 2 hours.
According to some embodiments of the invention, the temperature of the reaction in step c) is 200 to 270 ℃, preferably 240 to 260 ℃, and the reaction time is 10 to 60min, preferably 15 to 30min.
The method has the advantages of simple process, easy operation of steps, high production efficiency, adjustable product types, stable quality and wide application range of the produced polyether amide elastomer by adopting a continuous process to produce the polyether amide elastomer.
According to a second aspect, the present invention provides an apparatus for the continuous production of polyether amide elastomer comprising a prepolymerization tank, a tubular reactor and an extruder in series.
According to the above embodiment of the present invention, the number of the tubular reactors is two or more, depending on the reaction requirements.
According to some embodiments of the invention, the temperature of the tubular reactor can be controlled in sections, and the temperature of the tubular reactor can be controlled in sections, so that the reaction temperature can be accurately controlled, and the conversion rate can be improved.
According to some embodiments of the invention, the tubular reactor is temperature controlled in three stages.
According to some embodiments of the invention, the tubular reactor is internally provided with a pipe member and is internally provided with a heat conducting oil station.
According to some embodiments of the invention, the prepolymerization tank may be a vertical stirred tank, and the stirring paddle may be in the form of an anchor, a ribbon, a turbine, a paddle, a frame, a propeller, or the like. The upper part of the prepolymerization reactor is respectively provided with an exhaust port.
According to some embodiments of the invention, the extruder is a single screw extruder and/or a twin screw extruder, preferably a twin screw extruder.
In some preferred embodiments of the invention, a tubular reactor is adopted, so that polymerization reaction materials can be quickly and uniformly mixed, the heat exchange area is large, the reaction speed can be increased, the molecular weight of the obtained product is high, meanwhile, the polymerization reaction materials enter a double-screw extruder to continue to react, on the basis of the tubular reactor, the reaction materials further enter the double-screw extruder, and the double-screw extruder has the effects of strong mixing and vacuumizing, thereby being beneficial to promoting the further reaction of high-viscosity materials in the later stage of the reaction and improving the molecular weight and conversion rate of the product.
Detailed Description
The present invention will be further described with reference to specific examples.
Example 1:
a method for continuously producing polyether amide elastomer adopts a prepolymerization kettle, a tubular reactor and a double screw extruder which are connected in series to continuously produce polyether amide elastomer.
Low molecular weight carboxyl terminated polyamide PA6, molecular weight 1000g/mol, flow 5kg/hr; polytetrahydrofuran ether, molecular weight 1000g/mol, flow 5kg/hr, catalyst tetrabutyl titanate, flow 15g/hr. The materials enter a prepolymerization kettle through a conveying pump, the temperature of the prepolymerization kettle is 210 ℃, the gauge pressure is-0.02 MPa, the residence time is 1hr, the materials enter a tubular reactor I and a tubular reactor II sequentially through the conveying pump, the reaction temperature of the tubular reactor I is 230 ℃, the residence time is 1hr, the vacuum pressure in the reactor is-6000 Pa, the reaction temperature of the tubular reactor II is 250 ℃, the residence time is 1hr, and the vacuum pressure is-500 Pa. Feeding into a double-screw extruder via a conveying pump, wherein the temperature of the extruder is 250 ℃, the residence time is 20min, and finally feeding into a granulator, water-cooling granulation and drying.
Example 2:
a method for continuously producing polyether amide elastomer adopts a prepolymerization kettle, a tubular reactor and a double screw extruder which are connected in series to continuously produce polyether amide elastomer.
Low molecular weight carboxyl terminated polyamide PA12, molecular weight 1000g/mol, flow 5kg/hr; polytetrahydrofuran ether, molecular weight 1000g/mol, flow 5kg/hr, catalyst tetrabutyl titanate, flow 15g/hr. The materials enter a prepolymerization kettle through a conveying pump, the temperature of the prepolymerization kettle is 210 ℃, the gauge pressure is-0.02 MPa, the residence time is 1hr, the materials enter a tubular reactor I and a tubular reactor II sequentially through the conveying pump, the reaction temperature of the tubular reactor I is 230 ℃, the residence time is 1hr, the vacuum pressure in the reactor is-6000 Pa, the reaction temperature of the tubular reactor II is 250 ℃, the residence time is 1hr, and the vacuum pressure is-500 Pa. Feeding into a double-screw extruder via a conveying pump, wherein the temperature of the extruder is 250 ℃, the residence time is 20min, and finally feeding into a granulator, water-cooling granulation and drying.
Example 3:
a method for continuously producing polyether amide elastomer adopts a prepolymerization kettle, a tubular reactor and a double screw extruder which are connected in series to continuously produce polyether amide elastomer.
Low molecular weight carboxyl terminated polyamide PA12, molecular weight 1000g/mol, flow 5kg/hr; polytetrahydrofuran ether, molecular weight 2000g/mol, flow 10kg/hr, catalyst tetrabutyl titanate, flow 15g/hr. The materials enter a prepolymerization kettle through a conveying pump, the temperature of the prepolymerization kettle is 210 ℃, the gauge pressure is-0.02 MPa, the residence time is 1hr, the materials enter a tubular reactor I and a tubular reactor II sequentially through the conveying pump, the reaction temperature of the tubular reactor I is 230 ℃, the residence time is 1hr, the vacuum pressure in the reactor is-6000 Pa, the reaction temperature of the tubular reactor II is 250 ℃, the residence time is 1hr, and the vacuum pressure is-500 Pa. Feeding into a double-screw extruder via a conveying pump, wherein the temperature of the extruder is 250 ℃, the residence time is 20min, and finally feeding into a granulator, water-cooling granulation and drying.
Example 4:
a method for continuously producing polyether amide elastomer adopts a prepolymerization kettle, a tubular reactor and a double screw extruder which are connected in series to continuously produce polyether amide elastomer.
Low molecular weight carboxyl terminated polyamide PA12, molecular weight 1000g/mol, flow 5kg/hr; polytetrahydrofuran ether, molecular weight 2000g/mol, flow 10kg/hr, catalyst tetrabutyl titanate, flow 30g/hr. The materials enter a prepolymerization kettle through a conveying pump, the temperature of the prepolymerization kettle is 210 ℃, the gauge pressure is-0.02 MPa, the residence time is 1hr, the materials enter a tubular reactor I and a tubular reactor II sequentially through the conveying pump, the reaction temperature of the tubular reactor I is 230 ℃, the residence time is 1hr, the vacuum pressure in the reactor is-6000 Pa, the reaction temperature of the tubular reactor II is 250 ℃, the residence time is 1hr, and the vacuum pressure is-500 Pa. Feeding into a double-screw extruder via a conveying pump, wherein the temperature of the extruder is 250 ℃, the residence time is 20min, and finally feeding into a granulator, water-cooling granulation and drying.
Example 5:
a method for continuously producing polyether amide elastomer adopts a prepolymerization kettle, a tubular reactor and a double screw extruder which are connected in series to continuously produce polyether amide elastomer.
Low molecular weight carboxyl terminated polyamide PA610, molecular weight 1000g/mol, flow 10kg/hr; polytetrahydrofuran ether, molecular weight 600g/mol, flow 6kg/hr, catalyst tetrabutyl titanate, flow 20g/hr. The materials enter a prepolymerization kettle through a conveying pump, the temperature of the prepolymerization kettle is 210 ℃, the gauge pressure is-0.02 MPa, the residence time is 1hr, the materials enter a tubular reactor I and a tubular reactor II sequentially through the conveying pump, the reaction temperature of the tubular reactor I is 230 ℃, the residence time is 1hr, the vacuum pressure in the reactor is-6000 Pa, the reaction temperature of the tubular reactor II is 250 ℃, the residence time is 1hr, and the vacuum pressure is-500 Pa. Feeding into a double-screw extruder via a conveying pump, wherein the temperature of the extruder is 250 ℃, the residence time is 20min, and finally feeding into a granulator, water-cooling granulation and drying.
Example 6:
a method for continuously producing polyether amide elastomer adopts a prepolymerization kettle, a tubular reactor and a double screw extruder which are connected in series to continuously produce polyether amide elastomer.
Low molecular weight carboxyl terminated polyamide PA1010, molecular weight 1000g/mol, flow 10kg/hr; polytetrahydrofuran ether, molecular weight 1000g/mol, flow 10kg/hr, catalyst tetrabutyl titanate, flow 20g/hr. The materials enter a prepolymerization kettle through a conveying pump, the temperature of the prepolymerization kettle is 210 ℃, the gauge pressure is-0.02 MPa, the residence time is 1hr, the materials enter a tubular reactor I and a tubular reactor II sequentially through the conveying pump, the reaction temperature of the tubular reactor I is 230 ℃, the residence time is 1hr, the vacuum pressure in the reactor is-6000 Pa, the reaction temperature of the tubular reactor II is 250 ℃, the residence time is 1hr, and the vacuum pressure is-500 Pa (G). Feeding into a double-screw extruder via a conveying pump, wherein the temperature of the extruder is 250 ℃, the residence time is 20min, and finally feeding into a granulator, water-cooling granulation and drying.
Example 7
A method for continuously producing polyether amide elastomer adopts a prepolymerization kettle, a tubular reactor and a double screw extruder which are connected in series to continuously produce polyether amide elastomer.
Low molecular weight carboxyl terminated polyamide PA610, molecular weight 1000g/mol, flow 10kg/hr; polytetrahydrofuran ether, molecular weight 600g/mol, flow 2kg/hr, catalyst tetrabutyl titanate, flow 10g/hr. The materials enter a prepolymerization kettle through a conveying pump, the temperature of the prepolymerization kettle is 210 ℃, the gauge pressure is-0.02 MPa, the residence time is 1hr, the materials enter a tubular reactor I and a tubular reactor II sequentially through the conveying pump, the reaction temperature of the tubular reactor I is 230 ℃, the residence time is 1hr, the vacuum pressure in the reactor is-6000 Pa, the reaction temperature of the tubular reactor II is 250 ℃, the residence time is 1hr, and the vacuum pressure is-500 Pa. Feeding into a double-screw extruder via a conveying pump, wherein the temperature of the extruder is 250 ℃, the residence time is 20min, and finally feeding into a granulator, water-cooling granulation and drying.
Example 8
A method for continuously producing polyether amide elastomer adopts a prepolymerization kettle, a tubular reactor and a double screw extruder which are connected in series to continuously produce polyether amide elastomer.
Low molecular weight carboxyl terminated polyamide PA1010, molecular weight 1000g/mol, flow 10kg/hr; polytetrahydrofuran ether, molecular weight 1000g/mol, flow 60kg/hr, catalyst tetrabutyl titanate, flow 50g/hr. The materials enter a prepolymerization kettle through a conveying pump, the temperature of the prepolymerization kettle is 210 ℃, the gauge pressure is-0.02 MPa, the residence time is 1hr, the materials enter a tubular reactor I and a tubular reactor II sequentially through the conveying pump, the reaction temperature of the tubular reactor I is 230 ℃, the residence time is 1hr, the vacuum pressure in the reactor is-6000 Pa, the reaction temperature of the tubular reactor II is 250 ℃, the residence time is 1hr, and the vacuum pressure is-500 Pa. Feeding into a double-screw extruder via a conveying pump, wherein the temperature of the extruder is 250 ℃, the residence time is 20min, and finally feeding into a granulator, water-cooling granulation and drying.
Example 9
A method for continuously producing polyether amide elastomer adopts a prepolymerization kettle, a tubular reactor and a double screw extruder which are connected in series to continuously produce polyether amide elastomer.
Low molecular weight carboxyl terminated polyamide PA6, molecular weight 1000g/mol, flow 5kg/hr; polytetrahydrofuran ether, molecular weight 1000g/mol, flow 5kg/hr, catalyst tetrabutyl titanate, flow 15g/hr. The materials enter a prepolymerization kettle through a conveying pump, the temperature of the prepolymerization kettle is 210 ℃, the gauge pressure is-0.02 MPa, the residence time is 1hr, the materials enter a tubular reactor through the conveying pump successively, the reaction temperature is 260 ℃, and the residence time is 1hr and the vacuum pressure is-200 Pa. Feeding into a double-screw extruder via a conveying pump, wherein the temperature of the extruder is 250 ℃, the residence time is 20min, and finally feeding into a granulator, water-cooling granulation and drying.
Example 10
A method for continuously producing polyether amide elastomer adopts a prepolymerization kettle, a tubular reactor and a double screw extruder which are connected in series to continuously produce polyether amide elastomer.
Low molecular weight carboxyl terminated polyamide PA6, molecular weight 1000g/mol, flow 5kg/hr; polytetrahydrofuran ether, molecular weight 1000g/mol, flow 5kg/hr, catalyst tetrabutyl titanate, flow 15g/hr. The materials enter a prepolymerization kettle through a conveying pump, the temperature of the prepolymerization kettle is 250 ℃, the gauge pressure is-0.02 MPa, the residence time is 1hr, the materials enter a tubular reactor sequentially through the conveying pump, the temperature of the whole tubular reactor is controlled in three sections, the reaction temperature is 250 ℃,255 ℃,260 ℃, the residence time is 1hr, and the vacuum pressure is-200 Pa. Feeding into a double-screw extruder via a conveying pump, wherein the temperature of the extruder is 260 ℃, the residence time is 20min, and finally feeding into a granulator, water-cooling granulation and drying.
Example 11
A method for continuously producing polyether amide elastomer adopts a prepolymerization kettle, a tubular reactor and a double screw extruder which are connected in series to continuously produce polyether amide elastomer.
Low molecular weight carboxyl terminated polyamide PA6, molecular weight 1000g/mol, flow 5kg/hr; polytetrahydrofuran ether, molecular weight 1000g/mol, flow 5kg/hr, catalyst tetrabutyl titanate, flow 15g/hr. The materials enter a prepolymerization reactor through a conveying pump, the temperature of the prepolymerization reactor is 210 ℃, the gauge pressure is-0.02 MPa, the residence time is 1hr, the materials enter a tubular reactor I and a tubular reactor II sequentially through the conveying pump, the reaction temperature of the tubular reactor I is 250 ℃, the residence time is 0.5hr, the vacuum pressure in the reactor is-500 Pa, the reaction temperature of the tubular reactor II is 250 ℃, the residence time is 0.5hr, and the vacuum pressure is-200 Pa. Feeding into a double-screw extruder via a conveying pump, wherein the temperature of the extruder is 250 ℃, the residence time is 20min, and finally feeding into a granulator, water-cooling granulation and drying.
Example 12
A method for continuously producing polyether amide elastomer adopts a prepolymerization kettle, a tubular reactor and a double screw extruder which are connected in series to continuously produce polyether amide elastomer.
Low molecular weight carboxyl terminated polyamide PA6, molecular weight 1000g/mol, flow 5kg/hr; polytetrahydrofuran ether, molecular weight 1000g/mol, flow 5kg/hr, catalyst tetrabutyl titanate, flow 15g/hr. The materials enter a prepolymerization kettle through a conveying pump, the temperature of the prepolymerization kettle is 210 ℃, the gauge pressure is-0.02 MPa, the residence time is 1hr, the materials enter a tubular reactor I and a tubular reactor II sequentially through the conveying pump, the reaction temperature of the tubular reactor I is 230 ℃, the residence time is 1hr, the vacuum pressure in the reactor is-6000 Pa, the reaction temperature of the tubular reactor II is 250 ℃, the residence time is 1hr, and the vacuum pressure is-500 Pa. Finally, the mixture enters a granulator for water-cooling granulation and drying.
Example 13:
a method for continuously producing polyether amide elastomer adopts a prepolymerization kettle, a tubular reactor and a double screw extruder which are connected in series to continuously produce polyether amide elastomer.
Low molecular weight carboxyl terminated polyamide PA6, molecular weight 1000g/mol, flow 5kg/hr; polytetrahydrofuran ether, molecular weight 1000g/mol, flow 5kg/hr, catalyst tetrabutyl titanate, flow 15g/hr. The materials enter a prepolymerization kettle through a conveying pump, the temperature of the prepolymerization kettle is 210 ℃, the gauge pressure is-0.02 MPa, the residence time is 1hr, the materials enter a tubular reactor I and a tubular reactor II sequentially through the conveying pump, the reaction temperature of the tubular reactor I is 230 ℃, the residence time is 1hr, the vacuum pressure in the reactor is-6000 Pa, the reaction temperature of the tubular reactor II is 250 ℃, the residence time is 1hr, and the vacuum pressure is-500 Pa. Feeding into a double-screw extruder via a conveying pump, wherein the temperature of the extruder is 260 ℃, the residence time is 20min, and finally feeding into a granulator, water-cooling granulation and drying.
Example 14:
a method for continuously producing polyether amide elastomer adopts a prepolymerization kettle, a tubular reactor and a double screw extruder which are connected in series to continuously produce polyether amide elastomer.
Low molecular weight carboxyl terminated polyamide PA6, molecular weight 1000g/mol, flow 5kg/hr; polytetrahydrofuran ether, molecular weight 1000g/mol, flow 5kg/hr, catalyst tetrabutyl titanate, flow 15g/hr. The materials enter a prepolymerization kettle through a conveying pump, the temperature of the prepolymerization kettle is 210 ℃, the gauge pressure is-0.02 MPa, the residence time is 1hr, the materials enter a tubular reactor I and a tubular reactor II sequentially through the conveying pump, the reaction temperature of the tubular reactor I is 230 ℃, the residence time is 1hr, the vacuum pressure in the reactor is-6000 Pa, the reaction temperature of the tubular reactor II is 250 ℃, the residence time is 1hr, and the vacuum pressure is-500 Pa. Feeding into a double-screw extruder via a conveying pump, wherein the temperature of the extruder is 240 ℃, the residence time is 20min, and finally feeding into a granulator, water-cooling granulation and drying.
Example 15:
a method for continuously producing polyether amide elastomer adopts a prepolymerization kettle, a tubular reactor and a double screw extruder which are connected in series to continuously produce polyether amide elastomer.
Low molecular weight carboxyl terminated polyamide PA6, molecular weight 1000g/mol, flow 5kg/hr; polytetrahydrofuran ether, molecular weight 1000g/mol, flow 5kg/hr, catalyst tetrabutyl titanate, flow 15g/hr. The materials enter a prepolymerization kettle through a conveying pump, the temperature of the prepolymerization kettle is 210 ℃, the gauge pressure is-0.02 MPa, the residence time is 1hr, the materials enter a tubular reactor I and a tubular reactor II sequentially through the conveying pump, the reaction temperature of the tubular reactor I is 230 ℃, the residence time is 1hr, the vacuum pressure in the reactor is-6000 Pa, the reaction temperature of the tubular reactor II is 250 ℃, the residence time is 1hr, and the vacuum pressure is-500 Pa. Feeding into a double-screw extruder via a conveying pump, wherein the temperature of the extruder is 250 ℃, the residence time is 40min, and finally feeding into a granulator, water-cooling granulation and drying.
Example 16:
a method for continuously producing polyether amide elastomer adopts a prepolymerization kettle, a tubular reactor and a double screw extruder which are connected in series to continuously produce polyether amide elastomer.
Low molecular weight carboxyl terminated polyamide PA6, molecular weight 1000g/mol, flow 5kg/hr; polytetrahydrofuran ether, molecular weight 1000g/mol, flow 5kg/hr, catalyst tetrabutyl titanate, flow 15g/hr. The materials enter a prepolymerization kettle through a conveying pump, the temperature of the prepolymerization kettle is 210 ℃, the gauge pressure is-0.02 MPa, the residence time is 1hr, the materials enter a tubular reactor I and a tubular reactor II sequentially through the conveying pump, the reaction temperature of the tubular reactor I is 230 ℃, the residence time is 1hr, the vacuum pressure in the reactor is-6000 Pa, the reaction temperature of the tubular reactor II is 250 ℃, the residence time is 1hr, and the vacuum pressure is-500 Pa. Feeding into a double-screw extruder via a conveying pump, wherein the temperature of the extruder is 250 ℃, the residence time is 10min, and finally feeding into a granulator, water-cooling granulation and drying.
Test example:
(1) Relative viscosity
1g of polyether amide elastomer was weighed accurately, added to 100mL of 96% concentrated sulfuric acid, and after complete dissolution, the solution was put into a Ubbelohde viscometer, and the falling time (t) was measured at 25 ℃. The falling time (t) of 96% sulfuric acid was measured in the same manner 0 ). The relative viscosity can be obtained from the following formula:
relative viscosity = t/t 0
(2) Mechanical properties
Tensile strength and elongation at break were measured according to the method of ISO 527-2.
The test results are shown in table 1.
TABLE 1
It should be noted that the above-described embodiments are only for explaining the present invention and do not limit the present invention in any way. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (17)
1. A process for continuously producing a polyether amide elastomer comprising the steps of:
a) Carrying out prepolymerization reaction on low molecular weight polyamide, polyether and a catalyst to obtain a prepolymerization reaction material;
b) Feeding the prepolymerized reaction material obtained in the step a) into a tubular reactor for polymerization reaction to obtain a polymerization reaction material;
c) Feeding the polymerization reaction material obtained in the step b) into an extruder for extrusion to obtain the polyether amide elastomer;
the reaction temperature in the step a) is 200-250 ℃, the reaction pressure is 0-minus 0.09Mpa, and the reaction time is 0.5-2 h;
the reaction temperature in the step b) is 230-250 ℃, the vacuum degree of the reaction is 200-6000 Pa, and the reaction time is 0.5-2 h;
the extrusion temperature in the step c) is 200-270 ℃, and the extrusion time is 10-60 min.
2. The method according to claim 1, wherein the low molecular weight polyamide is selected from one or more of carboxyl terminated AABB type or AB type polyamides; and/or
The molecular weight of the low molecular weight polyamide is 200-5000 g/mol.
3. The method of claim 2, wherein the low molecular weight polyamide is selected from one or more of a carboxyl terminated polyamide PA6, a carboxyl terminated polyamide PA12, a carboxyl terminated polyamide PA610, and a carboxyl terminated polyamide PA 1010; and/or
The molecular weight of the low molecular weight polyamide is 500-1500 g/mol.
4. A method according to any one of claims 1-3, wherein the polyether is selected from one or more of hydroxyl-terminated and/or amino-terminated polyethers; and/or
The molecular weight of the polyether is 200-3000 g/mol.
5. The method of claim 4, wherein the polyether is selected from one or more of hydroxyl terminated polyethers; and/or
The molecular weight of the polyether is 600-2000 g/mol.
6. The method of claim 4, wherein the polyether is selected from polytetrahydrofuran ethers.
7. The method of claim 1, wherein the catalyst is selected from one or more of phosphoric acid, phosphorous acid, hypophosphorous acid, triphenyl phosphite.
8. The process according to claim 1, wherein the catalyst is selected from the group consisting of compounds of the general formula M (OR) 4 Wherein M is a titanium, zirconium or hafnium metal atom, R are the same or different and each is independently C 1 -C 24 An alkyl group.
9. The method of claim 8, wherein the catalyst is selected from one or more of tetraethyl titanate, tetrapropyl titanate, and tetrabutyl titanate.
10. The method according to any one of claims 1 to 3, 5 to 9, wherein the mass ratio of the low molecular weight polyamide, polyether and catalyst is 100 (10 to 1000): 0.01 to 1.0.
11. The method according to claim 10, wherein the mass ratio of the low molecular weight polyamide, polyether and catalyst is 100 (20-600): 0.1-0.5.
12. The method according to any one of claims 1-3, 5-9, 11, wherein the extrusion temperature in step c) is 240-260 ℃ and the extrusion time is 15-30 min.
13. The process according to any one of claims 1 to 3, 5 to 9, 11, characterized in that the apparatus for the continuous production of polyether amide elastomer comprises a prepolymerization tank, a tubular reactor and an extruder in series.
14. The method according to claim 13, wherein the tubular reactor is sectionally temperature controllable; the number of the reactors is more than two; and/or
The inside of the tubular reactor is provided with a pipe fitting component, and heat conduction oil is introduced into the tubular reactor.
15. The method of claim 14, wherein the tubular reactor is temperature controlled in three stages.
16. The method according to claim 13, wherein the extruder is a single screw extruder and/or a twin screw extruder.
17. The method according to any one of claims 14-16, wherein the extruder is a twin screw extruder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910625077.0A CN112210076B (en) | 2019-07-11 | 2019-07-11 | Method and device for continuously producing polyether amide elastomer |
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