阅读说明：本技术 包含官能化颗粒的聚合物基质复合材料及其制备方法 (Polymer matrix composites comprising functionalized particles and methods of making the same ) 是由 杰拉尔德·K·拉斯穆森 德里克·J·德纳 小克林顿·P·沃勒 巴拉特·R·阿查理雅 萨蒂德尔 于 2018-11-15 设计创作，主要内容包括：本发明提供了一种聚合物基质复合材料,所述聚合物基质复合材料包含多孔聚合物网络；以及分布在所述聚合物网络结构内的多个官能化颗粒,并且其中通过“气流阻力测试”所测量,所述聚合物基质复合材料在25℃下的气流阻力小于300秒/50cm<Sup>3</Sup>/500微米；并且其中所述聚合物基质复合材料具有至少0.3g/cm<Sup>3</Sup>的密度；及其制备方法。所述聚合物基质复合材料可用作例如过滤器。(The present invention provides a polymer matrix composite comprising a porous polymer network; and a plurality of functionalized particles distributed within the polymer network structure, and wherein the polymer matrix composite has an airflow resistance of less than 300 seconds/50 cm at 25 ℃ as measured by the airflow resistance test 3 500 μm; and wherein the polymer matrix composite has at least 0.3g/cm 3 (ii) a density of (d); and a method for preparing the same. The polymer matrix composite may be used, for example, as a filter.)

1. A polymer matrix composite, the polymer matrix composite comprising:

a porous polymer network; and

a plurality of functionalized particles distributed within the polymer network structure,

wherein the polymer matrix composite has an airflow resistance of less than 300 seconds/50 cm at 25 ℃ as measured by the airflow resistance test³500 μm.

2. The polymer matrix composite according to claim 1, wherein the functionalized particles are present in a range from 1 wt% to 99 wt%, based on the total weight of the functionalized particles and the polymer.

3. The polymer matrix composite according to any preceding claim, wherein the polymer matrix composite has at least 0.1g/cm³The density of (c).

4. The polymer matrix composite according to any preceding claim, wherein the polymer matrix composite has a porosity of less than 90%.

5. The polymer matrix composite according to any preceding claim, wherein the functionalized particles comprise at least one functional group capable of providing the particles with at least one of an absorbing function, an adsorbing function, a complexing function, a catalyzing function, a separating function, or a reagent function.

6. The polymer matrix composite according to any preceding claim, wherein the functionalized particles have an average particle size in a range from 0.1 microns to 5000 microns.

7. The polymer matrix composite according to any preceding claim, wherein the porous polymer network structure comprises at least one of: polyurethanes, polyesters, polyamides, polyethers, polycarbonates, polyimides, polysulfones, polyether sulfones, polyphenylene oxides, polyacrylates, polymethacrylates, polyacrylonitriles, polyolefins, styrene or styrene-based random and block copolymers, chlorinated polymers, fluorinated polymers or copolymers of ethylene and chlorotrifluoroethylene.

8. The polymer matrix composite according to any preceding claim wherein the porous polymer network structure comprises a plurality of interconnected morphologies that are phase separated.

9. The polymer matrix composite according to any preceding claim, wherein the porous polymer network structure comprises a number average molecular weight of 5 × 10⁴g/mol to 1 × 10⁷A polymer in the g/mol range, and wherein the polymer matrix composite is in the form of a layer having a thickness in the range of 50 microns to 7000 microns.

10. The polymer matrix composite according to any preceding claim, wherein the polymer matrix composite has a bubble point pressure of at least 0.5 psi.

11. A method of making the polymer matrix composite of any preceding claim, the method comprising:

combining a thermoplastic polymer, a solvent, and a plurality of functionalized particles to provide a slurry;

forming the slurry into an article;

heating the article in an environment to retain at least 90 wt% of the solvent in the article based on the weight of the solvent in the article and to dissolve at least 50 wt% of the thermoplastic polymer based on the total weight of the thermoplastic polymer; and

inducing phase separation of the thermoplastic polymer from the solvent to provide the polymer matrix composite.

12. The method of claim 11, further comprising removing at least a portion of the solvent from the shaped article after inducing phase separation of the thermoplastic polymer from the solvent.

13. The method of claim 12, wherein no solvent is removed from the shaped article.

14. The method of any one of claims 11 to 13, wherein inducing phase separation comprises thermally inducing phase separation.

15. The method of any one of claims 11 to 14, wherein the polymer in the slurry has a melting point, wherein the solvent has a boiling point, and wherein combining is performed below the melting point of the polymer in the slurry and below the boiling point of the solvent.

16. The method of any one of claims 11 to 15, wherein the polymer in the slurry has a melting point, and wherein inducing phase separation is performed below the melting point of the polymer in the slurry.

17. The method of any one of claims 11-16, further comprising at least one of stretching or compressing the polymer matrix composite.

18. The method of any one of claims 11 to 16, further comprising applying vibrational energy to the polymer matrix composite while applying the compressive force.

19. A method of making the polymer matrix composite according to any one of claims 1 to 10, the method comprising:

combining a thermoplastic polymer, a solvent for the thermoplastic polymer to be soluble therein, and a plurality of functionalized particles to form a suspension of functionalized particles in a miscible thermoplastic polymer-solvent solution;

inducing phase separation of the thermoplastic polymer from the solvent; and

removing at least a portion of the solvent to provide the polymer matrix composite.

20. The method of claim 19, wherein inducing phase separation comprises at least one of thermally induced phase separation or solvent induced phase separation.

21. The method of claim 20 wherein the polymer in the miscible thermoplastic polymer-solvent solution has a melting point, wherein the solvent has a boiling point, and wherein combining is conducted above the melting point of the miscible thermoplastic polymer-solvent solution and below the boiling point of the solvent.

22. The method of any one of claims 19 to 21, wherein the polymer in the miscible thermoplastic polymer-solvent solution has a melting point, and wherein inducing phase separation is performed below the melting point of the polymer in the miscible thermoplastic polymer-solvent solution.

23. The method of any one of claims 19-22, further comprising at least one of stretching or compressing the polymer matrix composite.

24. The method of any one of claims 19 to 22, further comprising applying vibrational energy to the polymer matrix composite while applying the compressive force.

25. A filter comprising the polymer matrix composite according to any one of claims 1 to 10.

Background

Chromatography resins are widely used in the biotechnology industry for the large-scale isolation and/or purification of various biomolecules, such as proteins, enzymes, vaccines, DNA and RNA. Column chromatography using high flow rates for purification is limited by particle size and stringent particle packing techniques to prevent bed cracking and contamination bypass. If the average size of the chromatographic resin particles is less than about 40 microns, the back pressure in the particle-filled chromatography column may become unacceptably large, especially for large columns that may be used for purification or separation of large biomolecules. While the average particle size can be as large as 2000 microns, typical average particle sizes are no greater than 200 microns. If the average particle size is greater than about 200 microns, the efficiency of the chromatographic process may be low, especially for purifying or separating large biological macromolecules (e.g., proteins) that typically have a low diffusion rate to the pores of the resin. For example, to obtain the same degree of separation or purification with larger resins as can be obtained using 40 to 200 micron resins, a greater amount of resin, a longer chromatography column, a slower flow rate, or a combination thereof may be required.

Disclosure of Invention

In one aspect, the present disclosure describes a polymer matrix composite comprising:

a porous polymer network structure; and

a plurality of functionalized particles distributed within the polymer network structure,

wherein the polymer matrix composite has an airflow resistance at 25 ℃ of less than 300 seconds/50 cm as measured by the "airflow resistance test" described in the examples³500 micron (in some embodiments, less than 250 seconds/50 cm)³500 micron, 200 second/50 cm³500 micron, 100 second/50 cm³500 micron, 50 second/50 cm³500 micron, 25 second/50 cm³500 micron, 20 second/50 cm³500 micron, 15 second/50 cm³500 micron, 10 second/50 cm³500 micron or even less than 5 seconds/50 cm³500 μm). As used herein, "functionalized particles" refers to particles comprising at least one functional group G capable of providing at least one of an adsorption function, a complexation function, a catalysis function, a separation function, or a reagent function to the particle.

In another aspect, the present disclosure describes a first method of making a polymer matrix composite described herein, the method comprising:

combining (e.g., mixing or blending) a thermoplastic polymer, a solvent, and a plurality of functionalized particles to provide a slurry;

shaping the slurry into an article (e.g., a layer);

heating the article in an environment to retain in the article at least 90% (in some embodiments, at least 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or even at least 99.5%) by weight of the solvent based on the weight of the solvent in the article, and to dissolve at least 50% (in some embodiments, at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, or even 100%) by weight of the thermoplastic polymer based on the total weight of the thermoplastic polymer; and

inducing phase separation of the thermoplastic polymer from the solvent to provide the polymer matrix composite.

In another aspect, the present disclosure describes a second method of making a polymer matrix composite described herein, the method comprising:

combining (e.g., mixing or blending) a thermoplastic polymer, a solvent for the thermoplastic polymer, and a plurality of functionalized particles to form a suspension of functionalized particles in a miscible thermoplastic polymer-solvent solution;

inducing phase separation of the thermoplastic polymer from the solvent; and

removing at least a portion of the solvent to provide the polymer matrix composite.

As used herein, "miscible" refers to the ability of substances to mix in all proportions (i.e., to completely dissolve in each other at any concentration) to form a solution, where for certain solvent-polymer systems, heat may be required to make the polymer miscible with the solvent. Conversely, if a large portion does not form a solution, the substances are immiscible. For example, butanone is significantly soluble in water, but the two solvents are immiscible because they do not dissolve in all proportions.

As used herein, "phase separation" refers to a process in which particles are uniformly dispersed in a homogeneous polymer-solvent solution that is transformed (e.g., by a change in temperature or solvent concentration) into a continuous three-dimensional polymer matrix composite. In the first method, the desired article is formed before the polymer becomes miscible with the solvent, and phase separation is a Thermally Induced Phase Separation (TIPS) method. In the second method, the polymer may be miscible with the solvent prior to forming the desired article. In the second method, phase separation is achieved by a Solvent Induced Phase Separation (SIPS) or thermally induced phase separation method using a wet or dry method.

In the SIPS wet process, the solvent dissolving the polymer is exchanged with a non-solvent to induce phase separation. The new exchange solvent in the system becomes the pore former for the polymer. In the SIPS dry method, a solvent dissolving a polymer is evaporated to induce phase separation. In the dry method, a non-solvent is also dissolved in the solution by the solvent that dissolves the polymer. This non-solvent for the polymer becomes a pore former for the polymer as the dissolution solvent evaporates. Since no additional exchange liquid is used, the process is considered to be "dry". Non-solvents are also generally volatile, but have a boiling point at least 30 ℃ lower than the solvent.

In the TIPS process, an elevated temperature is used to turn the non-solvent into a solvent for the polymer, and then the temperature is reduced to return the solvent to the non-solvent for the polymer. Effectively, when sufficient heat is removed, the hot solvent becomes a pore former and loses solvating power. The solvent used in the thermal phase separation process may be volatile or non-volatile.

Unexpectedly, in the first method of making a polymer matrix composite, the relatively high particle loading allows for the preparation of a slurry formable into a layer that retains its form when the solvent is heated to remain miscible with the polymer. The solvents used are generally volatile and are subsequently evaporated. In the second method of preparing polymer matrix composites using the TIPS process, the solvent used is generally non-volatile. In the second method of preparing a polymer matrix composite by the wet or dry SIPS method, the solvent is generally non-volatile for the wet method and volatile for the dry method.

Typically, the maximum particle loading that can be achieved in conventional particle-filled composites (e.g., dense polymer films and binders) is no greater than about 40 to 60 volume percent, based on the volume of the particles and binder. Incorporation of greater than 6 volume percent of particles into conventional particle-filled composites is generally not achievable because such high particle loading materials cannot be processed via coating or extrusion processes and/or the resulting composites become very brittle. Conventional composites also typically completely encapsulate the particles with a binder, thereby preventing access to the particle surface and minimizing potential particle-to-particle contact. Surprisingly, the high content of solvent and phase separated morphology obtained with the process described herein enables relatively high particle loadings to be achieved with relatively low amounts of high molecular weight binder. The high particle loading also helps to minimize the formation of a thin non-porous polymer layer that may form during phase separation. In addition, the polymer matrix composites described herein are relatively flexible and tend not to shed particles. While not wanting to be limited by theory, it is believed that another advantage of the embodiments of the polymer matrix composites described herein is that the particles are completely coated with the binder, thereby enabling a high degree of particle surface contact without masking due to the porous nature of the binder. The porous nature of the composite matrix allows for hydrodynamic flow or rapid diffusion through the interstitial pores of the particles. Slower diffusive transport typically occurs through the smaller pores of the porous particulate media. Retaining the high open surface area of the particles reduces the slow diffusion transport effect and thereby helps to provide high separation and separation capacity, as is typically present in depth filter media. Even at elevated temperatures (e.g., 135 ℃), high molecular weight binders do not flow readily in the absence of solvents, making steam sterilization possible.

The polymer matrix composites described herein can be used, for example, as filters or purification devices (e.g., absorbents, complexing agents, enzymes, or other protein-bearing supports) or chromatography articles. The polymer matrix composites described herein may be reusable or disposable, depending on the particular application.

In some embodiments, the polymer matrix composites described herein can be used to address the deficiencies of conventional column chromatography with limited practical particle size options. In some embodiments, the polymer matrix composites described herein can provide relatively high particle volumes, as well as relatively large surface areas to which the functionalized particles reach. Such polymer matrix composites may be, for example, in the form of one or more layers or in monolithic form, thereby avoiding the inherent problems of using particles in packed bed chromatography columns.

Drawings

Fig. 1 is a schematic illustration of an exemplary polymer matrix composite material described herein.

Fig. 2 is a schematic illustration of another exemplary polymer matrix composite described herein.

Fig. 3 is a schematic illustration of another exemplary polymer matrix composite described herein.

Fig. 4A and 4B show Scanning Electron Microscope (SEM) micrographs of a cross section of an exemplary polymer matrix composite (example 1) described herein.

Fig. 5A and 5B show Scanning Electron Microscope (SEM) micrographs of a cross section of an exemplary polymer matrix composite (example 2) described herein.

Fig. 6 shows a Scanning Electron Microscope (SEM) micrograph of a cross-section of an exemplary polymer matrix composite (example 3) described herein.

Fig. 7 shows a Scanning Electron Microscope (SEM) micrograph of a cross-section of an exemplary polymer matrix composite (example 4) described herein.

Detailed Description

In some embodiments, the functionalized particles are present in a range of from 1 to 99 wt.% (in some embodiments, in a range of from 5 to 99 wt.%, 10 to 99 wt.%, 5 to 98 wt.%, 10 to 98 wt.%, 25 to 98 wt.%, 50 to 98 wt.%, 60 to 98 wt.%, 70 to 98 wt.%, 80 to 98 wt.%, 90 to 98 wt.%, 93 to 98 wt.%, or even 95 to 98 wt.%) based on the total weight of the functionalized particles and the polymer (excluding any solvent).

The functionalized particles are capable of interacting with target species present within the fluid or gas with which they are contacted by virtue of the presence of one or more functional groups G. The particles may be organic or inorganic, porous or non-porous, and spherical or non-spherical, or one or more combinations thereof, depending on the intended end use "function" of the particle. The particles are typically polymeric, but need not be (e.g., they may be metal or glass). The one or more functional groups G may be attached directly to the particle surface, or may be attached to a linking group, which in turn is attached to the particle. One or more groups G may be incorporated into the particle during its synthesis or may be attached to the particle after its preparation by a variety of methods well known in the art.

Exemplary functionalized particles include chromatographic particles (e.g., those useful for purifying Chemical or biological species) exemplary chromatographic particles include organic and inorganic particles comprising functional groups useful for ion exchange, affinity, reverse phase, normal phase, size exclusion, multimodal, hydrophobic interaction, metal affinity, metal chelate, and chiral separation, e.g., exemplary functionalized particles (including chromatographic particles) are available from biorad, Hercules, CA, of hel, california (e.g., under the trade designations "unoppo hehale", "affiege L", "AFFI-PREP", "ro-PREP", "CFT", and "CHT"), general electric medical group of Pittsburgh, PA (e.g., under the trade designations "CAPTO", "hittra 2", "bse 2, phsche 2, phsey, p, and p, such as" nethery ", n, r 5, r, inc (e.g., trade designations" kohlik, p, inc., wo 587, p, inc., mercy, p., mercy, inc., mercy, p., mercy, inc., mercy, p., mercy, inc., mercy, p., mercy, inc., mercy, p., mercy, inc., mercy, p., mercy, inc., p., mercy, inc., p., mercy, inc., p.

Chromatographic particles can also be prepared by techniques known in the art (see, e.g., U.S. Pat. No. 5,292,840(Heilmann et al), 6,379,952(Rasmussen et al), 7,674,835(Rasmussen et al), 7,674,836(Rasmussen et al), 8,367,198(Wickert et al), 8,592,493(Shannon et al), 8,710,111(Wickert et al), 9,018,267(Shannon et al), and 9,056,316 (L awson et al), the disclosures of which are incorporated herein by reference.) exemplary functionalized particles also include directly covalently reactive particles (see, e.g., U.S. Pat. No. 5,993,935(Rasmussen et al), the disclosure of which is incorporated herein by reference).

Exemplary functionalized particles also include water-retaining zwitterionic gel electrolyte functionalized particles useful in antifouling applications. The functionalized particles can be grafted with both positively and negatively charged species to form a polyelectrolyte analyte.

Exemplary functionalized particles also include high surface area catalytic particles characterized by deposited nanogold catalysts. Deposited on high surface area TiO₂The nanogold on the particles catalyzes carbon monoxide to carbon dioxide, hydrogen to water, and formaldehyde to carbon dioxide and water.

Exemplary functionalized particles also include low surface area catalytic particles characterized by a deposited nanogold catalyst that will preferentially oxidize carbon monoxide to carbon dioxide. Such selective reactions can be used where it is desired to oxidize CO but not H₂For example, for fuel cells (see, for example, U.S. patent 8,314,046(Brady et al) and 7,955,570 (insey et al), the disclosures of which are incorporated herein by reference).

Exemplary functionalized particles also include nanosilver or nanosilver coated particles that will have antimicrobial properties. They may also act as indicators by blackening in the presence of hydrogen sulfide.

Useful guanidine-functionalized particles include those prepared from guanidine-functionalized silanes (see, e.g., U.S. Pat. No. 9,657,038(Griesgraber et al), U.S. Pat. publication No. 2018/0038862(Kshirsagar et al), and PCT publication No. 2016/149233 published 9/22 of 2016 and those prepared by crosslinking guanidine-functionalized polyethyleneimine G-PEI (see, e.g., U.S. Pat. publication No. 2017/0049926 (L anger-Anderson et al)), the disclosures of which are incorporated herein by reference.

In those embodiments where the functionalized particles are porous, it may be advantageous to use particles having an average particle size in the size range of 1 micron to 20 microns, as this tends to reduce the residence time required for the target species to diffuse into contact with functional group G.

Exemplary sizes of functionalized particles range from hundreds of nanometers to hundreds of micrometers in size. Exemplary shapes of the functionalized particles include irregular, platy, acicular, and spherical shapes, as well as agglomerated forms. The size of the agglomerates may range, for example, from a few micrometers up to and including a few millimeters.

In some embodiments, the functionalized particles have an average particle size (average length of longest dimension) in the range of 0.1 to 5000 microns (in some embodiments, in the range of 1 to 500 microns, 1 to 120 microns, 40 to 200 microns, or even 5 to 60 microns).

In some embodiments, the functionalized particles comprise first and second functionalized particles that differ (i.e., differ by hydrophobic interactions or cations or anions or affinities), thereby forming a mixed mode separation medium. In some embodiments, the first functionalized particle comprises a coating or particle derived from an amino (meth) acrylate monomer or derivative thereof, and the second functionalized particle comprises a hydrophobic functional group present in the amino acids tryptophan, phenylalanine, and leucine. In some embodiments, the first functionalized particles comprise anion exchange particles and the second functionalized particles comprise cation exchange particles. In some embodiments, mixed mode functional groups may be coated or polymerized on the same particle. In some embodiments, ionic monomers comprising a weak base, a strong base, a weak base salt, a strong base salt, or a combination thereof may be used in the preparation of the ion exchange particles. Mixed mode media can sometimes provide increased retention or separation capabilities for target species as compared to media having only one mode of interaction. Sometimes more than one different functionalized particle may be used to interact with two or more different target species simultaneously.

In some embodiments, the first functionalized particles have an average particle size (average length of the longest dimension) in a range from 0.1 micron to 5000 microns (in some embodiments, in a range from 1 micron to 500 microns, 1 micron to 120 microns, 40 microns to 200 microns, or even 5 microns to 60 microns), and the second functionalized particles have an average particle size (average length of the longest dimension) in a range from 0.1 microns to 5000 microns (in some embodiments, in a range from 1 micron to 500 microns, 1 micron to 120 microns, 40 microns to 200 microns, or even 5 microns to 60 microns).

In some embodiments, the first functionalized particles are present in a range of from 1 wt% to 99 wt% (in some embodiments, in a range of from 5 wt% to 99 wt%, 10 wt% to 99 wt%, 5 wt% to 98 wt%, 10 wt% to 98 wt%, 25 wt% to 98 wt%, 50 wt% to 98 wt%, 60 wt% to 98 wt%, 70 wt% to 98 wt%, 80 wt% to 98 wt%, 90 wt% to 98 wt%, 93 wt% to 98 wt%, or even 95 wt% to 98 wt%), and the second functionalized particles are present in a range of from 1 wt% to 99 wt% (in some embodiments, in a range of from 5 wt% to 99 wt%, 10 wt% to 99 wt%, 5 wt% to 98 wt%, or even 95 wt% to 98 wt%), based on the total weight of the first functionalized particles and the second functionalized particles, In the range of 10 to 98 wt.%, 25 to 98 wt.%, 50 to 98 wt.%, 60 to 98 wt.%, 70 to 98 wt.%, 80 to 98 wt.%, 90 to 98 wt.%, 93 to 98 wt.%, or even 95 to 98 wt.%).

In some embodiments, the polymer matrix composites described herein further comprise non-functionalized particles (i.e., are not functionalized particles). in some embodiments, the non-functionalized particles comprise polyamide particles (e.g., available under the trade designation "ORGASO L" from Arkema, inc., King of Prussia, PA) to serve as spacers to prevent pore collapse of particles sensitive to hydrocarbon diluents or heat required to dissolve the polymeric binder due to a heating or drying step.

In some embodiments, the non-functionalized particles have an average particle size (average length of longest dimension) in the range of 0.1 to 5000 micrometers (in some embodiments, in the range of 1 to 500 micrometers, 1 to 120 micrometers, 40 to 200 micrometers, or even 5 to 60 micrometers).

In some embodiments, the non-functionalized particles are present in a range of from 1 wt% to 99 wt% (in some embodiments, in a range of from 5 wt% to 99 wt%, 10 wt% to 99 wt%, 5 wt% to 98 wt%, 10 wt% to 98 wt%, 25 wt% to 98 wt%, 50 wt% to 98 wt%, 60 wt% to 98 wt%, 70 wt% to 98 wt%, 80 wt% to 98 wt%, 90 wt% to 98 wt%, 93 wt% to 98 wt%, or even 95 wt% to 98 wt%), based on the total weight of the functionalized particles in the polymer matrix composite.

In some embodiments, the polymer matrix composites described herein have at least 0.1g/cm³(in some embodiments, at least 0.15g/cm³、0.2g/cm³、0.25g/cm³、0.5g/cm³Or even at least 1g/cm³(ii) a In some embodiments, at 0.1g/cm³To 2g/cm³、0.1g/cm³To 1.5g/cm³、0.1g/cm³To 1g/cm³Or even 0.1g/cm³To 0.5g/cm³In range).

In some embodiments, the polymer matrix composites described herein have a porosity of at least 5% (in some embodiments, in the range of 5% to 90%, 10% to 90%, 20% to 80%, or even 30% to 60%).

In some embodiments, the polymer matrix composites described herein have at least 1m²(in some embodiments, at least 5 m)²/g、10m²/g、15m²/g、20m²/g、30m²/g、40m²G or even at least 50m²(ii)/g; in some embodiments, at 50m²G to 500m²In g or even 200m²G to 800m²In the range of/g). The advantage of a larger surface area may be an increased binding capacity. Exemplary particles having a relatively large useful surface area include those reported in U.S. patent 7,582,684(Rasmussen et al), the disclosure of which is incorporated herein by reference.

The polymer network structure may be described as a porous polymer network or a porous phase separated polymer network. Generally, the porous polymer network (as prepared) comprises an interconnected porous polymer network structure comprising a plurality of interconnected morphologies (e.g., at least one of fibrils, nodes, open cells, closed cells, lobed laces, strands, nodes, spheres, or honeycomb structures). The interconnected polymeric structures may adhere directly to the surface of the particles and act as a binder for the particles. In this regard, the spaces between adjacent particles (e.g., particles or agglomerate particles) may comprise a porous polymer network structure rather than a solid matrix material, thereby providing the desired porosity.

In some embodiments, the polymer network structure may comprise a three-dimensional network structure comprising an interconnected network of polymeric fibrils. In some embodiments, the average width of the individual fibrils is in the range of 10nm to 100nm (in some embodiments, in the range of 100nm to 500nm, or even in the range of 500nm to 5 microns).

In some embodiments, the particles are dispersed within the polymer network structure such that the outer surface of individual units of the particles (e.g., individual particles or individual agglomerate particles) are largely free from contact with the polymer network structure or are uncoated. In this regard, in some embodiments, the average area coverage percentage of the polymeric network structures on the outer surface of an individual particle (i.e., the percentage of the area of the outer surface in direct contact with the polymeric network structures) is no greater than 50% (in some embodiments, no greater than 40%, 30%, 25%, 20%, 10%, 5%, or even no greater than 1%) based on the total surface area of the outer surface of the individual particle.

In some embodiments, the polymer network structure does not penetrate the internal pores or interior surface area of the individual particles (e.g., the individual particles or individual agglomerate particles are largely not contacted or coated by the polymer network structure).

In some embodiments, the polymer network structure may comprise, consist essentially of, or consist of at least one thermoplastic polymer. Exemplary thermoplastic polymers include at least one of: polyurethanes, polyesters (e.g., polyethylene terephthalate, polybutylene terephthalate, and polylactic acid), polyamides (e.g., nylon 6, nylon 12, and polypeptides), polyethers (e.g., polyethylene oxide and polypropylene oxide), polycarbonates (e.g., bisphenol A polycarbonate), polyimides, polysulfones, polyethersulfones, polyphenylene ethers, polyacrylates (e.g., thermoplastic polymers formed by addition polymerization of one or more monomers comprising acrylate functionality), polymethacrylates (e.g., thermoplastic polymers formed by addition polymerization of one or more monomers comprising methacrylate functionality), polyolefins (e.g., polyethylene and polypropylene), styrene and styrene-based random and block copolymers, chlorinated polymers (e.g., polyvinyl chloride), fluoropolymers (e.g., polyvinylidene fluoride; tetrafluoroethylene, and polylactic acid), and polymers containing at least one of these monomers, Copolymers of hexafluoropropylene and vinylidene fluoride; copolymers of ethylene and tetrafluoroethylene; hexafluoropropylene; and polytetrafluoroethylene), and copolymers of ethylene and chlorotrifluoroethylene. In some embodiments, the thermoplastic polymer comprises a homopolymer or a copolymer (e.g., a block copolymer or a random copolymer). In some embodiments, the thermoplastic polymer comprises a mixture of at least two thermoplastic polymer types (e.g., a mixture of polyethylene and polypropylene or a mixture of polyethylene and polyacrylate). In some embodiments, the polymer can be at least one of polyethylene (e.g., ultra-high molecular weight polyethylene), polypropylene (e.g., ultra-high molecular weight polypropylene), polylactic acid, poly (ethylene-co-chlorotrifluoroethylene), and polyvinylidene fluoride. In some embodiments, the thermoplastic polymer is a single thermoplastic polymer (i.e., it is not a mixture of at least two thermoplastic polymer types). In some embodiments, the thermoplastic polymer consists essentially of polyethylene (e.g., ultra-high molecular weight polyethylene) or consists of polyethylene.

In some embodiments, the thermoplastic polymer used to prepare the polymer matrix composites described herein is a particle having a particle size of less than 1000 microns (in some embodiments, in the range of 1 micron to 10 microns, 10 microns to 30 microns, 30 microns to 100 microns, 100 microns to 200 microns, 200 microns to 500 microns, 500 microns to 1000 microns).

In some embodiments, the porous polymer network structure comprises at least one of: polyacrylonitrile, polyurethanes, polyesters, polyamides, polyethers, polycarbonates, polyimides, polysulfones, polyphenylene ethers, polyacrylates, polymethacrylates, polyolefins, styrene or styrene-based random and block copolymers, chlorinated polymers, fluorinated polymers or copolymers of ethylene and chlorotrifluoroethylene.

In some embodiments, the porous polymer network structure comprises a number average molecular weight of 5 × 10⁴g/mol to 1 × 10⁷In the g/mol range (in some embodiments, the number average molecular weight is 1 × 10⁶g/mol to 8 × 10⁶g/mol、2×10⁶g/mol to 6 × 10⁶g/mol or even 3 × 10⁶g/mol to 5 × 10⁶In the g/mol range). For the purposes of this disclosure, the number average molecular weight can be measured by techniques known in the art (e.g., Gel Permeation Chromatography (GPC)). GPC can be performed in a suitable solvent for the thermoplastic polymer, along with the use of narrow molecular weight distribution polymer standards (e.g., narrow molecular weight distribution polystyrene standards). Thermoplastic polymersGenerally characterized as partially crystalline, exhibiting a melting point. In some embodiments, the melting point of the thermoplastic polymer may be in the range of 120 ℃ to 350 ℃ (in some embodiments, in the range of 120 ℃ to 300 ℃, 120 ℃ to 250 ℃, or even 120 ℃ to 200 ℃). The melting point of the thermoplastic polymer can be measured by techniques known in the art (e.g., using a set temperature measured in a Differential Scanning Calorimetry (DSC) test with a 5mg to 10mg sample at a heating scan rate of 10 ℃/min while the sample is under a nitrogen atmosphere).

In some embodiments, the polymer network structure is a continuous network structure (i.e., the polymer phase includes a structure that is open-celled with continuous voids or pores that form interconnections between voids and extend throughout the structure). In some embodiments, at least 2% (in some embodiments, at least 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or even 100%) by volume of the polymer network structure may be a continuous polymer network structure. It should be noted that for the purposes of this disclosure, the volume fraction of the polymer matrix composite comprised of particles is not considered to be part of the polymer network structure. In some embodiments, the polymer network extends between two particles, thereby forming a network of interconnected particles.

The solvent (e.g., the first solvent) is selected such that it forms a miscible polymer-solvent solution. In some cases, elevated temperatures may be required to form a miscible polymer-solvent solution. The solvent may be a blend of at least two separate solvents. In some embodiments, when the polymer is a polyolefin (e.g., at least one of polyethylene and polypropylene), the solvent can be, for example, at least one of: mineral oil, tetralin, decalin, o-dichlorobenzene, cyclohexane toluene mixtures, dodecane, paraffin oil/wax, kerosene, isoparaffinic fluids, p-xylene/cyclohexane mixtures (1/1wt/wt), camphene, 1,2,4 trichlorobenzene, octane, orange oil, vegetable oil, castor oil or palm kernel oil. In some embodiments, when the polymer is polyvinylidene fluoride, the solvent can be, for example, ethylene carbonate, propylene carbonate, or 1,2, 3-triacetylAt least one of oxypropanes. The solvent may be removed, for example by evaporation. High vapor pressure solvents are particularly suitable for this removal process. However, if the first solvent has a low vapor pressure, it may be desirable for the second solvent, which has a higher vapor pressure, to extract the first solvent, followed by evaporation of the second solvent. For example, in some embodiments, when mineral oil is used as the first solvent, isopropanol or methyl nonafluorobutyl ether (C) is at elevated temperature (e.g., about 60 ℃)₄F₉OCH₃) Ethyl nonafluorobutyl ether (C)₄F₉OC₂H₅) And trans-1, 2-dichloroethylene (e.g., available under the trade designation NOVEC72DE from 3M Company of st paul, MN) may be used as the second solvent to extract the first solvent, followed by evaporation of the second solvent. In some embodiments, when at least one of vegetable oil or palm kernel oil is used as the first solvent, isopropanol at elevated temperatures (e.g., about 60 ℃) may be used as the second solvent. In some embodiments, when ethylene carbonate is used as the first solvent, water may be used as the second solvent.

These include viscosity modifiers (e.g., fumed silica, block copolymers, and waxes), plasticizers, heat stabilizers (e.g., such as, for example, available under the trade name "Irganox 1010" from ludwigshafen ag Germany (BASF, &lttttransfer = L "&gttl &/t &gtttudwigshafen, Germany)), biocides (e.g., silver and quaternary ammonium), flame retardants, antioxidants, dyes, pigments, and Ultraviolet (UV) stabilizers.

In some embodiments, the polymer matrix composites described herein are in the form of a layer having a thickness in the range of 50 micrometers to 7000 micrometers, wherein the thickness does not include the height of any protrusions extending from the base of the layer.

In some embodiments, the porous polymer network structure is prepared by induced phase separation of miscible thermoplastic polymer-solvent solutions. In some embodiments, the induced phase separation is at least one of thermally induced phase separation or solvent induced phase separation.

First method

A first method of making a polymer matrix composite as described herein comprises:

combining (e.g., mixing or blending) a thermoplastic polymer, a solvent, and a plurality of functionalized particles to provide a slurry;

shaping the slurry into an article (e.g., a layer);

heating the article in an environment to retain in the article at least 90% (in some embodiments, at least 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or even at least 99.5%) by weight of the solvent based on the weight of the solvent in the article, and to dissolve at least 50% (in some embodiments, at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, or even 100%) by weight of the thermoplastic polymer based on the total weight of the thermoplastic polymer; and

inducing phase separation of the thermoplastic polymer from the solvent to provide the polymer matrix composite.

If the particles are dense, the slurry is typically continuously mixed or blended to prevent or reduce settling or separation of the polymer and/or particles from the solvent. In some embodiments, the slurry is degassed to remove residual air using techniques known in the art.

The slurry can be shaped into an article using techniques known in the art, including knife coating, roll coating (e.g., roll coating through a defined nip), and coating through any number of different dies of suitable size or profile.

In some embodiments of the first process, the combining is conducted at least one temperature below the melting point of the polymer and below the boiling point of the solvent.

In some embodiments of the first process, the heating is conducted at least one temperature above the melting point of the miscible thermoplastic polymer-solvent solution and below the boiling point of the solvent.

In some embodiments of the first method, inducing phase separation is performed at least one temperature below the melting point of the polymer in the slurry. While not wanting to be bound, it is believed that in some embodiments, the solvent used to prepare the miscible blend with the polymer may cause a decrease in the melting point in the polymer. The melting point as described herein includes any melting point depression below the polymer solvent system.

In some embodiments of the first process, the solvent is a blend of at least two separate solvents. In some embodiments, when the polymer is a polyolefin (e.g., at least one of polyethylene or polypropylene), the solvent may be at least one of: mineral oil, tetralin, decalin, o-dichlorobenzene, cyclohexane toluene mixture, dodecane, paraffin oil/wax, kerosene, p-xylene/cyclohexane mixture (1/1wt/wt), camphene, 1,2,4 trichlorobenzene, octane, orange oil, vegetable oil, castor oil or palm kernel oil. In some embodiments, when the polymer is polyvinylidene fluoride, the solvent is at least one of ethylene carbonate, propylene carbonate, or 1,2,3 triacetoxypropane.

In some embodiments of the first process, the polymer network structure may be formed during phase separation. In some embodiments, the polymer network structure may be provided by induced phase separation of miscible thermoplastic polymer-solvent solutions. In some embodiments, phase separation is thermally induced (e.g., by Thermally Induced Phase Separation (TIPS) that is quenched to a temperature lower than the temperature used during heating). Cooling may be provided, for example, in air, liquid, or on a solid interface, and may be varied to control phase separation. The polymer network structure may be inherently porous (i.e., have pores). The pore structure may be open, enabling fluid communication from an interior region of the polymer network structure to an exterior surface of the polymer network structure and/or between a first surface of the polymer network structure and an opposing second surface of the polymer network structure.

In some embodiments of the methods described herein, the weight ratio of solvent to polymer is at least 9: 1. In some embodiments, the volume ratio of particles to polymer is at least 9: 1. In some embodiments, for ease of manufacturing, it may be desirable to form the layer at room temperature. Generally, during formation using phase separated layers, the relatively small pores are particularly prone to collapse during solvent extraction. The relatively high particle and polymer loadings achievable by the methods described herein may reduce pore collapse and produce a more uniform defect-free polymer matrix composite.

In some embodiments, the first method further comprises removing at least a portion of the solvent from the shaped article after inducing phase separation of the thermoplastic polymer from the solvent (in some embodiments, removing at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, 99.5, or even 100 percent by weight of the solvent based on the weight of the solvent in the shaped article).

In some embodiments of the first method, at least 90 wt% of the solvent is removed based on the weight of the solvent in the shaped article, wherein the shaped article has a first volume before at least 90 wt% of the solvent is removed based on the weight of the solvent in the shaped article, wherein the shaped article has a second volume after at least 90 wt% of the solvent is removed based on the weight of the solvent in the shaped article, and wherein the difference between the first volume and the second volume (i.e., (the first volume minus the second volume) divided by the first volume multiplied by 100) is less than 10% (in some embodiments, less than 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.75%, 0.5%, or even less than 0.3%). The volatile solvent can be removed from the polymer matrix composite, for example, by allowing the solvent to evaporate from at least one major surface of the polymer matrix composite. The evaporation may be assisted, for example, by the addition of at least one of heat, vacuum, or a gas stream. The evaporation of the flammable solvent can be accomplished in a solvent grade oven. However, if the first solvent has a low vapor pressure, then a higher vapor pressure can be usedThe first solvent is extracted with the second solvent under pressure, followed by evaporation of the second solvent. For example, in some embodiments, when mineral oil is used as the first solvent, isopropanol or methyl nonafluorobutyl ether (C) is at elevated temperature (e.g., about 60 ℃)₄F₉OCH₃) Ethyl nonafluorobutyl ether (C)₄F₉OC₂H₅) And trans-1, 2-dichloroethylene (e.g., available under the trade designation NOVEC72DE from 3M Company of st paul, MN) can be used as the second solvent to extract the first solvent, followed by evaporation of the second solvent. In some embodiments, when at least one of vegetable oil or palm kernel oil is used as the first solvent, isopropanol at elevated temperatures (e.g., about 60 ℃) may be used as the second solvent. In some embodiments, when ethylene carbonate is used as the first solvent, water may be used as the second solvent.

In some embodiments of the first method, the article has first and second major surfaces having ends perpendicular to the first and second major surfaces, and the ends are not constrained during solvent removal (i.e., no constraint is required during extraction or stretching). This can be done, for example, by drying a portion of the layer in an oven without restriction. Continuous drying may be achieved, for example, by drying a portion of the layer supported on the belt as it is conveyed through an oven. Alternatively, for example to facilitate removal of the non-volatile solvent, a portion of the layer may be continuously transported through a bath of compatible volatile solvent to exchange the solvent and then allow the layer to dry without restriction. However, not all of the non-volatile solvent needs to be removed from the layer during solvent exchange. Small amounts of non-volatile solvents may remain and act as plasticizers for the polymer.

In some embodiments of the first method, the shaped and phase separated article has a porosity of at least 5% (in some embodiments, at least 10%, 20%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or even at least 90%, in some embodiments, in a range from 25% to 90%) after solvent removal. This porosity is caused by phase separation of the polymer from the solvent, which initially leaves no unfilled voids because the pores in the polymer matrix composite are filled with solvent. After the solvent is completely or partially removed, or the article is stretched, the void spaces in the polymer matrix composite are exposed. Particle-to-particle interactions can minimize collapse or deformation of the porous polymer matrix composite due to capillary induced negative pressure during solvent drying.

In some embodiments of the first process, the solvent is not removed from the shaped article (even after inducing phase separation of the thermoplastic polymer from the solvent). This can be achieved, for example, by using a non-volatile solvent (e.g., mineral oil or wax) rather than completing the extraction/evaporation step. If unfilled pores are desired in the solvent-containing composite, they can optionally be stretched to open pores within the polymer and solvent matrix.

In general, it is desirable to remove the solvent to expose more functional surface area of the particles.

Second method

A second method of making the polymer matrix composite described herein comprises:

combining (e.g., mixing or blending) a thermoplastic polymer, a solvent for the thermoplastic polymer, and a plurality of functionalized particles to form a suspension of functionalized particles in a miscible thermoplastic polymer-solvent solution;

inducing phase separation of the thermoplastic polymer from the solvent; and

removing at least a portion of the solvent to provide the polymer matrix composite.

In some embodiments, the second method further comprises adding the functionalized particles to the miscible polymer-solvent solution prior to phase separation. The polymer network structure may be formed during the phase separation of the process. In some embodiments, the polymer network structure is prepared via induced phase separation of a miscible thermoplastic polymer-solvent solution. In some embodiments, phase separation is induced thermally (e.g., Thermally Induced Phase Separation (TIPS) by quenching to a lower temperature), chemically (e.g., Solvent Induced Phase Separation (SIPS) by replacing poor solvents with good solvents), or by solvent ratio changes (e.g., by evaporating one of the solvents). Other phase separation or pore formation techniques known in the art may also be used, such as discontinuous polymer blending (sometimes also referred to as Polymer Assisted Phase Inversion (PAPI)), moisture-induced phase separation, or vapor-induced phase separation. The polymer network structure may be inherently porous (i.e., have pores). The pore structure may be open, enabling fluid communication from an interior region of the polymer network structure to an exterior surface of the polymer network structure and/or between a first surface of the polymer network structure and an opposing second surface of the polymer network structure.

In some embodiments of the second method, the polymer in the miscible thermoplastic polymer-solvent solution has a melting point, wherein the solvent has a boiling point, and wherein the combining is performed at least one temperature above the melting point of the miscible thermoplastic polymer solution and below the boiling point of the solvent.

In some embodiments of the second method, the polymer in the miscible thermoplastic polymer-solvent solution has a melting point, and wherein inducing phase separation is performed at least one temperature below the melting point of the polymer in the miscible thermoplastic polymer-solvent solution. The thermoplastic polymer solvent mixture may be heated to facilitate dissolution of the thermoplastic polymer in the solvent. After the thermoplastic polymer has been separated from the solvent phase, at least a portion of the solvent may be removed from the polymer matrix composite using techniques known in the art, including evaporation of the solvent or solvent extraction of the solvent by a higher vapor pressure second solvent, followed by evaporation of the second solvent. In some embodiments, the solvent and second solvent (if used) may be removed from the polymer matrix composite in the range of 10 wt% to 100 wt% (in some embodiments, in the range of 20 wt% to 100 wt%, 30 wt% to 100 wt%, 40 wt% to 100 wt%, 50 wt% to 100 wt%, 60 wt% to 100 wt%, 70 wt% to 100 wt%, 80 wt% to 100 wt%, 90 wt% to 100 wt%, 95 wt% to 100 wt%, or even 98 wt% to 100 wt%).

The solvent is generally selected so that it is capable of dissolving the polymer and forming a miscible polymer-solvent solution. Heating the solution to an elevated temperature may facilitate dissolution of the polymer. In some embodiments, the combining of the polymer and the solvent is performed at least one temperature in the range of 20 ℃ to 350 ℃. The functionalized particles may be added in any or all combinations before the polymer is dissolved, after the polymer is dissolved, or at any time in between.

In some embodiments, the solvent is a blend of at least two separate solvents. In some embodiments, when the polymer is a polyolefin (e.g., at least one of polyethylene or polypropylene), the solvent may be at least one of: mineral oil, paraffin oil/wax, camphene, orange oil, vegetable oil, castor oil or palm kernel oil. In some embodiments, when the polymer is polyvinylidene fluoride, the solvent is at least one of ethylene carbonate, propylene carbonate, or 1,2,3 triacetoxypropane.

In some embodiments, the solvent may be removed, for example, by evaporation, with high vapor pressure solvents being particularly suitable for this removal process. However, if the first solvent has a low vapor pressure, the first solvent may be extracted using a second solvent having a higher vapor pressure, followed by evaporation of the second solvent. For example, in some embodiments, when mineral oil is used as the first solvent, isopropanol or methyl nonafluorobutyl ether (C) is at elevated temperature (e.g., about 60 ℃)₄F₉OCH₃) Ethyl nonafluorobutyl ether (C)₄F₉OC₂H₅) And trans-1, 2-dichloroethylene (available under the trade designation NOVEC72DE from 3M company of saint paul, MN, 3M company) may be used as the second solvent to extract the first solvent, followed by evaporation of the second solvent. In some embodiments, when at least one of vegetable oil or palm kernel oil is used as the first solvent, isopropanol at elevated temperatures (e.g., about 60 ℃) may be used as the second solvent. In some embodiments, when ethylene carbonate is used as the firstWhen a solvent is used, water may be used as the second solvent.

Typically, the blended mixture is shaped into a layer prior to curing of the polymer during phase separation. The polymer is dissolved in a solvent (which allows for the formation of a miscible thermoplastic solvent solution), and the functionalized particles are dispersed to form a blended mixture that is shaped into an article (e.g., a layer) followed by phase separation (e.g., for TIPS temperature reduction, for SIPS solvent evaporation or solvent exchange with a non-solvent). Layer formation can be carried out using techniques known in the art, including knife coating, roll coating (e.g., by roll coating defining a nip), and extrusion (e.g., extrusion through a die having an appropriate layer size (i.e., width and thickness of the die gap)). In an exemplary embodiment, the mixture has a paste-like consistency and is formed into a layer by extrusion, for example through a die having appropriate layer dimensions (i.e., width and thickness of the die gap). After shaping the slurry into a layer in which the thermoplastic polymer is miscible in its solvent, the polymer phase separation is then induced. Phase separation may be induced using a number of techniques, including at least one of thermally induced phase separation or solvent induced phase separation. Thermally induced phase separation may occur when the temperature at which induced phase separation is performed is lower than the combined temperature of the polymer, solvent, and functionalized particles. If the combination is carried out at near room temperature, this can be achieved by cooling the miscible polymer-solvent solution, or by first heating the miscible polymer-solvent solution to an elevated temperature (either during or after combination) and then reducing the temperature of the miscible polymer-solvent solution, thereby inducing phase separation of the thermoplastic polymer. In both cases, cooling can result in phase separation of the polymer from the solvent. Solvent-induced phase separation may be performed by adding a second solvent that is a poor solvent for the polymer to the miscible polymer-solvent solution, or may be achieved by removing at least a portion of the solvent of the miscible polymer-solvent solution (e.g., evaporating at least a portion of the solvent of the miscible polymer-solvent solution), thereby inducing phase separation of the polymer. A combination of phase separation techniques (e.g., thermally induced phase separation and solvent induced phase separation) may be employed. Thermally induced phase separation can be advantageous because it also facilitates dissolution of the polymer when the combination is performed at elevated temperatures. In some embodiments, the thermally induced phase separation is performed at least one temperature in the range of 5 ℃ to 300 ℃ (in some embodiments in the range of 5 ℃ to 250 ℃,5 ℃ to 200 ℃,5 ℃ to 150 ℃, 15 ℃ to 300 ℃, 15 ℃ to 250 ℃, 15 ℃ to 200 ℃, 15 ℃ to 130 ℃, or even 25 ℃ to 110 ℃) below the combined temperature.

After inducing phase separation, at least a portion of the solvent may be removed, thereby forming a porous polymer matrix composite layer having a polymer network structure and functionalized particles distributed within the thermoplastic polymer network structure. Optionally, after inducing phase separation, stretching the solvent-filled structure, thereby forming a porous polymer matrix composite layer having a polymer network structure, a solvent, and particles distributed within the thermoplastic polymer network structure.

The solvent may be removed by evaporation, and high vapor pressure solvents are particularly suitable for this removal process. However, if the first solvent has a low vapor pressure, the first solvent may be extracted using a second solvent having a higher vapor pressure, followed by evaporation of the second solvent. In some embodiments, the solvent and second solvent (if used) may be removed from the polymer matrix composite in the range of 10 wt% to 100 wt% (in some embodiments, in the range of 20 wt% to 100 wt%, 30 wt% to 100 wt%, 40 wt% to 100 wt%, 50 wt% to 100 wt%, 60 wt% to 100 wt%, 70 wt% to 100 wt%, 80 wt% to 100 wt%, 90 wt% to 100 wt%, 95 wt% to 100 wt%, or even 98 wt% to 100 wt%).

In some embodiments, the first and second methods further comprise at least one of stretching or compressing the polymer matrix composite. That is, after inducing phase separation, the formed polymer network structure may be stretched or compressed, for example, to tune the airflow resistance of the polymer matrix composite. For example, stretching or compression of the polymer matrix composite may be accomplished by conventional calendering or tentering processes known in the art.

In some embodiments in which the network structure is plastically deformed by at least a compressive force, vibrational energy may be imparted during application of the compressive force. In some of these embodiments, the polymer composite is in the form of a strip having an infinite length, and the step of applying a compressive force is performed as the strip passes through the nip. A tensile load may be applied during passage through this nip. For example, a nip may be formed between two rolls, wherein at least one roll applies vibrational energy; between the roller and the strip, at least one of which applies vibration energy; or between two strips, at least one of which applies vibration energy. The application of the compressive force and the vibrational energy can be accomplished in a continuous roll-to-roll manner or in a step and repeat manner. In other embodiments, the compressive force step is performed on, for example, discrete layers between the plate and the platen, wherein at least one of the plate and the platen applies vibrational energy. In some embodiments, the vibrational energy is in the ultrasonic range (e.g., 20kHz), but other ranges are deemed suitable. For more details on plastically deforming a network structure, see co-pending patent application with U.S. serial No. 62/578,732 filed on 30/10/2017, the disclosure of which is incorporated herein by reference.

In some embodiments, the polymer matrix composites described herein may be wrapped around a 0.5mm (in some embodiments, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1mm, 2mm, 3mm, 4mm, 5mm, 1cm, 5cm, 10cm, 25cm, 50cm, or even 1m) rod without breaking.

In some embodiments of both the first and second methods, the polymer matrix composites described herein have first and second opposing planar major surfaces. In some embodiments, the polymer matrix composites described herein have opposing first and second major surfaces, wherein the first major surface is non-planar (e.g., curved). Referring to fig. 1, an exemplary polymer matrix composite 100 described herein has opposing first and second major surfaces 101 and 102. The first major surface 101 is non-planar.

The planar and non-planar major surfaces can be provided, for example, by coating or extruding the slurry onto a patterned substrate (e.g., a pad, belt, die, or tool). Alternatively, for example, a die with shaped slots may be used to form a non-flat surface during a coating or extrusion process. Alternatively, for example, the structure may be formed before and/or after the phase separation has occurred before and/or after the solvent is removed by molding or shaping the layer with a patterning tool.

In some embodiments of both the first and second methods, the polymer matrix composites described herein have first protrusions extending outwardly from the first major surface, and in some embodiments, have second protrusions extending outwardly from the second major surface. In some embodiments, the first protrusion is integral with the first major surface, and in some embodiments, the second protrusion is integral with the second major surface. Exemplary projections include at least one of a post, rail, hook, cone, continuous rail, continuous multidirectional rail, hemisphere, cylinder, or multi-lobed cylinder. In some embodiments, the protrusion has a cross-section in at least one of: circular, square, rectangular, triangular, pentagonal, other polygonal, sinusoidal, chevron, or multi-lobed.

Referring to fig. 2, exemplary polymer matrix composites 200 described herein have a first protrusion 205 extending outwardly from first major surface 201 and an optional second protrusion 206 extending outwardly from second major surface 202.

The protrusions may be provided, for example, by coating or extrusion between patterned substrates (e.g., liners, belts, dies, or tools). Alternatively, a die with shaped slots may be used to form the projections during the coating or extrusion process. Alternatively, for example, the structure may be formed after phase separation has occurred before and/or after solvent is removed by molding or shaping the film between patterning tools.

In some embodiments of both the first and second methods, the polymer matrix composites described herein have a first depression extending into the first major surface, and in some embodiments, have a second depression extending into the second major surface. Exemplary depressions include at least one of a groove, slot, inverted pyramid, hole (including through hole or blind hole), or dimple. Referring to fig. 3, exemplary polymer matrix composite 300 described herein has a first depression 307 extending into first major surface 301 and a second depression 308 extending into second major surface 302.

The depressions may be provided, for example, by coating or extrusion between patterned substrates (e.g., liners, belts, dies, or tools). Alternatively, for example, a die having a shaping slot may be used to form the depression during the coating or extrusion process. Alternatively, for example, the structure may be formed after phase separation has occurred before and/or after solvent is removed by molding or shaping the film between patterning tools.

In some embodiments, the polymer matrix composites described herein further comprise a reinforcing material (e.g., attached to, partially within, and/or within the polymer matrix composite). Exemplary reinforcing materials include fibers, strands, nonwovens, wovens, fabrics, meshes, and films. The reinforcement material may be laminated to the polymer matrix composite, for example, by thermal, adhesive, or ultrasonic lamination. The reinforcing material may be embedded within the polymer matrix composite, for example, during a coating or extrusion process. The reinforcement material may be located, for example, between major surfaces, on one major surface, or on both major surfaces of the composite material. More than one type of reinforcing material may be used.

The polymer matrix composites described herein can be used, for example, as filters or purification devices (absorbents, complexing agents, enzymes, or other protein-bearing supports) or chromatography articles. The polymer matrix composites described herein may be reusable or disposable, depending on the particular application. For more details on general use, see, for example, U.S. patent 5,993,935(Rasmussen et al), the disclosure of which is incorporated herein by reference. For example, the composite material may be used to remove microbial contamination from drinking water. For more details on the removal of microbial contamination from drinking water in general, see, for example, applications having U.S. patent publication US2018/0038862 published on 8.2.2018 and PCT publication 2016/149233 published on 22.9.2016, the disclosures of which are incorporated herein by reference.

For example, the polymer matrix composites described herein can be used as filtration media for selectively binding and removing target biological materials or biological species, including relatively neutral or charged biological materials (e.g., viruses and other microorganisms, acidic carbohydrates, proteins, nucleic acids, endotoxins, bacteria, cells, and cell debris) from a biological sample. Articles comprising the polymer matrix composites described herein may also include conventional components such as housings, holders, and adapters.

If desired, the efficiency of binding and trapping the biomaterial can be improved by using multiple stacked or layered polymer matrix composites as the filter element. Accordingly, the filter element may comprise at least one polymer matrix composite layer as described herein. The individual layers of the filter element may be the same or different. The porosity of the layer, the type of functionalized particles, and the like may vary. The filter element may also include an upstream pre-filter layer and/or a downstream support layer. The various layers may be planar or folded, as desired.

Examples of suitable prefilter and support layer materials include any suitable porous membranes of polypropylene, polyester, polyamide, resin-bonded or binderless fibers (e.g., glass fibers), and other synthetic materials (e.g., woven and non-woven fleece structures); sintered materials (e.g., polyolefins, metals, and ceramics); a yarn; filter paper (e.g., a mixture of fibers, cellulose, polyolefin, and binder); and a polymer film.

Useful articles for biomaterial capture or filtration applications include filter housings, filter cartridges having one or more of the above-described filter elements, and filter assemblies having one or more of the above-described filter elements. Filter types may include plate and frame filters, plate filters, depth filters, cartridge filters, bag filters, capsule filters, cross-flow filters, Tangential Flow Filters (TFF), or chromatographic devices. The article may be used to implement a method of capturing or removing a biological material or biological species of interest, the method comprising (a) providing at least one article comprising at least one filter element as described above; and (b) allowing the flowing biological solution containing the target biological material to be sprayed onto the upstream surface of the filter element for a sufficient time to effect binding of the target biological material.

Exemplary embodiments

A polymer matrix composite comprising:

a porous polymer network structure; and

a plurality of functionalized particles distributed within the polymer network structure,

wherein the polymer matrix composite has an airflow resistance at 25 ℃ of less than 300 seconds/50 cm as measured by the "airflow resistance test" described in the examples³500 micron (in some embodiments, less than 250 seconds/50 cm)³500 micron, 200 second/50 cm³500 micron, 100 second/50 cm³500 micron, 50 second/50 cm³500 micron, 25 second/50 cm³500 micron, 20 second/50 cm³500 micron, 15 second/50 cm³500 micron, 10 second/50 cm³500 micron or even less than 5 seconds/50 cm³500 μm).

The polymer matrix composite of exemplary embodiment 1A, wherein the functionalized particles are present in a range of 1 to 99 wt.% (in some embodiments, in a range of 5 to 99 wt.%, 10 to 99 wt.%, 5 to 98 wt.%, 10 to 98 wt.%, 25 to 98 wt.%, 50 to 98 wt.%, 60 to 98 wt.%, 70 to 98 wt.%, 80 to 98 wt.%, 90 to 98 wt.%, 93 to 98 wt.%, or even 95 to 98 wt.%) based on the total weight of the functionalized particles and the polymer (not including any solvent).

3A. exemplary embodiment of A according to any of the precedingThe polymer matrix composite of embodiment, wherein the polymer matrix composite has a molecular weight of at least 0.1g/cm³Within the range (in some embodiments, at least 0.15 g/cm)³、0.2g/cm³、0.25g/cm³、0.5g/cm³Or even at least 1g/cm³(ii) a In some embodiments, at 0.1g/cm³To 2g/cm³、0.1g/cm³To 1.5g/cm³、0.1g/cm³To 1g/cm³Or even 0.1g/cm³To 0.5g/cm³In range).

The polymer matrix composite according to any of the preceding a exemplary embodiments, wherein the polymer matrix composite has a porosity of at least 5% (in some embodiments, in the range of 5% to 90%, 10% to 90%, 20% to 80%, or even 30% to 60%).

The polymer matrix composite of any preceding a exemplary embodiment, wherein the functionalized particles comprise first and second functionalized particles that are different (i.e., have different functionalities (e.g., different ionic affinities or hydrophobic interactions).

The polymer matrix composite according to exemplary embodiment 5A, wherein the first functionalized particles comprise anion exchange particles, and wherein the second functionalized particles comprise cation exchange particles.

The polymer matrix composite of exemplary embodiments 5A or 6A, wherein the first functionalized particles have an average particle size (average length of longest dimension) in a range from 0.1 to 5000 micrometers (in some embodiments, in a range from 1 to 500 micrometers, 1 to 120 micrometers, 40 to 200 micrometers, or even 5 to 60 micrometers), and wherein the second functionalized particles have an average particle size (average length of longest dimension) in a range from 0.1 to 5000 micrometers (in some embodiments, in a range from 1 to 500 micrometers, 1 to 120 micrometers, 40 to 200 micrometers, or even 5 to 60 micrometers).

The polymer matrix composite according to any one of exemplary embodiments 5A to 7A, wherein the first functionalized particles are present in a range of from 1 wt% to 99 wt% (in some embodiments, in a range of from 5 wt% to 99 wt%, 10 wt% to 99 wt%, 5 wt% to 98 wt%, 10 wt% to 98 wt%, 25 wt% to 98 wt%, 50 wt% to 98 wt%, 60 wt% to 98 wt%, 70 wt% to 98 wt%, 80 wt% to 98 wt%, 90 wt% to 98 wt%, 93 wt% to 98 wt%, or even 95 wt% to 98 wt%), based on the total weight of the first functionalized particles and the second functionalized particles, and wherein the second functionalized particles are present in a range of from 1 wt% to 99 wt% (in some embodiments, in the range of 5 to 99, 10 to 99, 5 to 98, 10 to 98, 25 to 98, 50 to 98, 60 to 98, 70 to 98, 80 to 98, 90 to 98, 93 to 98, or even 95 to 98) weight percent.

The polymer matrix composite of any preceding a exemplary embodiment, wherein the functionalized particles comprise at least one of inorganic particles or organic particles that participate in removing a target moiety from at least one of a fluid stream or a gas stream.

The polymer matrix composite according to any one of exemplary embodiments 1A to 6A, 8A, or 9A, wherein the functionalized particles have an average particle size (average length of longest dimension) in a range from 0.1 microns to 5000 microns (in some embodiments, in a range from 1 micron to 500 microns, 1 micron to 120 microns, 40 microns to 200 microns, or even 5 microns to 60 microns).

The polymer matrix composite according to any one of exemplary embodiments 1A to 6A or 8A to 10A, further comprising non-functionalized particles.

The polymer matrix composite according to exemplary embodiment 11A, wherein the non-functionalized particles comprise at least one of an inorganic material or an organic material that does not participate in removing a target moiety from at least one of a fluid stream or a gas stream.

13a. the polymer matrix composite of exemplary embodiments 11A or 12A, wherein the non-functionalized particles have an average particle size (average length of longest dimension) in a range from 0.1 microns to 5000 microns (in some embodiments, in a range from 1 micron to 500 microns, 1 micron to 120 microns, 40 microns to 200 microns, or even 5 microns to 60 microns).

The polymer matrix composite according to any one of exemplary embodiments 10A to 12A, wherein the non-functionalized particles are present in a range of 1 to 99 wt% (in some embodiments, in a range of 5 to 99 wt%, 10 to 99 wt%, 5 to 98 wt%, 10 to 98 wt%, 25 to 98 wt%, 50 to 98 wt%, 60 to 98 wt%, 70 to 98 wt%, 80 to 98 wt%, 90 to 98 wt%, 93 to 98 wt%, or even 95 to 98 wt%) based on the total weight of the polymer matrix composite.

15a. the polymer matrix composite according to any preceding a exemplary embodiment, wherein the porous polymer network structure comprises at least one of: polyurethanes, polyesters, polyamides, polyethers, polycarbonates, polyimides, polysulfones, polyether sulfones, polyphenylene oxides, polyacrylates, polymethacrylates, polyacrylonitriles, polyolefins, styrene or styrene-based random and block copolymers, chlorinated polymers, fluorinated polymers or copolymers of ethylene and chlorotrifluoroethylene.

The polymer matrix composite according to any preceding a exemplary embodiment, wherein the porous polymer network structure comprises a plurality of interconnected morphologies that are phase separated (e.g., at least one of fibrils, nodes, open cells, closed cells, lobed laces, strands, nodes, spheres, or honeycomb structures).

17a. according to any preceding exemplary embodiment of aThe polymer matrix composite of wherein the porous polymer network structure comprises a number average molecular weight of 5 × 10⁴g/mol to 1 × 10⁷In the g/mol range (in some embodiments, at 1 × 10)⁶g/mol to 8 × 10⁶g/mol、2×10⁶g/mol to 6 × 10⁶g/mol or even 3 × 10⁶g/mol to 5 × 10⁶In the g/mol range).

18a. the polymer matrix composite according to any preceding a exemplary embodiment, wherein the polymer matrix composite is in the form of a layer having a thickness in the range of 50 microns to 7000 microns.

The polymer matrix composite of any preceding example embodiment of a, wherein the porous polymer network structure is prepared by induced phase separation of a miscible thermoplastic polymer-solvent solution.

The polymer matrix composite according to exemplary embodiment 19A, wherein the induced phase separation is at least one of thermally induced phase separation and solvent induced phase separation.

21a. the polymer matrix composite according to any preceding a exemplary embodiment, having at least 1m²(in some embodiments, at least 5 m)²/g、10m²/g、15m²/g、20m²/g、30m²/g、40m²G or even at least 50m²(ii)/g; in some embodiments, at 50m²G to 500m²In g or even 200m²G to 800m²In the range of/g).

22a. the polymer matrix composite according to any preceding a exemplary embodiment, having opposing first and second planar major surfaces.

23a. the polymer matrix composite according to any preceding a exemplary embodiment, having opposing first and second major surfaces, wherein the first major surface is non-planar (e.g., curved or no flat surface projections therebetween).

The polymer matrix composite according to exemplary embodiments 22A or 23A, wherein the first major surface has a first protrusion extending outwardly from the first major surface. In some embodiments, the protrusion is integral with the first major surface.

25a. the polymer matrix composite of exemplary embodiment 24A, wherein the first protrusion is at least one of a post, rail, hook, cone, continuous rail, continuous multidirectional rail, hemisphere, cylinder, or multi-lobed cylinder.

The polymer matrix composite according to any one of exemplary embodiments 22A to 25A, wherein the first major surface has a first depression extending into the first major surface.

The polymer matrix composite according to exemplary embodiment 26A, wherein the first depression is at least one of a groove, a slot, an inverted pyramid, a hole (including a through hole or a blind hole), or a dimple.

28a. the polymer matrix composite according to any one of exemplary embodiments 24A to 27A, wherein the second major surface has a second protrusion extending outwardly from the second major surface.

29a. the polymer matrix composite of exemplary embodiment 28A, wherein the second protrusion is at least one of a post, rail, hook, cone, continuous rail, continuous multidirectional rail, hemisphere, cylinder, or multi-lobed cylinder.

The polymer matrix composite according to any one of exemplary embodiments 24A to 29A, wherein the second major surface has a second depression extending into the second major surface.

31a. the polymer matrix composite according to exemplary embodiment 30A, wherein the second recess is at least one of a groove, a slot, an inverted pyramid, a hole (including a through hole or a blind hole), or a dimple.

The polymer matrix composite of any of the foregoing a exemplary embodiments, wherein the polymer matrix composite has a bubble point pressure of at least 0.5psi (in some embodiments, at least 0.75psi, 1psi, 1.5psi, 2psi, 3psi, 4psi, 5psi, 10psi, 15psi, 20psi, 25psi, 30psi, 35psi, 40psi, 45psi, 50psi, 55psi, 60psi, 65psi, 70psi, 75psi, 80psi, or even at least 75 psi).

The polymer matrix composite of any preceding a exemplary embodiment, further comprising a reinforcing agent (e.g., partially therein and/or attached thereto).

34a. the polymer matrix composite according to any preceding a exemplary embodiment, which can be wrapped around a 0.5mm (in some embodiments, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1mm, 2mm, 3mm, 4mm, 5mm, 1cm, 5cm, 10cm, 25cm, 50cm, or even 1m) rod without breaking.

The polymer matrix composite according to any of the preceding a exemplary embodiments, comprising at least one of a viscosity modifier (e.g., fumed silica, block copolymer, and wax), a plasticizer, a thermal stabilizer (e.g., such as, for example, BASF, &lttttransition & &gttl &ttt/t &gttudwigshafen, Germany, available under the trade name "Irganox 1010" from BASF of ladishhong, Germany), an antimicrobial agent (e.g., silver and quaternary ammonium), a flame retardant, an antioxidant, a dye, a pigment, or an Ultraviolet (UV) stabilizer.

A method of making a polymer matrix composite according to any of the foregoing a exemplary embodiments, the method comprising:

combining (e.g., mixing or blending) a thermoplastic polymer, a solvent, and a plurality of functionalized particles to provide a slurry;

shaping the slurry into an article (e.g., a layer);

heating the article in an environment to retain in the article at least 90% (in some embodiments, at least 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or even at least 99.5%) by weight of the solvent based on the weight of the solvent in the article, and to dissolve at least 50% (in some embodiments, at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, or even 100%) by weight of the thermoplastic polymer based on the total weight of the thermoplastic polymer; and

inducing phase separation of the thermoplastic polymer from the solvent to provide the polymer matrix composite.

The method of exemplary embodiment 1B, further comprising removing at least a portion of the solvent from the shaped article after inducing phase separation of the thermoplastic polymer from the solvent (in some embodiments, removing at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, 99.5, or even 100 percent by weight of the solvent based on the weight of the solvent in the shaped article).

The method of exemplary embodiment 2B, wherein at least 90 wt.% of the solvent is removed, based on the weight of the solvent in the shaped article, wherein the shaped article has a first volume prior to removal of at least 90 weight percent of the solvent based on the weight of the solvent in the shaped article, wherein the shaped article has a second volume after removal of at least 90 weight percent of the solvent based on the weight of the solvent in the shaped article, and wherein the difference between the first volume and the second volume (i.e. (the first volume minus the second volume) divided by the first volume multiplied by 100) is less than 10% (in some embodiments, less than 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.75%, 0.5%, or even less than 0.3%).

The method of exemplary embodiment 3B, wherein the article has a first major surface and a second major surface having ends perpendicular to the first major surface and the second major surface, and wherein the ends are not restrained during the solvent removal.

The method of exemplary embodiments 3B or 4B, wherein after the solvent removal, the shaped article has a porosity of at least 5% (in some embodiments, at least 10%, 20%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or even at least 90%, in some embodiments, in a range of 25% to 90%).

The method of exemplary embodiment 1B, wherein the solvent is not removed from the shaped article (even after inducing phase separation of the thermoplastic polymer from the solvent).

The method of any preceding B exemplary embodiment, wherein inducing phase separation comprises thermally inducing phase separation.

The method of any preceding B exemplary embodiment, wherein the polymer in the slurry has a melting point, wherein the solvent has a boiling point, and wherein combining is performed below the melting point of the polymer in the slurry and below the boiling point of the solvent.

The method of any preceding B exemplary embodiment, wherein the polymer in the slurry has a melting point, and wherein inducing phase separation is performed below the melting point of the polymer in the slurry.

The method of any preceding B exemplary embodiment, further comprising at least one of stretching or compressing the polymer matrix composite.

The method of any of exemplary embodiments 1B-9B, further comprising applying vibrational energy to the polymer matrix composite while applying the compressive force.

The method of any preceding B exemplary embodiment, wherein the porous polymer network structure comprises at least one of: polyacrylonitrile, polyurethanes, polyesters, polyamides, polyethers, polycarbonates, polyimides, polysulfones, polyether sulfones, polyphenylene oxides, polyacrylates, polymethacrylates, polyolefins, styrene or styrene-based random and block copolymers, chlorinated polymers, fluorinated polymers or copolymers of ethylene and chlorotrifluoroethylene.

The method of any preceding B exemplary embodiment, wherein the porous polymer network structure comprises a plurality of interconnected morphologies (e.g., at least one of fibrils, nodes, open cells, closed cells, lobed laces, strands, nodes, spheres, or honeycomb structures).

The method of any preceding B exemplary embodiment, wherein the porous polymer network structure is prepared by induced phase separation of a miscible thermoplastic polymer-solvent solution.

The method of exemplary embodiment 14B, wherein inducing phase separation comprises thermally inducing phase separation.

A method of making a polymer matrix composite according to any preceding exemplary embodiment of a, the method comprising:

combining (e.g., mixing or blending) a thermoplastic polymer, a solvent for the thermoplastic polymer, and a plurality of functionalized particles to form a suspension of functionalized particles in a miscible thermoplastic polymer-solvent solution;

inducing phase separation of the thermoplastic polymer from the solvent; and

removing at least a portion of the solvent to provide the polymer matrix composite.

The method of exemplary embodiment 1C, wherein inducing phase separation comprises at least one of thermally induced phase separation or solvent induced phase separation.

The method of any preceding C exemplary embodiment, wherein the polymer in the miscible thermoplastic polymer-solvent solution has a melting point, wherein the solvent has a boiling point, and wherein combining is performed above the melting point of the miscible thermoplastic polymer-solvent solution and below the boiling point of the solvent.

The method of any preceding C exemplary embodiment, wherein the polymer in the miscible thermoplastic polymer-solvent solution has a melting point, and wherein inducing phase separation is performed below the melting point of the polymer in the miscible thermoplastic polymer-solvent solution.

The method of any preceding C exemplary embodiment, further comprising at least one of stretching or compressing the polymer matrix composite.

The method of any of exemplary embodiments 1C-4C, further comprising applying vibrational energy to the polymer matrix composite while applying the compressive force.

The method of any preceding C exemplary embodiment, wherein the porous polymer network structure comprises at least one of: polyacrylonitrile, polyurethanes, polyesters, polyamides, polyethers, polycarbonates, polyimides, polysulfones, polyether sulfones, polyphenylene oxides, polyacrylates, polymethacrylates, polyolefins, styrene or styrene-based random and block copolymers, chlorinated polymers, fluorinated polymers or copolymers of ethylene and chlorotrifluoroethylene.

The method of any preceding C exemplary embodiment, wherein the porous polymer network structure comprises a plurality of interconnected morphologies (e.g., at least one of fibrils, nodes, open cells, closed cells, lobed laces, strands, nodes, spheres, or honeycomb structures).

A filter (e.g., a plate and frame filter, a plate filter, a depth filter, a cartridge filter, a capsule filter, a bag filter, a cross-flow filter, a Tangential Flow Filtration (TFF), or a chromatography device) comprising the polymer matrix composite according to any of the foregoing exemplary embodiments a.

Advantages and embodiments of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention. All parts and percentages are by weight unless otherwise indicated.