Method of using apparatus for polymerizing or devolatilizing composition

Abstract

To provide apparatuses for polymerizing or devolatilizing a composition with particularly high melt viscosity.SOLUTION: An apparatus 1 comprises: a first reaction vessel 10 defining a first interior chamber 20; and at least one circulation loop 60 external to the first reaction vessel and defining a passage channel 65. The first reaction vessel comprises: at least one first collar 30a providing access to the interior chamber; and at least one first probe assembly 40a supported by the first collar. The first probe assembly comprises an emitter for emitting light that polymerizes, crosslinks, or polymerizes and crosslinks the composition. The circulation loop comprises: a pump 70; at least one second collar 80 providing access to the passage channel; and at least one second probe assembly 90 supported by the second collar. The second probe assembly comprises an emitter 100 for emitting light that polymerizes, crosslinks, or polymerizes and crosslinks the composition.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] [CROSS REFERENCE TO RELATED APPLICATIONS] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 135,771, filed January 11, 2021, the entire disclosure of which is incorporated herein by reference.

[0002] FIELD OF THEINVENTION This invention relates generally to apparatus for polymerizing or devolatilizing compositions, particularly compositions of high melt viscosity, and methods of using such apparatus. [Background technology]

[0003] FIELD OF THEINVENTION This invention relates generally to apparatus for polymerizing or devolatilizing compositions, particularly compositions of high melt viscosity, and methods of using such apparatus.

[0004] In commercial production of materials such as polymers used in coatings, mastics, and adhesives, it can take hours or even days to convert starting materials, including, for example, monomers, initiators, and any solvents or vehicles, into the final reaction product. Any changes to the equipment or process steps that reduce the time of the process are desirable from a cost and time standpoint, allowing manufacturers to increase throughput in a given amount of time. It would be particularly beneficial if these cycle time reductions not only maintained but improved the quality of the materials.

[0005] If the polymer is in neat molten form, without a solvent or carrier, it can become highly viscous as molecular weight increases during production, making mixing of the reaction products difficult. Furthermore, the high viscosity of the polymer melt makes removal of residual volatiles, such as unreacted monomers, problematic. Thus, traditional means for reducing cycle times and removing unwanted volatile residues in solvent-based and emulsion-based polymerizations can be challenging in processes that result in high molecular weight polymers in neat molten form during both the polymerization and devolatilization stages.

[0006] The apparatus and method of the present invention are directed to these, as well as other important ends. Summary of the Invention

[0007] FIELD OF THEINVENTION This invention relates generally to an apparatus for polymerizing or devolatilizing compositions, particularly compositions of high melt viscosity, and methods of using such an apparatus.

[0008] In one aspect, the present invention is directed to an apparatus 1 for polymerizing or devolatilizing a composition. The apparatus comprises a first reaction vessel 10 defining a first internal chamber 20 and at least one circulation loop 60 external to the first reaction vessel and defining a passage channel 65. The first reaction vessel has at least one first collar 30 providing access to the internal chamber and at least one first probe assembly 40 supported by the first collar. The first probe assembly has an emitter 50 for emitting light that polymerizes, crosslinks, or polymerizes and crosslinks the composition. The circulation loop has a pump 70, at least one second collar 80 providing access to the passage channel, and at least one second probe assembly 90 supported by the second collar. The second probe assembly has an emitter 100 for emitting light that polymerizes, crosslinks, or polymerizes and crosslinks the composition.

[0009] In certain preferred aspects, the apparatus comprises any of the devices, for example a circulation loop, having at least one mixer 110, at least one injector 120 for entraining agent, a heat exchanger 130, and an analyzer 140.

[0010] In another aspect, the invention is directed to a method comprising the steps of forming a photopolymerizable reaction mixture in a reaction vessel, where the photopolymerizable reaction mixture has monomer, a first photoinitiator, and a second photoinitiator that is substantially non-photoreactive at an activation wavelength of the first photoinitiator, exposing the photopolymerizable reaction mixture to actinic radiation at at least one activation wavelength of the first photoinitiator to at least partially polymerize the monomer to form a molten composition in the reaction vessel, where the molten composition has a polymer melt and any unreacted monomer, and circulating at least a portion of the molten composition outside the reaction vessel.

[0011] The apparatus and method of the present invention utilize, among other things, a circulation loop with a subsurface (i.e., within the material reaction) light emitter that polymerizes, crosslinks, or polymerizes and crosslinks the composition. The circulation loop also promotes mixing from the top to the bottom of the first reaction vessel. The addition of an optional heat exchanger, particularly one located downstream of the light emitter in the circulation loop, helps to better maintain the temperature after the exiting stream (which is hotter due to the heat of polymerization) that passes under the surface of the light emitter. This temperature control supplements any jacket cooling used in the circulation loop. The addition of an optional entrainer injector in the circulation loop further improves the removal of unwanted volatile residues during devolatilization. Finally, the addition of an optional sensor in the circulation allows for better monitoring of the reaction and reaction products, especially if real-time, on-line or in-line analysis can be performed rather than off-line.

[0012] This summary is provided as a general introduction to some embodiments of the present invention and is not intended to be limiting. Additional exemplary embodiments, including variations and alternative configurations of the present invention, are provided herein. [Brief description of the drawings]

[0013] The accompanying drawings, which are included to provide a further understanding of the invention and which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention. As will be understood, the subject matter described herein is capable of other and different embodiments, and its several details can be modified in various respects, all without departing from the subject matter claimed. The drawings and description are therefore to be regarded as illustrative and not restrictive. In the drawings:

[0014] [Figure 1] 1 shows an apparatus of one embodiment of the present invention, with one reaction vessel shown.

[0015] [Diagram 2] 1 shows an apparatus of one embodiment of the present invention in which two reaction vessels are shown.

[0016] [Diagram 3] 1 shows an apparatus of one embodiment of the present invention in which a first plurality of probe assemblies are shown on top of a first reaction vessel.

[0017] [Figure 4] 1 illustrates an apparatus of one embodiment of the present invention, with a single probe assembly shown in the circulation loop.

[0018] [Figure 5A] 1 shows various views of an exemplary release device, which is one embodiment of a heat exchanger 130. [Figure 5B] 1 shows various views of an exemplary release device, which is one embodiment of a heat exchanger 130. [Figure 5C] 1 shows various views of an exemplary release device, which is one embodiment of a heat exchanger 130. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] [Definition] As used above, and throughout this disclosure, the following terms, unless otherwise indicated, shall be understood to have the following meanings:

[0020] As used herein, the terms "comprises," "comprises," "includes," "includes," "has," "having," or other variations thereof are intended to be open ended and cover a non-exclusive inclusion. For example, a process, method, article, or device that comprises a list of elements is not necessarily limited to only those elements, and may include other elements not expressly listed or inherent to such process, method, article, or device. Additionally, the use of "a" or "an" is used to describe elements and configurations described herein. This is merely for convenience and to give a general sense of the scope of the invention. As used herein, "one" or "at least one" should be read to include, and the singular also includes the plural, unless otherwise clear by context. As used herein, the term "about," when referring to measurable values ​​such as amounts, temporal durations, and the like, is meant to encompass a variation of ±10%, preferably ±8%, more preferably ±5%, even more preferably ±1%, and even more preferably ±0.1% from the stated value, as such variations are appropriate to implement the disclosed methods.

[0021] As used herein, "composition" means a material that is capable of undergoing a chemical reaction, such as polymerization, during the course of which the chemical structure may change, e.g., from an initial mixture of one or more monomers, an initiator, any medium or solvent, and any other additives, to a material having the polymerized residue of one or more monomers, and all intermediate stages in between.

[0022] "Collar" as used herein means a visual access point that is transparent to at least a particular wavelength of light. Suitable examples of collars as used in the context of the present invention include, but are not limited to, a port, a nozzle, or a side glass.

[0023] "Entraining agent" as used herein means a substance, usually a fluid, used to trap volatiles such as residual monomers and solvents and remove them, for example, when pressure is reduced in a vessel. Suitable examples of entraining agents include, but are not limited to, steam, condensed water, nitrogen, argon, or carbon dioxide, or mixtures thereof.

[0024] As used herein, "analyzer" refers to a device or system capable of making measurements of material flowing through a circulation loop. The analyzer may be capable of operating in-line or online. Suitable examples of analyzers include, but are not limited to, Fourier transform infrared spectrometers (FTIR), viscometers, refractometers, and the like.

[0025] As used herein, "actinic radiation" refers to light capable of producing chemical changes through radiant energy, particularly in the visible (wavelengths of about 380-750 nanometers) and ultraviolet (wavelengths of about 10-400 nm) portions of the spectrum.

[0026] [Device] In a first embodiment, the present invention is directed to an apparatus 1 for polymerizing or devolatilizing a composition. As shown with reference to FIG. 1, the apparatus comprises a first reaction vessel 10 defining a first internal chamber 20 and at least one circulation loop 60, external to the first reaction vessel and defining a passage channel 65. The first reaction vessel has at least one first collar 30a, 30b providing access to the internal chamber and at least one first probe assembly 40a, 40b supported by the first collar. The first probe assembly has an emitter 50 for emitting light that polymerizes, crosslinks, or polymerizes and crosslinks the composition. The circulation loop has a pump 70, at least one second collar 80 providing access to the passage channel, and at least one second probe assembly 90 supported by the second collar. The second probe assembly has an emitter 100 for emitting light that polymerizes, crosslinks, or polymerizes and crosslinks the composition.

[0027] In a particular embodiment of the apparatus, the circulation loop further comprises a mixer 110 .

[0028] In a particular embodiment of the apparatus, the circulation loop further comprises an injector 120 for at least one entraining agent. In a particular embodiment, the entraining agent is a material selected from steam, condensed water, nitrogen, argon, or carbon dioxide, or mixtures thereof. Steam is preferred.

[0029] In certain embodiments of the apparatus, the circulation loop further comprises a heat exchanger 130. In certain embodiments, the heat exchanger is a release device 500, such as the device shown in Figures 5A, 5B, and 5C. In Figures 5A, 5B, and 5C, a nozzle 510 is the inlet and can be connected to an external circulation loop 60. A bottom flange 520 can be attached directly to the top of the reactor 10. Figure 5A is a side view of the release device with the release device lid 530 attached to the body / vessel (not shown). The hatched area indicates the heat transfer fluid. Figure 5B is another side view (rotated 90°) of the release device with the lid removed, showing that the outer shell of the body is covered. Figure 5C is a bottom view of the body 540 of the release / heat exchanger vessel.

[0030] In certain embodiments of the apparatus, the circulation loop further comprises an analyzer 140. In certain embodiments, the analyzer is at least one device selected from the group consisting of a Fourier transform infrared spectrometer, a viscometer (such as a rotating cylinder or dynamic mechanical spectrometer), and a refractometer.

[0031] In a particular embodiment of the device, the circulation loop further comprises a filter 125, in particular a particulate filter.

[0032] In a particular embodiment of the apparatus shown with reference to FIG. 3, the first probe assembly further comprises light tubes 314A, 314B, 314C extending from emitters 312A, 312B, 312C and positioned at least partially within the internal chamber of the reaction vessel, adjustable positioning devices 316A, 316B, 316C for controlling the position of the light tubes within the internal chamber of the first reaction vessel, and covers 317A, 317B, 317C positioned at distal ends 315A, 315, 315C of the light tubes and transparent or substantially transparent to the passage of light emitted from the emitters.

[0033] In the particular embodiment of the device shown with reference to Figure 4, the second probe assembly 310D disposed in the circulation loop further includes a light pipe 314D extending from the emitter towards the passage channel 60. A collar 330D is also shown.

[0034] In a particular embodiment of the apparatus, the pump is a gear pump, preferably located below the first reaction vessel.

[0035] In certain embodiments of the present apparatus, the first reaction vessel further comprises at least one agitator 190.

[0036] In certain embodiments, the apparatus further comprises at least one condenser 200 and a return line 210 to the first reaction vessel 1. In other embodiments, the apparatus also further comprises at least one condensate storage tank 220 and an optional secondary storage tank 225 between the condenser and the return line. The first inner chamber 20 is connected to the condenser 200 via line 205.

[0037] In certain embodiments, the light is actinic radiation.

[0038] In certain embodiments, the apparatus further comprises at least one supply line 230 for the constituents of the composition (monomer 230a and initiator 230b), the at least one supply line being connected to the first internal chamber.

[0039] In the particular embodiment shown with reference to FIG. 2, the apparatus 2 further comprises a second reaction vessel 240 defining a second internal chamber 250 and at least one passageway 260 between the second reaction vessel and the first reaction vessel.

[0040] In certain embodiments, the first and second probe assemblies are positionable at least one location selected from the group consisting of a surface location, an angled surface location, a subsurface location, and an angled subsurface location. In certain embodiments, the device comprises a single first or second probe assembly. In certain other embodiments, the device comprises a plurality of first or second probe assemblies.

[0041] In certain embodiments, the first collar and the at least one first probe assembly are disposed along a top wall of the first reaction vessel. In certain other embodiments, the first collar and the at least one first probe assembly are disposed along a side wall of the reaction vessel. In certain other embodiments, the first collar and the at least one first probe assembly are disposed along a bottom wall of the reaction vessel.

[0042] In certain embodiments, the first and second reaction vessels further comprise a mixing device or mixer.

[0043] In one embodiment, the present invention is directed to an apparatus for polymerizing and / or crosslinking an adhesive or pre-adhesive composition, the apparatus comprising: a first reaction vessel defining a first internal chamber; a circulation loop having at least one sight glass installed therein and providing visual access to a passage channel; at least one sight glass installed in a wall of the first reaction vessel and providing visual access to the first internal chamber; and at least one probe assembly adjacent to each of the sight glasses, wherein each probe assembly has an emitter for emitting light for polymerizing and / or crosslinking the composition, the probe assemblies being positioned such that light emitted from the emitter is directed to the sight glass and passed into the first internal chamber or passage channel of the reaction vessel, the sight glass being transparent or substantially transparent to the passage of light emitted from the associated emitter.

[0044] In certain embodiments, the probe assembly further comprises a light pipe disposed between the sight glass and the emitter. The sight glass may be disposed along a top wall, a side wall, and / or a bottom wall of the first reaction vessel.

[0045] In certain embodiments, the present invention is directed to an apparatus for polymerizing and / or crosslinking an adhesive or pre-adhesive composition, the apparatus comprising a first reaction vessel defining a first internal chamber and at least one baffle disposed within the first internal chamber of the reaction vessel. The vessel has a mixing device having at least one blade. The baffle has at least one emitter for emitting light to polymerize and / or crosslink the composition. The baffle may be a unidirectional light emitting baffle having a single face that emits light. The baffle may be oriented within the first internal chamber such that upon operation of the mixing device or mixer, at least one blade moves toward the single face of the baffle that emits light. An optional second reaction vessel may also include the same or a different mixing device or mixer.

[0046] [method] In certain embodiments, the invention is directed to a method comprising the steps of forming a photopolymerizable reaction mixture in a reaction vessel, where the photopolymerizable reaction mixture has monomer, a first photoinitiator, and a second photoinitiator that is substantially non-photoreactive at an activation wavelength of the first photoinitiator; exposing the photopolymerizable reaction mixture to actinic radiation at at least one activation wavelength of the first photoinitiator to at least partially polymerize the monomer to form a molten composition in the reaction vessel, where the molten composition has a polymer melt and any unreacted monomer; and circulating at least a portion of the molten composition outside the reaction vessel.

[0047] In certain embodiments, the method further comprises mixing the molten composition with an entraining agent to form a conversion mixture having the polymer melt, any unreacted monomer, and the entraining agent.

[0048] In certain embodiments, the method further comprises irradiating the molten composition with actinic radiation at at least one activation wavelength of the first photoinitiator to polymerize unreacted monomers to form an irradiation conversion mixture.

[0049] In certain embodiments, the method further comprises the steps of mixing the melt composition with an entraining agent to form a conversion mixture having a polymer melt, unreacted monomer, and the entraining agent, and irradiating the conversion mixture with actinic radiation at at least one activation wavelength of the first photoinitiator to polymerize the unreacted monomer to form an irradiated conversion mixture.

[0050] In certain embodiments, the method further comprises removing heat from the polymer melt.

[0051] In certain embodiments, the method further comprises inspecting the polymer melt, such as by using a technique selected from the group consisting of Fourier transform infrared spectroscopy, rheology, and refractive index measurements.

[0052] In certain embodiments, the method further comprises distilling the unreacted monomer and the entraining agent in separate vessels.

[0053] Further details of certain features of the apparatus and method of the present invention are known from US-A-5,772,851 and US-A1-2017 / 0240783, which are incorporated herein in their entirety.

[0054] When ranges for physical properties, such as molecular weight, or chemical properties, such as chemical formula, are used herein, all combinations and subcombinations of ranges of specific embodiments therein are intended to be included.

[0055] The disclosures of each patent, patent application, and publication cited or described in this specification are hereby incorporated by reference in their entirety.

[0056] Those skilled in the art will recognize that numerous changes and modifications can be made to the preferred embodiments of the present invention and that such changes and modifications can be made without departing from the true spirit of the invention, and it is therefore intended that the appended claims will cover all such equivalent variations that fall within the true spirit and scope of the invention.

Claims

1. An apparatus (1) for polymerizing or devolatilizing a composition, the apparatus comprising: A first reaction vessel (10) defining a first internal chamber (20), said first reaction vessel comprising: at least one first collar (30) providing access to said interior chamber; at least one first probe assembly (40) supported by the first collar; the first probe assembly having the first reaction vessel (10) having an emitter (50) for emitting light that polymerizes, crosslinks, or polymerizes and crosslinks the composition; At least one circulation loop (60) external to the first reaction vessel and defining a passage channel, the circulation loop comprising: A pump (70); at least one second collar (80) providing access to said passage channel; at least one second probe assembly (90) supported by said second collar; the second probe assembly having and said circulation loop (60) having an emitter (100) for emitting light that polymerizes, crosslinks, or polymerizes and crosslinks said composition.

2. The circulation loop further comprises a mixer (110).

2. The apparatus of claim 1.

3. The circulation loop further comprises an injector (120) for at least one entraining agent.

3. Apparatus according to claim 1 or 2.

4. The entraining agent is a material selected from steam, condensed water, nitrogen, argon, or carbon dioxide, or mixtures thereof; An apparatus according to any one of claims 1 to 3.

5. The circulation loop further comprises a heat exchanger (130). An apparatus according to any one of claims 1 to 4.

6. The circulation loop further comprises an analyzer (140). An apparatus according to any one of claims 1 to 5.

7. The analyzer is at least one device selected from the group consisting of a Fourier transform infrared spectrometer, a viscometer, and a refractometer. An apparatus according to any one of claims 1 to 6.

8. The first probe assembly (310A, 310B, 310C) a light tube (314A, 314B, 314C) extending from the emitter (312A, 312B, 312C) and disposed at least partially within the interior chamber of the reaction vessel; an adjustable positioning device (316A, 316B, 316C) for controlling the position of the light tube within the inner chamber of the first reaction vessel; a cover (317A, 317B, 317C) disposed on the distal end (315A, 315B, 315C) of the light pipe, the cover being transparent or substantially transparent to the passage of light emitted from the emitter; The apparatus of claim 1 further comprising:

9. The second probe assembly (90) further comprises a light pipe (314D) extending from the emitter toward the passage channel (65). An apparatus according to any one of claims 1 to 8.

10. The pump is a gear pump and is disposed below the first reaction vessel. An apparatus according to any one of claims 1 to 9.

11. The first reaction vessel further comprises at least one agitator (190). An apparatus according to any one of claims 1 to 10.

12. At least one condenser (200); a return line (210) to the first reactor; The apparatus of any one of claims 1 to 11, further comprising:

13. At least one condensate storage tank (220) between the condenser and the return line. The apparatus of claim 12 further comprising:

14. the light is actinic radiation; Apparatus according to any one of claims 1 to 13.

15. The apparatus further comprises at least one supply line (230) for the constituents of the composition, the at least one supply line is connected to the first internal chamber; Apparatus according to any one of claims 1 to 14.

16. a second reaction vessel (240) defining a second interior chamber (250); at least one passageway (260) between said second reaction vessel and said first reaction vessel; The apparatus of any one of claims 1 to 15, further comprising:

17. 1. A method, comprising: forming a photopolymerizable reaction mixture in a reaction vessel; wherein the photopolymerizable reaction mixture comprises A monomer, A first photopolymerization initiator; a second photoinitiator that is substantially non-photoreactive at the activation wavelength of the first photoinitiator; It has exposing the photopolymerizable reaction mixture to actinic radiation at at least one activation wavelength of the first photoinitiator to at least partially polymerize the monomers to form a molten composition in the reaction vessel; wherein the molten composition comprises a polymer melt and any unreacted monomers; circulating at least a portion of the molten composition outside of the reaction vessel; A method comprising the steps of:

18. mixing the melt composition with the entraining agent to form a conversion mixture having the polymer melt, any unreacted monomer, and the entraining agent; 20. The method of claim 17, further comprising:

19. exposing the molten composition to actinic radiation at at least one activation wavelength of the first photoinitiator to polymerize the unreacted monomers to form an irradiation conversion mixture; 19. The method of claim 17 or 18, further comprising:

20. mixing the melt composition with the entraining agent to form a conversion mixture having the polymer melt, the unreacted monomer, and the entraining agent; exposing the molten composition to actinic radiation at at least one activation wavelength of the first photoinitiator to polymerize the unreacted monomers to form an irradiation conversion mixture; The method of any one of claims 17 to 19, further comprising:

21. removing heat from the polymer melt; The method of any one of claims 17 to 20, further comprising:

22. inspecting the polymer melt; The method of any one of claims 17 to 21, further comprising:

23. The inspection is a technique selected from the group consisting of Fourier transform infrared spectroscopy, rheology, and refractive index measurement.

23. The method of claim 22.

24. distilling the unreacted monomer and the entraining agent into separate vessels; The method of any one of claims 17 to 23, further comprising:

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