CN112480638A - Preparation method of transparent toughening master batch - Google Patents

Preparation method of transparent toughening master batch Download PDF

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Publication number
CN112480638A
CN112480638A CN202011442661.1A CN202011442661A CN112480638A CN 112480638 A CN112480638 A CN 112480638A CN 202011442661 A CN202011442661 A CN 202011442661A CN 112480638 A CN112480638 A CN 112480638A
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transparent
porous polymer
master batch
toughening
toughening agent
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陶慷
许亮
洪江
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Nanjing Xuzhi Material Technology Co ltd
Jiangsu Jitri Advanced Polymer Materials Research Institute Co Ltd
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Nanjing Xuzhi Material Technology Co ltd
Jiangsu Jitri Advanced Polymer Materials Research Institute Co Ltd
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
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    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2433/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
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    • C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
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    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds

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  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The invention belongs to the field of modification of high polymer materials, and particularly relates to a preparation method of a transparent toughening master batch, which comprises the following steps: adding the porous polymer into a stirrer, stirring at normal temperature, uniformly spraying the transparent liquid toughening agent on the surface of the porous polymer through a sprayer, controlling the spraying time to be more than 10 minutes, stirring and mixing for 10-30 minutes, standing until the surface of the porous polymer is dried, and obtaining the transparent toughening master batch. The preparation method is simple and can be used for industrial production, and the provided transparent toughening master batch is beneficial to uniformly dispersing the liquid toughening agent in the matrix material, so that the toughness of the matrix material is obviously improved, and the transparency of the material is not reduced.

Description

Preparation method of transparent toughening master batch
Technical Field
The invention belongs to the field of modification of high polymer materials, and particularly relates to a preparation method of a transparent toughening master batch.
Background
The transparent polymer material has a light transmittance of 80% or more in daily light, and is widely used in the fields of electronics, electricity, packaging, buildings, medical supplies, optical fibers, optical components and the like due to its unique optical properties, light weight, high strength, easy processing and the like. The main transparent polymer materials used in the present invention are Polycarbonate (PC), Polystyrene (PS), polymethyl methacrylate (PMMA), Polyamide (PA), polyethylene terephthalate (PET), etc., and in the processing and application of these resins, it is often necessary to toughen and modify them to widen the application range.
A common toughening method is to fill the plastic with a powdered or granular toughening agent or a toughening masterbatch to improve its toughness. Patent No. CN101712788B discloses a toughening master batch for polystyrene, which can greatly improve the toughness of polystyrene material, but also reduce the transparency of the material. In order to improve the toughness of the material without affecting the transparency of the material, transparent toughening agents appear on the market.
The transparent toughening agent can not only improve the toughness of the material, but also can not influence the transparency of the material and the physical properties of other aspects. Patent No. CN108047684A reports a transparent PC resin powder or particle toughening agent and a processing method thereof, patent No. CN103059432B discloses a preparation method of a transparent toughening polystyrene functional color master batch, and both patents propose a powder or particle transparent toughening agent, but the adopted preparation method has complex process, needs blending, granulation or grinding into powder, and needs to adopt a powdery base material in order to ensure that the toughening agent is uniformly dispersed, so that the cost of quantitative production is higher. A liquid transparent toughening agent for plastics is reported in a patent with a patent number of CN102558866A, and a patent with a patent number of CN103421265B discloses a transparent PMMA toughening agent, wherein the two toughening agents are both transparent liquid toughening agents, so that although the toughness of the material can be increased without influencing the transparency of the material, the addition process of the toughening agent is complex, additional liquid adding equipment needs to be added, and the addition mode of the toughening agent can influence the dispersion degree of the toughening agent in a matrix and influence the toughening effect on matrix resin.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of a transparent toughening master batch. The invention has simple operation and can be produced industrially, and the prepared transparent toughening master batch can uniformly disperse the liquid toughening agent in the matrix material, obviously improve the toughness of the matrix material and simultaneously can not reduce the transparency of the material.
In order to solve the technical problems, the invention adopts the technical scheme that:
a preparation method of a transparent toughening master batch comprises the following steps: adding the porous polymer into a stirrer, and stirring at normal temperature; and uniformly spraying the transparent liquid toughening agent on the surface of the porous polymer through a sprayer, controlling the spraying time to be more than 10 minutes, stirring and mixing for 10-30 minutes, and standing until the surface of the porous polymer is dried to obtain the transparent toughening master batch.
Further, the components are calculated according to parts by weight: 30-90 parts of porous polymer and 10-70 parts of transparent liquid toughening agent.
Further, the porous polymer is one of a PC porous polymer, a PS porous polymer, a PET porous polymer, a PMMA porous polymer, and a PA6 porous polymer.
Further, the particle size of the porous polymer is 0.5-10 mm, the porosity is not less than 20%, and the bulk density is 50-350 kg/m3。
Further, the transparent liquid toughening agent is one or more of a hyperbranched silicon compound, liquid silicone rubber and a transparent epoxy toughening agent.
Further, the stirring speed of the stirrer is controlled to be 20-300 rpm.
Compared with the prior art, the preparation method of the transparent toughening master batch provided by the invention has the following beneficial effects:
(1) the porous polymer adopted in the invention can be adjusted according to the type of the modified matrix, and the prepared transparent toughening master batch has good compatibility with the matrix, can obviously improve the toughness of the matrix, and does not influence the transparency of the matrix material.
(2) The transparent toughening master batch is used for modifying matrix resin, so that the uniform dispersion degree of the toughening agent in a modified matrix can be further improved, and the modification effect is further improved.
(3) The preparation method is simple in preparation process, can be directly applied to injection molding process products, can accurately control the content of the transparent liquid toughening agent in the master batch, and can prepare the toughening master batch with high content of 70%, so that the toughening effect of the toughening agent on matrix resin can be regulated and controlled, and the performance requirements of the products under different use conditions can be met.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, it being understood that the examples described herein are intended only to illustrate and explain the present invention and are not intended to limit the present invention.
Example 1
The raw materials and weight ratio of each component in the embodiment are as follows:
50 parts of a porous PC polymer (particle size 3mm, bulk density 200 kg/m)3Porosity 50%); 50 parts of hyperbranched silicon compound transparent liquid toughening agent.
The method for preparing the transparent toughening master batch in the embodiment is as follows:
the PC porous polymer was added to a stirrer and stirred at normal temperature with the stirring speed of the stirrer being 100 rpm. Adding the hyperbranched silicon compound transparent liquid toughening agent into a stirrer through a canning sprayer, and uniformly spraying the toughening agent on the surface of the PC porous polymer, wherein the spraying time is controlled to be 20 minutes. And after the addition is complete, stirring and mixing for 30 minutes, and then standing until the surface of the PC porous polymer is dry and free of greasy feeling, so that the transparent toughened PC master batch is obtained. By utilizing the structural characteristics of the PC porous polymer, the liquid toughening agent is uniformly dispersed in the internal pore channels of the PC porous polymer, and the prepared PC master batch is blended with the PC matrix resin and extruded and granulated by a double-screw extruder.
Example 2
The raw materials and weight ratio of each component in the embodiment are as follows:
30 parts of a PS cellular polymer (particle size 7mm, bulk density 50 kg/m)3Porosity 80%); 70 parts of transparent epoxy toughening agent.
The method for preparing the transparent toughening master batch in the embodiment is as follows:
the PS porous polymer is added into a stirrer and stirred at normal temperature, and the stirring speed of the stirrer is 200 rpm. Adding the transparent epoxy toughening agent into a stirrer through a canned sprayer, and uniformly spraying the transparent epoxy toughening agent on the surface of the PS porous polymer, wherein the spraying time is controlled to be 15 minutes. And after the addition is complete, stirring and mixing for 25 minutes, and then standing until the surface of the PS porous polymer is dry and has no greasy feeling, so that the transparent toughened PS master batch is obtained. By utilizing the structural characteristics of the PS porous polymer, the liquid toughening agent is uniformly dispersed in the internal pore channels of the PS porous polymer, the prepared PS master batch and the PS matrix resin are blended, and the mixture is extruded and granulated by a double-screw extruder.
Example 3
The raw materials and weight ratio of each component in the embodiment are as follows:
70 parts of PS cellular polymer (particle size 2mm, bulk density 300 kg/m)3Porosity 30%); 30 parts of liquid silicone rubber transparent toughening agent.
The method for preparing the transparent toughening master batch in the embodiment is as follows:
the PS porous polymer is added into a stirrer and stirred at normal temperature, and the stirring speed of the stirrer is 150 rpm. Adding the liquid silicon rubber toughening agent into a stirrer through a canned sprayer, and uniformly spraying the liquid silicon rubber toughening agent on the surface of the PS porous polymer, wherein the spraying time is controlled to be 10 minutes. And after the addition is complete, stirring and mixing for 10 minutes, and then standing until the surface of the PS porous polymer is dry and has no greasy feeling, so that the transparent toughened PS master batch is obtained. By utilizing the structural characteristics of the PS porous polymer, the liquid toughening agent is uniformly dispersed in the internal pore channels of the PS porous polymer, the prepared PS master batch and the PS matrix resin are blended, and the mixture is extruded and granulated by a double-screw extruder.
Example 4
The raw materials and weight ratio of each component in the embodiment are as follows:
40 parts of PMMA porous polymer (particle size 3mm, bulk density 250 kg/m)3Porosity 60%); 60 parts of hyperbranched silicon compound transparent liquid toughening agent.
The method for preparing the transparent toughening master batch in the embodiment is as follows:
adding the PMMA porous polymer into a stirrer, and stirring at normal temperature, wherein the stirring speed of the stirrer is 300 rpm. Adding the hyperbranched silicon compound toughening agent into a stirrer through a canning sprayer, and uniformly spraying the hyperbranched silicon compound toughening agent on the surface of the PMMA porous polymer, wherein the spraying time is controlled to be 15 minutes. And after the addition is complete, stirring and mixing for 15 minutes, and then standing until the surface of the PMMA porous polymer is dry and free of greasy feeling, so that the transparent toughened PMMA master batch is obtained. By utilizing the structural characteristics of the PMMA porous polymer, the liquid toughening agent is uniformly dispersed in the internal pore channels of the PMMA porous polymer, the prepared PMMA master batch is blended with PMMA matrix resin, and the mixture is extruded and granulated through a double-screw extruder.
Example 5
The raw materials and weight ratio of each component in the embodiment are as follows:
90 parts of PA6 cellular polymer (particle size 1mm, bulk density 350 kg/m)3Porosity 20%); 10 parts of transparent epoxy toughening agent.
The method for preparing the transparent toughening master batch in the embodiment is as follows:
the PA6 porous polymer was added to a stirrer and stirred at room temperature with the stirrer speed of 20 rpm. The transparent epoxy toughening agent is added into a stirrer through a canned sprayer and uniformly sprayed on the surface of the PA6 porous polymer, and the spraying time is controlled to be 10 minutes. And after the addition is complete, stirring and mixing for 20 minutes, and then standing until the surface of the PA6 porous polymer is dry and has no greasy feeling, so that the transparent toughened PA6 master batch is obtained. By utilizing the structural characteristics of the PA6 porous polymer, the liquid toughening agent is uniformly dispersed in the internal pore channels of the PA6 porous polymer, the prepared PA6 master batch is blended with PA6 matrix resin, and the mixture is extruded and granulated by a double-screw extruder.
Example 6
The raw materials and weight ratio of each component in the embodiment are as follows:
80 parts of a porous PET polymer (particle size 2mm, bulk density 300 kg/m)3Porosity 30%); 20 parts of hyperbranched silicon compound transparent liquid toughening agent.
The method for preparing the transparent toughening master batch in the embodiment is as follows:
the PET porous polymer is added into a stirrer, and the stirring is carried out at normal temperature, wherein the stirring speed of the stirrer is 80 rpm. Adding the hyperbranched silicon compound toughening agent into a stirrer through a canning sprayer, and uniformly spraying the hyperbranched silicon compound toughening agent on the surface of the PET porous polymer, wherein the spraying time is controlled to be 10 minutes. And after the addition is complete, stirring and mixing for 15 minutes, and then standing until the surface of the PET porous polymer is dry and has no greasy feeling, so that the transparent toughened PET master batch is obtained. By utilizing the structural characteristics of the PET porous polymer, the liquid toughening agent is uniformly dispersed in the internal pore channels of the PET porous polymer, the prepared PET master batch is blended with the PET matrix resin, and the mixture is extruded and granulated by a double-screw extruder.
The transparent toughening master batch prepared in the embodiments 1-6 of the invention is blended with matrix resin thereof, extruded and granulated, and the obtained toughening resin is respectively prepared into standard test samples according to test standards HG/T3841-. The test results are shown in table 1.
TABLE 1 test results of toughened resins and blank samples for each example
Figure BDA0002822990370000051
As can be seen from various test data in Table 1, the transparent toughening master batch provided by the invention has a good toughening effect, can significantly improve the impact strength of matrix resin, does not affect the transparency of matrix material, has a simple preparation process, is less in the addition amount of the transparent toughening master batch in the matrix resin, and can significantly reduce the production cost.
Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the invention as defined by the appended claims. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. The preparation method of the transparent toughening master batch is characterized by comprising the following steps: adding the porous polymer into a stirrer, and stirring at normal temperature; and uniformly spraying the transparent liquid toughening agent on the surface of the porous polymer through a sprayer, controlling the spraying time to be more than 10 minutes, stirring and mixing for 10-30 minutes, and standing until the surface of the porous polymer is dried to obtain the transparent toughening master batch.
2. The preparation method of the transparent toughening master batch according to claim 1, wherein the components are calculated according to parts by weight: 30-90 parts of porous polymer and 10-70 parts of transparent liquid toughening agent.
3. The method for preparing the transparent toughening master batch according to claim 1, wherein the porous polymer is one of a PC porous polymer, a PS porous polymer, a PET porous polymer, a PMMA porous polymer and a PA6 porous polymer.
4. The preparation method of the transparent toughening master batch according to claim 1, wherein the particle size of the porous polymer is 0.5-10 mm, the porosity is not less than 20%, and the bulk density is 50-350 kg/m3。
5. The method for preparing the transparent toughening master batch according to claim 1, wherein the transparent liquid toughening agent is one or more of a hyperbranched silicon compound, a liquid silicone rubber and a transparent epoxy toughening agent.
6. The method for preparing the transparent toughening master batch according to claim 1, wherein the stirring speed of the stirrer is controlled to be 20-300 rpm.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2114663A1 (en) * 1993-02-05 1994-08-06 Joshua B. Sweeney Microporous polymer structures
DE19900487A1 (en) * 1999-01-08 2000-07-13 Cognis Deutschland Gmbh Process for the production of loadable plastic foams
CN102558866A (en) * 2011-12-12 2012-07-11 彭朕财 Liquid transparent toughening agent for plastics
CN104744841A (en) * 2015-03-24 2015-07-01 合肥创新轻质材料有限公司 Adsorption type thermosensitive cross-linking agent masterbatch and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
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CA2114663A1 (en) * 1993-02-05 1994-08-06 Joshua B. Sweeney Microporous polymer structures
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