CN111410709B - Gas phase polymerization method for catalyzing olefin homogeneous polymerization by late transition metal catalyst - Google Patents
Gas phase polymerization method for catalyzing olefin homogeneous polymerization by late transition metal catalyst Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a gas-phase polymerization method for catalyzing olefin homogeneous polymerization by using a late transition metal catalyst, which comprises the following steps: dissolving a mixture of a late transition metal catalyst and a cocatalyst in a molar ratio of 1: 1-1: 3 in a volatile organic solvent to form a catalyst solution; charging the resulting catalyst solution into a pressure reactor and uniformly coating it on the wall of the pressure reactor, thereby forming a catalyst membrane layer on the wall after the volatile organic solvent is volatilized; and introducing olefin gas, and enabling the olefin to contact and react with the catalyst film layer at the reaction pressure of 1-10 atmospheric pressures and the reaction temperature of 20-80 ℃, thereby obtaining the required olefin polymer. The homogeneous gas phase polymerization method can synthesize polyolefin materials with excellent performance, and can regulate and control the mechanical properties of the polyolefin materials by controlling the polymerization conditions. In addition, the homogeneous gas phase polymerization method of the invention significantly reduces the use of organic solvents, and belongs to an economic and environment-friendly olefin polymerization mode.
Description
Technical Field
The invention relates to the field of synthetic high-molecular polyolefin materials, in particular to a gas-phase polymerization method for catalyzing olefin homogeneous polymerization by using a late transition metal catalyst.
Background
Polyolefin materials are indispensable in production and living as well as industrial application, and have wide application. Since the discovery of heterogeneous titanium and chromium catalysts in the 1950 s, the polyolefin industry has rapidly progressed, and by 2015 the global production of polyolefin has reached 1.78 billion tons, making the polyolefin industry a multi-billion dollar business. Because of the superior performance of heterogeneous systems in terms of product morphology control, avoidance of reactor fouling and applicability in continuous polymerization processes, the commercial production of polyolefins has been dominated by the use of heterogeneous systems such as Ziegler-Natta and Phillips catalysts; however, contrary to the heterogeneous catalytic polymerization system widely used in the polyolefin industry, the heterogeneous nature of the homogeneous system can provide a solution for the "plug and play" catalyst strategy in the existing industrial polyolefin synthesis, so the research focus of the researchers in the academic research of polyolefin, especially in the field of late transition metal catalysts, has been focused on the homogeneous system. Although the heterogeneous system catalytic polymerization process in the industry is quite mature, the existing methods need to use a large amount of organic solvent to serve as a reaction solvent and an eluent in the process flow, and have the problems that polyolefin needs to be dried and the like; this places high demands on the work-up process of the olefin polymerization industry and the resulting emission of organic waste streams has a large environmental impact.
Therefore, there is still a need in the art to provide an improved process for preparing polyolefin materials to simplify the process of preparing polyolefin materials while reducing the emission of organic waste streams in order to achieve a "green chemistry" compliant polyolefin synthesis.
Disclosure of Invention
In order to overcome one or more of the problems of the prior art, the present invention provides a gas phase polymerization method for the homogeneous polymerization of olefins using a late transition metal catalyst, which has a simple process and does not require the use of a large amount of organic solvents, and particularly, the gas phase polymerization process of olefins does not involve the discharge of organic waste liquid at all, thereby realizing the synthesis of polyolefins meeting the "green chemistry" requirements.
In view of this, the present invention provides a gas phase polymerization process for the homogeneous polymerization of olefins catalyzed by a late transition metal catalyst, the gas phase polymerization process comprising:
dissolving a mixture of a late transition metal catalyst and a cocatalyst in a molar ratio of 1: 1-1: 3 in a volatile organic solvent to form a catalyst solution;
loading the obtained catalyst solution into a pressure reactor and uniformly coating the catalyst solution on the wall of the pressure reactor, thereby forming a catalyst membrane layer on the wall of the pressure reactor after the volatile organic solvent is volatilized; and
introducing olefin gas and reacting at a reaction pressure of 1-10 atm and a reaction temperature of 20-80 ℃ to obtain the desired olefin polymer,
wherein,
the late transition metal catalyst is an alpha-diimine palladium catalyst;
the cocatalyst is tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate.
In a preferred embodiment, the molar ratio of the late transition metal catalyst to the cocatalyst is 1: 1.5 to 1: 2.5.
In a preferred embodiment, the alpha-diimine palladium-based catalyst is one or more of the following formulas 1 to 8:
wherein Me represents a methyl group and Ph represents a phenyl group.
In a preferred embodiment, the cocatalyst is sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate or potassium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate.
In a preferred embodiment, the olefin is a gaseous alpha-olefin; preferably the gaseous alpha-olefin is ethylene, propylene or 1-butene; more preferably ethylene.
In a preferred embodiment, the volatile organic solvent is dichloromethane or trichloromethane.
In a further preferred embodiment, 0.1 to 0.5mL of the volatile organic solvent is used based on 1. mu. mol of the late transition metal catalyst.
In a preferred embodiment, the reaction time is 2 to 15 hours.
The beneficial effects of the present invention include, but are not limited to, the following aspects:
in the gas phase polymerization process of the present invention, a catalyst film layer is formed on the wall of a pressure reactor by using a specific late transition metal catalyst and a specific co-catalyst in a mixture of a specific ratio, and gaseous olefins are brought into contact with the catalyst film layer on the wall of the reactor for reaction. Because the catalyst membrane layer generates the porous polymer carrier, an organic liquid solvent or an additional solid material in the existing liquid phase method or gas-liquid two-phase method is not needed to be used as a polymerization carrier, and a quenching reaction step is not needed correspondingly, so that the production cost is greatly reduced, the process flow is simplified, and zero organic waste liquid discharge can be realized in the olefin polymerization process, thereby realizing the green chemical polyolefin synthesis.
In addition, compared with the existing liquid phase method or gas-liquid two-phase system polymerization method, the catalyst film layer formed by the method has a significantly larger contact surface area, so that the homogeneous polymerization of olefin can be completed more quickly, the required product can be directly obtained without post-treatment after the reaction, and the industrial production efficiency can be significantly improved.
In addition, with the gas phase polymerization method of the present invention, in the case of using a mixture of a specific late transition metal catalyst and a specific co-catalyst in a specific ratio, the microstructure of polyolefin can be controlled by controlling the olefin pressure and reaction temperature of the reaction, thereby obtaining polyolefins of different mechanical properties.
In addition, with the gas phase polymerization process of the present invention, a desired polyolefin product can be obtained in a higher yield, and the obtained polyolefin has a higher molecular weight and has good mechanical properties such as elongation at break, recovery rate, and the like.
Drawings
FIG. 1 shows the results of mechanical property tests of olefin polymers obtained by a gas phase polymerization method according to an example of the present invention, wherein (a) to (d) are elongation at break-stress graphs, and (e) to (h) are elastic recovery-stress graphs, and (a) and (e) are the test results of application example 5; (b) and (f) are test results of application example 6, (c) and (g) are test results of application example 13, and (d) and (h) are test results of application example 7.
Detailed Description
The inventors of the present invention have found, through extensive and intensive studies on olefin polymerization processes, that the post-transition metal catalysts exhibit different polymerization activities in different polymerization modes and the mechanical properties of the resulting polymers, and unexpectedly obtained a novel gas phase polymerization process of the present invention through studies on different polymerization modes of different post-transition metal catalysts and continuous optimization of design.
More specifically, the present invention forms a catalyst film layer on the wall of a reactor after the volatilization of a volatile organic solvent by using a mixture of a specific late transition metal catalyst and a specific co-catalyst in a specific ratio and forming the mixture into a catalyst solution that can be coated on the wall of the reactor with a very small amount of the volatile organic solvent. The formed catalyst membrane layer can form a porous polymer carrier, so that a metal center can be ensured to move along a polymer chain in the olefin polymerization process, and a proper site is found for effective olefin double bond bonding, so that an organic liquid solvent or an additional solid material is not required to be used as a polymerization carrier in the polymer polymerization process; meanwhile, the formed catalyst membrane layer has a significantly larger contact surface area, so that homogeneous polymerization of olefin can be more rapidly completed, and pure polyolefin product can be directly obtained without post-treatment such as precipitation, separation and drying required for liquid phase polymerization after the reaction.
The gas-phase polymerization method for catalyzing olefin homogeneous polymerization by using the late transition metal catalyst provided by the invention comprises the following steps: dissolving a mixture of a late transition metal catalyst and a promoter in a volatile organic solvent to form a catalyst solution; loading the obtained catalyst solution into a pressure reactor and uniformly coating the catalyst solution on the wall of the pressure reactor, thereby forming a catalyst membrane layer on the wall of the pressure reactor after the volatile organic solvent is volatilized; and introducing olefin gas, and reacting at a reaction pressure of 1-10 atm and a reaction temperature of 20-80 ℃ to obtain the required olefin polymer.
In the present invention, the late transition metal catalyst used is an α -diiminepalladium-based catalyst, and the co-catalyst used is tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate. In the present invention, the mixing molar ratio of the late transition metal catalyst and the cocatalyst is in the range of 1: 1 to 1: 3, preferably in the range of 1: 1.5 to 1: 2.5, and for example, may be 1: 2. The inventors of the present invention have found that when the mixing molar ratio of the late transition metal catalyst to the cocatalyst is lower than the above range, the catalyst activation is not thorough, the reaction rate is significantly reduced, and the mechanical properties of the obtained olefin polymer are poor; when the mixing molar ratio of the late transition metal catalyst to the cocatalyst is higher than the above range, part of the catalyst may be deactivated, and the mechanical properties of the obtained olefin polymer may be also poor.
In the present invention, preferably, the α -diimine palladium-based catalyst used may be one or more of the following formulas 1 to 8, which are obtained, for example, according to the literature ((1) Angew. chem. int. Ed.2015, 54, 9948-.
Wherein Me represents a methyl group and Ph represents a phenyl group.
In the present invention, preferably, as the co-catalyst, examples of tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate that may be used include, but are not limited to, sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate or potassium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, which is commercially available from Annaiji chemical company, for example, sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate having a product model number of E0609160250 may be used, for example.
In the present invention, before the olefin polymerization reaction is carried out, in order to form a desired catalyst film layer on the wall of the reactor, it is necessary to first mix the late transition metal catalyst and the cocatalyst at a molar ratio of 1: 1 to 1: 3, and then dissolve the resulting mixture in an appropriate amount of a volatile organic solvent to form a catalyst solution.
In the present invention, preferably, the volatile organic solvent used is dichloromethane or chloroform. The inventors of the present invention have found that not only is dichloromethane or chloroform easily available and inexpensive as a volatile organic solvent, but also when dichloromethane or chloroform is used as a volatile organic solvent of the present invention, dichloromethane or chloroform can be used in a significantly smaller amount than other volatile organic solvents for the same amount of the above mixture, for example, only 0.1 to 0.5mL of the volatile organic solvent may be used based on 1 μmol of the late transition metal catalyst. Accordingly, such a smaller amount of volatile solvent can be more rapidly volatilized after the formed catalyst solution is applied to the reactor wall, and a more uniform catalyst film layer can be formed, thereby speeding up the entire reaction process, while also reducing possible solvent recovery problems or environmental pollution problems, accordingly.
In the present invention, preferably, the olefin used for gas phase polymerization may be a gaseous α -olefin; more preferably, the gaseous alpha-olefin used is ethylene, propylene or 1-butene; most preferably, ethylene is used. Such olefins are typically stored in high pressure gas cylinders and are connected to and fed to the reactor as required by lines with flow and pressure control valves.
In the gas-phase polymerization process of the present invention, an olefin gas such as ethylene is introduced so that the pressure in the pressure reactor is in the range of 1 to 10 atmospheres (atm), for example, 8atm, and at such a reaction pressure, the polymerization can be rapidly completed and an olefin polymer having desired mechanical properties can be obtained. In contrast, when the pressure is lower than 1 atmosphere, the reaction is too slow and the resulting polymer has poor mechanical properties; when the pressure is higher than 10 atmospheres, the reaction is too fast, and the mechanical properties of the obtained polymer are also poor.
In the gas phase polymerization process of the present invention, the polymerization reaction is carried out at a reaction temperature of 20 to 80 ℃, preferably at a normal temperature of 25 ℃. The inventors have found that when the reaction temperature is below 20 ℃, the reaction rate is too slow and the resulting polymer has poor mechanical properties; when the reaction temperature is higher than 80 ℃, the reaction rate is too high, so that the implosion phenomenon can be generated, and at the moment, a part of the active centers of the catalyst metal can be covered by the polymer generated by the implosion, which is not beneficial to the growth of molecular chains, even leads to the early termination of the polymerization, so that the molecular weight difference of the obtained polymer is large, and the mechanical property of the obtained polymer is poor.
In the present invention, the polymerization reaction time is usually 2 to 15 hours, for example, 12 hours under the above reaction conditions.
In the present invention, there is no particular requirement for the pressure reactor to be used as long as the polymerization reaction can be effected at the above-mentioned pressure and temperature. Preferably, the pressure reactor used may be a stainless steel autoclave, a thick-walled glass pressure reactor, or the like. In order to be able to monitor the progress of the reaction by eye, a transparent thick-walled glass pressure reactor is more preferable.
In the present invention, preferably, after the connection of the ethylene feed line to the reactor and before the application of the catalyst solution, the reactor is first dried under vacuum and preferably, for example, at 90 ℃ for a certain time, for example, over 1h, and then the reactor is kept at the desired reaction temperature, for example, by a water bath or an oil bath, before the application of the catalyst solution is carried out.
In the present invention, after the polymerization reaction is completed, the pressure reactor is vented to obtain a polymer.
It is understood that within the scope of the present invention, one or more, even all, of the individual features specifically described herein may be combined independently of each other to form new or preferred embodiments. For reasons of space, they will not be described in detail.
Examples
The following examples are presented to illustrate specific embodiments of the invention and data are presented including gas phase polymerization data for various catalysts and test data for the resulting polymers, all sensitive materials stored in a glove box and ethylene gas purified by a water removal and oxygen removal column.
All preparations of the following examples were carried out according to standard Schlenk techniques.
The reagents used in the following examples were obtained from commercial sources without specific reference and used without purification (if necessary, dehydration drying treatment was carried out).
The branching degree of the polymer obtained in the following examples was obtained by nuclear magnetic resonance using a deuterated solvent which was dried and distilled before use. Except where otherwise indicated, the context of the present invention,1h and13c NMR spectra were recorded on a JNM-ECZ600R spectrometer at room temperature.
In the following examples, the molecular weights and molecular weight distributions of the polymers obtained from the different catalysts were determined by Gel Permeation Chromatography (GPC) using trichlorobenzene as solvent at 150 ℃ and calibrated using polystyrene standards.
In the following property Test examples, the obtained polymer was melt-pressed at 150 ℃ to obtain Test samples (dimensions of 12mm long x 2mm wide x 0.5mm thick), and then a tensile Test was conducted at room temperature by a Universal Test Machine (UTM2502) at 10 mm/min. Three samples were tested for each polymer and the results shown are the average.
In the examples below, DSC was performed by means of DSC Q2000 from TA Instruments. The resulting sample was rapidly heated to 150 ℃ and held for 5 minutes to remove the thermal history, then cooled to-50 ℃ at a rate of 10K/min, and finally reheated to 150 ℃ at the same rate under a nitrogen stream (50mL/min), with the maximum endothermic point being taken as the melting temperature (Tm).
In the following examples, the aforementioned α -diimine palladium complexes of the formulae 1 to 8 (as late transition metal catalysts) and sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate (NaBARF, as cocatalyst) were used in a molar ratio of 1: 2, respectively, as catalysts 1 to 8, respectively.
Synthesis examples 1 to 8: gas phase polymerization of ethylene using catalysts 1-8 to obtain ethylene homopolymers
In a glove box or fume hood, 10. mu. mol of the corresponding α -diimine palladium complex of formulae 1-8 (as late transition metal catalyst) and 20. mu. mol of sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate (NaBARF, as cocatalyst) were mixed in 2mL of dichloromethane in a narrow-neck flask and dissolved with sufficient stirring to give a catalyst solution.
The obtained catalyst solution was poured along the reactor wall into a dried 350mL glass thick-walled pressure reactor and uniformly coated on the reactor wall by gentle shaking, and a catalyst film layer was formed on the reactor wall after the methylene chloride solvent was volatilized.
The reactor having the catalyst membrane layer formed on the wall thereof was connected to an ethylene high pressure gas cylinder through a vacuum line, and after evacuating air, ethylene gas was loaded through a control valve on the line to maintain an ethylene pressure of 8atm in the reactor, followed by reaction at 25 ℃ for 12 hours. After the reaction was completed, the pressure reactor was vented to obtain a polyolefin polymer, and the results are shown in Table 1.
TABLE 1
aThe unit of activity is 104g/(mol Pd·h)；
bMnIs the number average molecular weight of the resulting ethylene homopolymer;
cPDI is the molecular weight distribution of the resulting ethylene homopolymer;
dbrs is the degree of branching of the resulting ethylene homopolymer, i.e. the number of methyl groups per 1000 methylene groups;
etm is the melting point of the ethylene homopolymer obtained;
fthe melting point of the polymer of synthesis example 1 was not measured (indicated as "-").
Synthesis examples 9 to 14: the gas-phase polymerization of ethylene at different reaction pressures, times and temperatures was examined using the same catalyst (i.e., catalyst 6)
The reaction procedure was the same as in Synthesis example 6 above except that the gas phase polymerization was carried out while changing the reaction pressure, time and temperature as shown in Table 2 below, and the desired ethylene homopolymer was obtained, the results of which are shown in Table 2.
TABLE 2
aThe unit of activity is 104g/(mol Pd·h)；
bMnIs the number average molecular weight of the resulting ethylene homopolymer;
cPDI is the molecular weight distribution of the resulting ethylene homopolymer;
dbrsthe degree of branching of the resulting ethylene homopolymer, i.e. the number of methyl groups per 1000 methylene groups;
eTmthe melting point of the resulting ethylene homopolymer;
comparative examples 1 to 7: synthesis of ethylene polymers by solution polymerization
For comparison, the above catalyst 6 was also used under the same conditions of reaction temperature (25 ℃ C.), time (4h) and pressure (8atm) as those of the above Synthesis example 10 except that the reaction process was a solution polymerization process in the presence of different solvents shown in the following Table 3, wherein the reaction process was substantially similar to that described above except that 50mL of the corresponding solvents (wherein the organic solvents used were each from Tianjin Fuyu Fine chemical Co., Ltd., purity was analytical purity) were used. This solution polymerization required quenching of the reaction by adding methanol and precipitation of the formed polymer using an excess of methanol, followed by filtration and vacuum drying at 45 ℃ for 36 hours to obtain the desired polymers as shown in table 3 (the reaction results of synthesis example 10 are listed for more visual comparison).
TABLE 3
aThe unit of activity is 104g/(mol Pd·h)；
bMnIs the number average molecular weight of the resulting ethylene homopolymer;
cPDI is the molecular weight distribution of the resulting ethylene homopolymer;
dbrsthe degree of branching of the resulting ethylene homopolymer, i.e. the number of methyl groups per 1000 methylene groups;
eTmthe melting point of the resulting ethylene homopolymer;
performance test examples 1 to 4
The ethylene polymers obtained in the foregoing Synthesis examples 5, 6, 7 and 13 were respectively subjected to melt-compression at 150 ℃ to obtain Test specimens (having dimensions of 12mm long x 2mm wide x 0.5mm thick), and then subjected to a tensile Test or a stress/strain Test at a rate of 10mm/min at room temperature by means of a Universal Test Machine (UTM 2502). Three samples were tested for each polymer and the results shown are the average.
The elastic recovery (SR) is a result measured after the test sample is stretched to an elongation length three times (i.e., 300%) as long as its original length and then restored to a stress zero state by applying an external force, and thus repeated ten times.
FIG. 1 shows the results of mechanical property tests of olefin polymers obtained by a gas phase polymerization method according to an example of the present invention, wherein (a) to (d) are elongation at break-stress graphs, and (e) to (h) are elastic recovery rate-stress graphs, and (a) and (e) are the test results of application example 5; (b) and (f) are test results of application example 6, (c) and (g) are test results of application example 13, and (d) and (h) are test results of application example 7.
Wherein the elongation at break is the ratio of the elongation length of the test sample at break to its initial length in a radial tensile test; the breaking stress is the maximum tensile force that can be borne on the test specimen in the radial tensile test; the elastic recovery (SR) is calculated according to the following formula:
in the formula Lo-the original length of the test sample without the application of an external force; l is1-the length of the test sample after elongation under the application of an external force; l is2-the length of the test sample after removal of the external force.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A gas phase polymerization process for the homogeneous polymerization of olefins catalyzed by a late transition metal catalyst, the gas phase polymerization process comprising:
dissolving a mixture of a late transition metal catalyst and a cocatalyst in a molar ratio of 1: 1-1: 3 in a volatile organic solvent to form a catalyst solution;
loading the obtained catalyst solution into a pressure reactor and uniformly coating the catalyst solution on the wall of the pressure reactor, thereby forming a catalyst membrane layer on the wall of the pressure reactor after the volatile organic solvent is volatilized; and
introducing olefin gas, and enabling the olefin to contact and react with the catalyst film layer under the reaction pressure of 1-10 atmospheric pressure and the reaction temperature of 20-80 ℃ so as to obtain the required olefin polymer,
wherein,
the late transition metal catalyst is an alpha-diimine palladium catalyst;
the cocatalyst is tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate.
2. The gas phase polymerization process of claim 1, wherein the molar ratio of the late transition metal catalyst to the cocatalyst is from 1: 1.5 to 1: 2.5.
3. The gas-phase polymerization process according to claim 1, wherein the alpha-diimine palladium-based catalyst is one or more of the following formulas 1 to 8:
wherein Me represents a methyl group and Ph represents a phenyl group.
4. The gas-phase polymerization process of claim 1, wherein the cocatalyst is sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate or potassium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate.
5. The gas-phase polymerization process of claim 1, wherein the olefin is a gaseous alpha-olefin.
6. The gas-phase polymerization process of claim 5, wherein the gaseous alpha-olefin is ethylene, propylene or 1-butene.
7. The gas-phase polymerization process of claim 5, wherein the gaseous alpha-olefin is ethylene.
8. The gas-phase polymerization process of claim 1, wherein the volatile organic solvent is dichloromethane or trichloromethane.
9. The gas-phase polymerization process according to claim 8, wherein 0.1 to 0.5mL of the volatile organic solvent is used based on 1. mu. mol of the late transition metal catalyst.
10. The gas-phase polymerization process according to claim 1, wherein the reaction time is 2 to 15 hours.
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