WO2015141540A1 - ポリフェニレンスルフィド多孔質体およびその製造方法、ポリフェニレンスルフィド-熱可塑性樹脂ブロック共重合体およびその製造方法 - Google Patents
ポリフェニレンスルフィド多孔質体およびその製造方法、ポリフェニレンスルフィド-熱可塑性樹脂ブロック共重合体およびその製造方法 Download PDFInfo
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- WO2015141540A1 WO2015141540A1 PCT/JP2015/057173 JP2015057173W WO2015141540A1 WO 2015141540 A1 WO2015141540 A1 WO 2015141540A1 JP 2015057173 W JP2015057173 W JP 2015057173W WO 2015141540 A1 WO2015141540 A1 WO 2015141540A1
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- polyphenylene sulfide
- thermoplastic resin
- block copolymer
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 291
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 291
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 105
- -1 polyphenylene Polymers 0.000 title claims description 93
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- 238000004519 manufacturing process Methods 0.000 title claims description 65
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- 239000000126 substance Substances 0.000 abstract description 23
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- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical class C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
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- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 4
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- ODPYDILFQYARBK-UHFFFAOYSA-N 7-thiabicyclo[4.1.0]hepta-1,3,5-triene Chemical class C1=CC=C2SC2=C1 ODPYDILFQYARBK-UHFFFAOYSA-N 0.000 description 4
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 235000012239 silicon dioxide Nutrition 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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Images
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Definitions
- the present invention relates to a polyphenylene sulfide porous body and a method for producing the same, and also relates to a polyphenylene sulfide-thermoplastic resin block copolymer and a method for producing the same, and relates to polyphenylene having excellent heat resistance and chemical resistance and excellent balance between mechanical properties and permeation performance.
- the present invention relates to a sulfide porous body.
- Porous materials are used for separation membranes, battery separators, low dielectric constant materials, adsorbents, catalyst carriers, filters, and the like.
- separation membranes are used in the electronics industry, chemical industry, machinery industry, water for process use, production of drinking water by seawater desalination, separation and concentration of useful substances in the manufacture of pharmaceuticals, foods and cosmetics, and medical fields such as artificial kidneys and plasma separation membranes. And is used in a wide range of fields. Recently, it is also being used in the field of environmental energy such as recovery of carbon dioxide gas generated from fossil fuel.
- the membrane separation process does not involve a phase transition such as gas from liquid, it is also attracting attention as a separation process with a small energy load compared to distillation, etc., and can withstand harsh use environments such as high temperature and high pressure.
- separation membranes with excellent heat resistance and chemical resistance.
- Organic membranes and inorganic membranes are known as conventional separation membrane materials, and organic membrane materials such as cellulose acetate, polysulfone, polyethersulfone, polyacrylonitrile, polypropylene, polyamide, and polyvinylidene fluoride are known. Is mentioned. Although conventional organic films have the advantage of higher productivity than inorganic films, there are few materials that can achieve both heat resistance and chemical resistance and low cost, and there are cases where applications are limited.
- examples of the material for the inorganic film include zeolite, ceramic, glass, and metal. (For example, Non-Patent Document 1).
- PPS polyphenylene sulfide
- Patent Documents 5 and 6 As another method for producing a PPS porous body, a method for forming a microporous material by stretching PPS is described (for example, Patent Documents 5 and 6).
- a block copolymer comprising a PPS oligomer having a carboxyl group at the end of the PPS chain and a polyester is also known (for example, Patent Document 7).
- Non-Patent Document 1 Although the inorganic film described in Non-Patent Document 1 has relatively high heat resistance and chemical resistance, since it is difficult to process into a hollow fiber shape, the problem is that the membrane area per unit volume is reduced, and the cost is high. There was a problem that the membrane performance was not stable.
- the block copolymer in the method of Patent Document 7 has been studied for compounding with polyester for the purpose of imparting flexibility to PPS, and the polyester is removed from the block copolymer to obtain a porous body. There is no mention of consideration. Further, even when the polyester is removed from the block copolymer, the PPS of the porous body has a low molecular weight, so that there are problems of low heat resistance and chemical resistance and low mechanical properties.
- An object of the present invention is to provide a PPS porous body having high heat resistance and chemical resistance and having both mechanical properties and permeation performance.
- the polyphenylene sulfide porous body of the present invention has the following constitution. That is, A polyphenylene sulfide porous body having a porous region having a porous structure and a non-porous region having substantially no porous structure on the surface.
- the method for producing a polyphenylene sulfide-thermoplastic resin block copolymer of the present invention has the following constitution. That is, A method for producing a polyphenylene sulfide-thermoplastic resin block copolymer in which a polyphenylene sulfide (A) having a reactive functional group at the terminal, a thermoplastic resin (B), and a bifunctional linking agent (C) are reacted. .
- polyphenylene sulfide-thermoplastic resin block copolymer of the present invention is a polyphenylene sulfide-thermoplastic resin block copolymer in which a polyphenylene sulfide unit and a thermoplastic resin unit are bonded via a linking group containing a secondary alcohol. Polymer.
- the manufacturing method of the polyphenylene sulfide porous body of this invention has the following structure. That is, A method for producing a polyphenylene sulfide porous body in which a thermoplastic resin component is decomposed and removed from the polyphenylene sulfide-thermoplastic resin block copolymer or the polyphenylene sulfide-thermoplastic resin block copolymer obtained by the production method.
- the average area ratio of the porous region on the surface is preferably 10 to 80%.
- the nonporous region is preferably continuous on the surface.
- the porous polyphenylene sulfide of the present invention preferably has a porosity of 10 to 80%.
- the porous polyphenylene sulfide of the present invention is preferably composed of polyphenylene sulfide having a number average molecular weight (Mn) of 6,000 to 100,000.
- the reactive functional group of polyphenylene sulfide (A) is an amino group, carboxyl group, hydroxyl group, mercapto group, isocyanato group, silanol group, acid anhydride It is preferably a group selected from the group consisting of a physical group, an epoxy group, and derivatives thereof.
- the bifunctional linking agent (C) is preferably an epoxy resin.
- the epoxy resin preferably contains a halogen atom.
- the number average molecular weight of the epoxy resin is preferably 300 or more.
- the epoxy resin preferably has an epoxy equivalent of 200 g / ep or more.
- the polyphenylene sulfide unit and the linking group are bonded via a structure selected from the group consisting of secondary amine, ester, ether, sulfide, amide and siloxane. It is preferable.
- the linking group preferably contains a halogen atom.
- the number average molecular weight (Mn) of the polyphenylene sulfide unit is preferably in the range of 6,000 to 100,000.
- the polyphenylene sulfide-thermoplastic resin block copolymer of the present invention preferably has a number average molecular weight (Mn) in the range of 10,000 to 2,000,000.
- PPS porous body in the present invention has, on its surface, a porous region having a porous structure and a non-porous region having substantially no porous structure.
- the porous region is a scanning electron microscope (SEM) image obtained by observing the surface of a porous body, and is a porous structure in which the distance between pores is 5 times or less of the pore diameter and at least three adjacent pores are gathered.
- SEM scanning electron microscope
- This is a circumscribed area, and specifically refers to an area where a large number of holes exist as shown in 1 of FIG.
- the inter-hole distance refers to the shortest linear distance between the outer peripheral part of the hole and the outer peripheral part of the adjacent hole.
- hole refers to the space
- the non-porous region having substantially no porous structure refers to a region other than the porous region as shown in 2 of FIG. 1, that is, a region in which the distance between pores is 5 times or more.
- the porous region has a function as a flow path when filling or transmitting a fluid such as gas or liquid from the outside to the inside of the PPS porous body or from the inside to the outside.
- the non-porous region has a function as a support portion that improves mechanical strength such as tension, compression, and bending of the PPS porous body. Therefore, by using a PPS porous body having a porous region and a non-porous region on the surface, both mechanical strength and fluid permeation performance can be achieved.
- the average area ratio of the porous region is 10 to 80% because both mechanical characteristics and fluid permeation performance can be achieved.
- the average area ratio of the porous region is more preferably 20% or more, and further preferably 30% or more.
- the average area ratio of the porous region is more preferably 75% or less, and further preferably 70% or less.
- the average area ratio of the porous region refers to the area of the porous region (S) and the entire surface area (S ′) in an image obtained by observing the surface of the PPS porous body with a scanning electron microscope at a magnification of 1,300 times. ),
- the area ratio of the porous region calculated by the following equation is measured at an arbitrary 10 points, and the average value is taken.
- the reason why the mechanical properties are improved when the area ratio of the porous region is within the above range is estimated as follows.
- a porous body with a high average area ratio of the porous region cracks are generated in the hole branches when an external force such as tension, compression, bending, etc. is applied, which makes the whole structure easy. Destroyed.
- the porous body having a low average area ratio of the porous region is less likely to be destroyed because the non-porous region on the surface has a function of retaining the entire structure of the PPS porous body. Therefore, it is preferable that the non-porous region is continuous on the surface because the mechanical strength is improved.
- the nonporous region is continuous on the surface, as shown in FIG. 1, the nonporous region is the sea component, and the porous region is the island component.
- the tensile strength is preferably 50 MPa or more.
- the porosity of the PPS porous body of the present invention is preferably 10 to 80%.
- the porosity is a volume fraction of the pores with respect to the volume of the PPS porous body, and can be obtained by the following equation.
- Porosity (%) ⁇ (apparent volume ⁇ actual volume) / apparent volume ⁇ ⁇ 100
- the apparent volume is the volume of the entire PPS porous body including pores.
- an actual volume is a volume which a resin component occupies among PPS porous bodies, and calculates
- the porosity of the PPS porous body is within the above preferred range, the pressure loss when the fluid permeates the porous body is reduced, and the permeation performance can be improved. In addition, the efficiency of adsorption and desorption of substances can be increased, and the filling efficiency can be increased when compounding with other materials. On the other hand, mechanical strength such as tension, compression and bending is not impaired.
- the porosity is more preferably 20% or more, and further preferably 30% or more. Further, the porosity is more preferably 70% or less, and further preferably 65% or less.
- the PPS porous body produced by the stretching method is oriented in a specific direction, it has anisotropy in mechanical properties.
- the PPS porous body of the present invention has an isotropic structure, etc. The mechanical properties are excellent.
- the average pore diameter of the PPS porous material of the present invention is not particularly limited, but examples thereof include a range of 0.01 to 1 ⁇ m.
- the average pore diameter was observed with a scanning electron microscope at a magnification of 100,000 times at any 10 cross-sections in which the PPS porous body was formed by the cross section polisher method (CP method)
- the pore size in each observation image was The diameter is measured, and the average value is taken as the average pore diameter.
- the PPS porous body of the present invention may contain subcomponents such as resin components and additives other than PPS.
- the subcomponent may be simply mixed with PPS, or may be bonded to PPS by a chemical bond.
- a component containing a halogen atom is contained as a subcomponent, the flame retardancy of the PPS porous body is improved, and among them, a component containing a bromine atom is more preferred.
- Inclusion of a halogen atom can be detected by, for example, energy dispersive X-ray spectroscopy (EDX).
- EDX energy dispersive X-ray spectroscopy
- it is preferable that a fibrous filler is contained as another subcomponent because the mechanical strength of the PPS porous body can be further improved.
- the number average molecular weight (Mn) of the PPS of the PPS porous material of the present invention is 6,000 or more, the PPS inherent heat resistance and chemical resistance are exhibited, and the porous material has excellent mechanical properties such as mechanical strength and durability.
- 10,000 or more is more preferable, and 15,000 or more is more preferable because a mass is obtained.
- the upper limit of the number average molecular weight is not particularly limited, but is preferably 100,000 or less because of excellent moldability.
- the molecular weight of PPS is measured by gel permeation chromatography, which is a type of size exclusion chromatography, and is calculated in terms of polystyrene.
- said number average molecular weight (Mn) means the number average molecular weight of PPS containing the said other structural component, when other structural components, such as a coupling agent, are connected with the PPS porous body.
- the macro form of the PPS porous body is not particularly limited, and various forms such as a fiber, a film, a sheet, a resin molded product, and a powder can be employed.
- a separation membrane it is preferably used as a hollow fiber membrane or a sheet-like flat membrane, and a hollow fiber membrane is particularly preferred because the membrane area per module increases.
- the fluid permeation performance is higher than that of a structure having only a non-porous region on the surface.
- the permeation performance is a permeation amount when a fluid permeates from one surface of the porous body to the other surface per unit time and unit area under a certain pressure, that is, a permeation flow rate.
- the PPS-thermoplastic resin block copolymer of the present invention comprises a polyphenylene sulfide (A ), The thermoplastic resin (B), and the bifunctional linking agent (C), and the component of the thermoplastic resin (B) is removed from the block copolymer.
- A polyphenylene sulfide
- B thermoplastic resin
- C bifunctional linking agent
- PPS (A) is a prepolymer having a repeating structure of a phenylene sulfide unit represented by the following general formula (I) and having a reactive functional group at the terminal.
- the reactive functional group at the PPS end refers to a functional group that can react with a linking agent to form a chemical bond.
- the reactive functional group at the PPS end is a functional group selected from the group consisting of amino group, carboxyl group, hydroxyl group, mercapto group, isocyanato group, silanol group, acid anhydride group, epoxy group and derivatives thereof. Is preferred. If the terminal structure of the PPS is such a reactive functional group, the reactivity with the linking agent is high, and the block copolymerization reaction between the PPS and the thermoplastic resin can proceed in a short time with high efficiency.
- a PPS-thermoplastic resin block copolymer having thermoplasticity can be produced.
- a functional group selected from an amino group, a carboxyl group, a hydroxyl group, and a mercapto group can be particularly preferably exemplified.
- a method of adding a sulfide compound (functional group introducing agent) having a reactive functional group when polymerizing PPS, or a reactive functional group after polymerizing PPS is a method in which a sulfide compound (functional group introducing agent) having a reaction is added and reacted.
- sulfide compounds include bis (4-aminophenyl) sulfide, bis (4-carboxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfide, and oligomers thereof.
- the number average molecular weight (Mn) of PPS (A) used for the block copolymerization reaction in the present invention is preferably 6,000 to 100,000. If the number average molecular weight is within this range, the PPS porous body obtained can have an equivalent number average molecular weight, and a PPS porous body excellent in heat resistance, chemical resistance and mechanical properties can be obtained.
- thermoplastic resin (B) of the present invention can be reacted with the bifunctional linking agent (C) to form a chemical bond, and is hydrolyzed, pyrolyzed, and oxidatively decomposed under the condition that PPS is not decomposed.
- Any thermoplastic resin can be used as long as it is not particularly limited.
- thermoplastic resins include polyester, polycarbonate, polyamide, liquid crystal polymer, polyphenylene ether, polyimide, polyetherimide, polysulfone, polyethersulfone, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyvinyl chloride , Polyacrylonitrile, polyvinyl alcohol, polyacetal, polyarylate, elastomer, polymethyl methacrylate, epoxy resin and the like.
- the reactive functional group that reacts with the bifunctional linking agent can be used after being modified by chemical bonding to the thermoplastic resin.
- the thermoplastic resin (B) is preferably a resin having high thermal stability and easy decomposition and removal. Therefore, polyester, polycarbonate, polyamide, liquid crystal polymer, and polyarylate are preferable, and polyester, polycarbonate, and polyamide are more preferable from the viewpoint of cost. Among these, aromatic polyesters are more preferable because they have relatively high heat resistance and can be easily hydrolyzed and removed with an aqueous alkali solution.
- thermoplastic resin (B) any polyester may be used as long as it is a polyester obtained by polymerizing a dicarboxylic acid or dicarboxylic acid alkyl ester and a diol, or a polyester obtained by polymerizing a lactide.
- the use of polyethylene terephthalate or polybutylene terephthalate obtained by using an acid or its dimethyl ester and ethylene glycol or 1,4-butanediol is preferable because a PPS porous body can be produced at low cost.
- any polycarbonate can be obtained by a phosgene method in which a dihydroxydiaryl compound and phosgene are reacted or a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted.
- a polycarbonate produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and phosgene may be mentioned, for example, a polycarbonate produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and phosgene.
- thermoplastic resin (B) polylactams obtained by ring-opening polymerization of cyclic lactam, polyamides obtained by polycondensation of ⁇ -aminocarboxylic acid, and polyamides obtained by polycondensation of diamine and dicarboxylic acid
- Any of semi-aromatic polyamides may be used, and examples thereof include nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 6/612, and the like.
- melt viscosity of PPS and thermoplastic resin generally, the closer the melt viscosity of PPS and thermoplastic resin is, that is, the closer the melt viscosity ratio of PPS and thermoplastic resin is to 1, the closer PPS and thermoplastic resin are.
- the melt viscosity means the viscosity at the temperature and shear rate during the reaction.
- a bifunctional linking agent (C) is used as a linking agent for block copolymerization of PPS (A) and the thermoplastic resin (B).
- the linking agent in the present invention is a compound or resin having two reactive functional groups in the molecule that can react with PPS or a thermoplastic resin to form a chemical bond.
- the functional group include an epoxy group, an oxazoline group, an isocyanato group, a silanol group, an alkoxysilane group, an amino group, a carboxyl group, an acid anhydride group, and a carbodiimide.
- the block copolymer when there are three or more reactive functional groups in the molecule, there is a case where the block copolymer cannot be obtained by reacting with PPS and a thermoplastic resin to be crosslinked. Therefore, in order to produce a thermoplastic block copolymer, it is necessary to be a bifunctional linking agent.
- the reactive functional group of the linking agent is an epoxy group, that is, if the linking agent is an epoxy resin, it reacts with various functional groups such as amine, carboxylic acid, alcohol, aromatic alcohol, thiol, isocyanate, silanol, and acid anhydride to chemistry. It is preferable because a bond can be formed and the reaction can proceed in a short time and with high efficiency.
- an epoxy resin in the case of using an epoxy resin as a coupling agent will be described in detail in the section (4).
- the linking agent preferably contains a halogen atom in the molecule. Since halogen atoms have a larger atomic weight than carbon atoms, nitrogen atoms, and oxygen atoms, the inclusion of halogen atoms increases the molecular weight of the linking agent and causes sublimation and evaporation during the production of PPS-thermoplastic resin block copolymers. It becomes possible to suppress. Further, the flame retardancy of the PPS-thermoplastic resin block copolymer can be improved by utilizing the self-extinguishing property of the halogen atom.
- the number of halogen atoms contained in one molecule of the linking agent is not particularly limited, and a linking agent containing one or more halogen atoms in the molecule can be used.
- the heat resistance of the linking agent means that the linking agent has high thermal stability in a nitrogen atmosphere at 300 ° C. and 1 atm. Specifically, in a thermogravimetry (TG) apparatus, the weight retention rate is 50 wt. % Or more. Here, the weight retention is calculated by the following equation. The weight retention is preferably 75% by weight or more because the heat resistance of the linking agent becomes higher and the reaction rate of the block copolymerization reaction is improved.
- Weight retention (% by weight) (post-measurement binder weight (g)) / (pre-measurement binder weight (g)) ⁇ 100
- a PPS-thermoplastic resin block copolymer when producing a PPS-thermoplastic resin block copolymer, it can be produced under non-catalytic conditions, but the reaction can also be carried out in the presence of a catalyst.
- a catalyst When a catalyst is added, PPS and a thermoplastic resin react directly, and it has the effect that the reaction rate of a block copolymerization reaction improves.
- Examples of the catalyst that can be used in the production method include a catalyst used in producing a polyester, specifically, manganese, cobalt, used as a catalyst for an esterification reaction in producing a polyester, Compounds such as zinc, titanium, calcium, etc., compounds used for transesterification, such as magnesium, manganese, calcium, cobalt, zinc, lithium, titanium, and further used for polymerization reactions, antimony, titanium, aluminum, tin, A compound such as germanium can be exemplified.
- the PPS component and the thermoplastic resin component are not only connected via a connecting agent, but terminal structures derived from the repeating units of each component may be directly connected to each other.
- a plurality of PPS units and thermoplastic resin units may be present in one molecule of the block copolymer. That is, not only a diblock copolymer or a triblock copolymer but also a multiblock copolymer of tetrablock or more may be used.
- the mixing ratio of the PPS (A), the thermoplastic resin (B), and the bifunctional linking agent (C) can be set as appropriate, but the PPS is 10 to 90 wt% relative to the total weight of the PPS, the thermoplastic resin, and the linking agent. %, And more preferably 20 to 80% by weight.
- the mixing ratio of PPS is within this preferable range, the reaction rate of the block copolymerization reaction tends to be high, and the morphology tends to be uniform.
- the thermoplastic resin is preferably 10 to 95% by weight, more preferably 20 to 90% by weight, based on the total weight.
- thermoplastic resin when the PPS and the thermoplastic resin are block copolymerized, the thermoplastic resin is less likely to become a dispersed component (island component), and the thermoplastic resin component can be removed to make it porous. It becomes easy.
- the mixing ratio of the linking agent is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight, based on the total weight.
- the mixing ratio of the linking agent is preferably determined appropriately from the number average molecular weight of PPS or thermoplastic resin, the number of functional groups in the molecular chain, and the like.
- the order in which the binder is added is not particularly limited, and may be mixed and reacted simultaneously with the PPS and the thermoplastic resin, or after the PPS and the binder or the thermoplastic resin and the binder are mixed and reacted in advance. Furthermore, it is also possible to mix and react a thermoplastic resin or PPS. Moreover, you may add a coupling agent, after mixing PPS and a thermoplastic resin previously.
- the temperature at which a mixture containing PPS, a thermoplastic resin, and a binder is heated and reacted depends on the molecular weight of PPS, the type and molecular weight of the thermoplastic resin, the type and molecular weight of the binder, etc.
- the temperature is preferably equal to or higher than the temperature at which the thermoplastic resin melts. As a specific example, it is preferably 290 ° C. or higher, and more preferably 295 ° C. or higher.
- an upper limit of reaction temperature it can illustrate that it is 400 degrees C or less, It is preferable that it is 380 degrees C or less, It is more preferable that it is 350 degrees C or less, It is further more preferable that it is 320 degrees C or less.
- reaction temperature is in such a preferable range, thermal decomposition of PPS and the thermoplastic resin can be suppressed during the reaction, and sublimation, evaporation, and thermal decomposition of the binder can be suppressed.
- the temperature at which PPS and the thermoplastic resin melt can be measured by a differential scanning calorimeter (DSC).
- the polymerization atmosphere in the production method of the PPS-thermoplastic resin block copolymer of the present invention is, for example, a reaction under an inert atmosphere such as nitrogen, helium or argon, or a reaction under reduced pressure or high pressure. It can be adopted as appropriate.
- an organic polar solvent may be included in the reaction system during the block copolymerization reaction.
- the organic polar solvent means a solvent in which at least a part of PPS, thermoplastic resin and linking agent can be dissolved at the reaction temperature.
- the reaction temperature when using an organic polar solvent may be any temperature at which PPS and thermoplastic resin dissolve, but is preferably 180 ° C. or higher, more preferably 200 ° C. or higher.
- the upper limit of the reaction temperature is not particularly limited, but is preferably 260 ° C or lower, and more preferably 250 ° C or lower. If it is below the upper limit of the said preferable reaction temperature, there is no possibility that a coupling agent will decompose
- additives may be added to the PPS-thermoplastic resin block copolymer as long as the object of the present invention is not impaired.
- These other additives include fibrous inorganic fillers, non-fibrous inorganic fillers, fibrous organic fillers, sizing agents, silane coupling agents, antiwear agents, mold release agents, anti-coloring agents, plasticizers, Antioxidants, UV absorbers, heat stabilizers, lubricants, mold release agents, antistatic agents, antiblocking agents, colorants including dyes and pigments, flame retardants, flame retardant aids, foaming agents, antibacterial agents, etc. It is done. It is preferable to add a fibrous filler because the mechanical strength of the PPS porous body can be improved.
- the PPS-thermoplastic resin block copolymer can adopt various shapes such as resin molded products, films, sheets, fibers, and powders. In the case of a fiber or a film, it can be stretched.
- the PPS porous body may be produced by any method as long as the thermoplastic resin component can be chemically decomposed and removed from the PPS-thermoplastic resin block copolymer, and any method such as hydrolysis, thermal decomposition, or oxidative decomposition is used. be able to. Among these, the method of removing by hydrolysis is preferably used.
- thermoplastic resin (B) When polyester, polycarbonate, or polyamide is used as the thermoplastic resin (B), swelling of the matrix component by the solvent can be suppressed as long as it is a method of hydrolyzing and removing with an acidic aqueous solution or an alkaline aqueous solution. This is preferable because the removal time can be shortened.
- an alkaline aqueous solution is more preferable because hydrolysis efficiency is high and removal in a short time is possible.
- polyamide it is preferable to remove with acidic aqueous solution.
- alkaline aqueous solution Although it does not specifically limit about the kind of alkaline aqueous solution, It is preferable to use the hydroxide of an alkali metal, the hydroxide of an alkaline-earth metal, and from the balance of cost, availability, and a hydrolysis rate, sodium hydroxide, It is preferable to use potassium hydroxide.
- the concentration of the alkaline aqueous solution is preferably in the range of 0.10 to 10M.
- concentration of the alkaline aqueous solution is within the above preferred range, the time required for decomposition and removal can be reduced, while the viscosity of the aqueous solution does not become too high and the efficiency of decomposition and removal does not decrease.
- the temperature of the alkaline aqueous solution is preferably 60 to 120 ° C. from the viewpoint of the hydrolysis rate of the thermoplastic resin component, and from the viewpoint of removal efficiency, treatment under pressure and stirring of the aqueous solution are also preferred.
- the treatment liquid After removing the thermoplastic resin component, it is preferable to remove the remaining treatment liquid with an appropriate solvent. For example, when treatment with an acid or aqueous alkali solution is used, the treatment liquid is washed with ion-exchanged water after the treatment and then dried. It is preferable.
- thermoplastic resin component in the block copolymer is decomposed and removed to form pores, while the PPS component is not decomposed to form branches and non-porous regions in the porous region. Therefore, the PPS porous body of the present invention can be manufactured.
- Production method of PPS (A) As an example of the production method of PPS (A), cyclic PPS (a) is heated in the presence of a sulfide compound having a reactive functional group. Production method (A1) and production method (A2) of PPS (A) in which a mixture containing at least a sulfidizing agent, a dihalogenated aromatic compound, an organic polar solvent, and a monohalogenated compound having a reactive functional group is heated.
- the addition amount of the sulfide compound in the production method (A1) of PPS (A) is preferably 0.01 to 25 mol% per mol of the phenylene sulfide structural unit of cyclic PPS (a), preferably 0.01 to 15 mol. % Is more preferable, 0.01 to 10 mol% is more preferable, and 0.01 to 5 mol% is particularly preferable.
- the addition amount of the sulfide compound is within the above preferable range, the introduction of the reactive functional group into the obtained PPS is sufficient, while there is no disadvantage such as a decrease in the molecular weight of the obtained PPS and an increase in raw material cost.
- the heating temperature for producing PPS (A) by the production method (A1) is preferably a temperature at which the reaction mixture composed of the cyclic PPS (a) and the sulfide compound having a reactive functional group melts. Under such temperature conditions, an excessively long time is not required to obtain PPS (A).
- the temperature at which the cyclic PPS (a) melts cannot be uniquely indicated because it varies depending on the composition and molecular weight of the cyclic PPS (a) and the environment during heating. By analyzing a) with a differential scanning calorimeter, it is possible to grasp the melting solution temperature.
- heating temperature 180 ° C or more can be illustrated, preferably 200 ° C or more, more preferably 220 ° C or more, still more preferably 240 ° C or more.
- the lower limit of the heating temperature is within this preferred temperature range, the cyclic PPS (a) is melted and dissolved, and PPS (A) can be obtained in a short time.
- heating temperature 400 degrees C or less can be illustrated, Preferably it is 360 degrees C or less, More preferably, it is 340 degrees C or less. If the upper limit of the heating temperature is equal to or lower than this temperature, adverse effects on the properties of PPS (A) obtained by an undesirable side reaction tend to be suppressed.
- the reaction time varies depending on the content of the cyclic compound in the cyclic PPS (a) to be used, the number of repetitions (i), various characteristics such as molecular weight, the type of sulfide compound used, and the conditions such as the heating temperature. Therefore, although it cannot be defined uniformly, it is preferable to set so that the above-mentioned undesirable side reaction does not occur.
- the heating time include 0.01 to 100 hours, preferably 0.05 to 20 hours, and more preferably 0.05 to 10 hours.
- the heating of the cyclic PPS (a) in the presence of a sulfide compound having a reactive functional group can also be performed under conditions that do not substantially contain a solvent.
- the temperature can be raised in a short time, the reaction rate is high, and PPS (A) tends to be easily obtained in a short time.
- the substantially solvent-free condition means that the solvent is 10 wt% or less with respect to the cyclic PPS (a), and more preferably 3 wt% or less.
- the polymerization reaction of PPS (A) may be performed in a mold for producing a molded product as well as performed by a method using a normal polymerization reaction apparatus, or performed using an extruder or a melt kneader. Any apparatus equipped with a heating mechanism can be used without particular limitation, and known methods such as a batch method and a continuous method can be employed.
- the reaction is preferably performed in a non-oxidizing atmosphere, and is preferably performed under reduced pressure.
- it is preferable to make it the pressure reduction conditions after making the atmosphere in a reaction system once non-oxidizing atmosphere.
- the non-oxidizing atmosphere is an atmosphere in which the oxygen concentration in the gas phase in contact with the cyclic PPS is 5% by volume or less, preferably 2% by volume or less, and more preferably contains substantially no oxygen, that is, nitrogen, helium, argon, etc.
- a nitrogen atmosphere is preferred from the viewpoints of economy and ease of handling.
- 50 kPa or less is preferable, 20 kPa or less is more preferable, and 10 kPa or less is more preferable.
- 0.1 kPa or more can be illustrated and 0.2 kPa or more is more preferred.
- the reaction can be performed under pressure.
- the atmosphere in the reaction system is once changed to a non-oxidizing atmosphere and then the pressure is changed.
- the pressurized condition means that the inside of the system in which the reaction is carried out is higher than atmospheric pressure, and there is no particular upper limit, but 0.2 MPa or less is preferable from the viewpoint of easy handling of the reaction apparatus.
- This production method (A1) is a production method in which the introduction rate of the terminal reactive functional group of PPS is high and the molecular weight can be increased. Therefore, the yield in the block copolymerization reaction can be improved, and the block copolymer can have a high molecular weight.
- A2 Production method of PPS (A)
- A2 As a second preferred production method of PPS (A), a production method (A2) in which a mixture containing at least a sulfidizing agent, a dihalogenated aromatic compound, an organic polar solvent, and a monohalogenated compound having a reactive functional group is heated. Is mentioned.
- the amount of the dihalogenated aromatic compound used in the production method (A2) is 0.8 mol or more and 1.5 mol per mol of the sulfidizing agent from the viewpoint of suppressing decomposition and efficiently obtaining PPS having a viscosity suitable for processing.
- the range is less than, preferably 0.9 mol or more and less than 1.1 mol, more preferably 0.95 mol or more and less than 1.05 mol.
- the amount of the organic polar solvent used as the polymerization solvent for PPS is not particularly limited, but from the viewpoint of stable reactivity and economy, 2.5 mol or more per mol of the sulfidizing agent.
- a monohalogenated compound having a reactive functional group is added when producing PPS.
- the amount of the monohalogenated compound used is 0.01 per mol of the dihalogenated aromatic compound. It is preferably in the range of ⁇ 10 mol%, more preferably in the range of 0.1 to 8 mol%, and further preferably in the range of 1 to 5 mol%.
- the amount of the monohalogenated compound is within the above preferred range, the introduction rate of the reactive terminal in the resulting PPS (A) does not tend to be low, while the molecular weight of PPS is reduced and mechanical properties are not exhibited. Nor.
- the total amount of halogenated compounds such as dihalogenated aromatic compounds and monohalogenated compounds is preferably within a specific range, and the total amount of halogenated compounds is 0.98 mol or more per 1 mol of the sulfidizing agent.
- the amount is preferably less than 1.10 mol, more preferably from 1.00 mol to less than 1.08 mol, and even more preferably from 1.03 mol to less than 1.07 mol.
- the addition timing of the monohalogenated compound is not particularly limited, and it may be added at any time during the dehydration step, at the start of polymerization, or during polymerization.
- the addition time of the monohalogenated compound is preferably a time when the conversion rate of the dihalogenated aromatic compound is less than 80%, and a time when it is less than 70%. Is more preferable. From this point of view, it is most preferable to add from the completion of the dehydration step to the start of polymerization, at the start of polymerization, that is, simultaneously with the dihalogenated aromatic compound.
- the sulfidizing agent can be used in the form of a hydrate or an aqueous mixture.
- the organic polar solvent and the sulfide are used before adding the dihalogenated aromatic compound or monohalogenated compound. It is preferable to carry out a dehydration step in which the temperature of the mixture containing the agent is raised to remove excess water out of the system.
- the dehydration method is not particularly limited, but desirably, an alkali metal hydrosulfide and an alkali metal hydroxide are used as an organic polar solvent in an inert gas atmosphere at a temperature ranging from room temperature to 150 ° C., preferably from room temperature to 100 ° C.
- the temperature is raised to at least 150 ° C. or more, preferably 180 to 260 ° C. under normal pressure or reduced pressure, and water is distilled off.
- the amount of water in the system at the stage when this dehydration step is completed is preferably 0.9 to 1.1 mol per mol of the fed sulfiding agent.
- the amount of water in the system is an amount obtained by subtracting the amount of water removed from the system from the amount of water charged in the dehydration step.
- a polymerization step is performed in which the reaction product prepared in the dehydration step is brought into contact with a dihalogenated aromatic compound or a monohalogenated compound in an organic polar solvent to cause a polymerization reaction.
- the sulfiding agent and the polyhalogenated aromatic compound are added to the organic polar solvent, desirably in an inert gas atmosphere at a temperature of 100 to 220 ° C., preferably 130 to 200 ° C. These raw materials may be charged in any order or simultaneously.
- This polymerization reaction is preferably performed in a temperature range of 200 ° C. or higher and lower than 280 ° C.
- the reaction is continued for a certain time at 245 ° C. or more and less than 280 ° C.
- the reaction is performed at a constant temperature at 200 ° C. or more and less than 245 ° C. for a certain time.
- the reaction is continued for a certain period of time by raising the temperature to 245 ° C. or more and less than 280 ° C., after performing the reaction at a constant temperature at 200 ° C. or more and less than 245 ° C., particularly 230 ° C. or more and less than 245 ° C.
- Examples include a method of raising the temperature to less than 280 ° C. and completing the reaction in a short time.
- the atmosphere in which the above-described polymerization reaction is performed is preferably a non-oxidizing atmosphere, and is preferably performed in an inert gas atmosphere such as nitrogen, helium, and argon, particularly from the viewpoint of economy and ease of handling. It is preferable to carry out in a nitrogen atmosphere.
- the reaction pressure in the polymerization reaction is not particularly limited because it cannot be defined unconditionally depending on the type and amount of raw materials and solvent used, or the polymerization reaction temperature.
- PPS (A) can be recovered from the polymerization reaction product obtained by the above-described method and used for the block copolymerization reaction.
- the above-described polymerization reaction product contains PPS and an organic polar solvent, and may contain unreacted raw materials, water, by-product salts and the like as other components.
- There is no particular limitation on the method for recovering PPS from such a reaction mixture For example, if necessary, a part or most of the organic polar solvent is removed by an operation such as distillation, and then the solubility in PPS components is low and organic.
- a method of recovering PPS (A) as a solid by mixing with a polar solvent and bringing it into contact with a solvent having a solubility in by-product salt as necessary under heating can be exemplified.
- Solvents having such characteristics are generally relatively polar solvents, and preferred solvents differ depending on the type of organic polar solvent and by-product salt used, but are not limited.
- water, methanol, ethanol, propanol, isopropanol Alcohols typified by butanol and hexanol, ketones typified by acetone, methyl ethyl ketone, and acetates typified by ethyl acetate, butyl acetate, etc., and water, methanol and Acetone is preferred and water is particularly preferred.
- PPS (A) It is possible to reduce the amount of organic polar solvent and by-product salt contained in PPS (A) by performing the treatment with such a solvent. Since PPS (A) is precipitated as a solid component by this treatment, it can be recovered using a known solid-liquid separation method. Examples of the solid-liquid separation method include separation by filtration, centrifugation, and decantation. These series of treatments can be repeated several times as necessary, and the amount of the organic polar solvent and by-product salt contained in the PPS (A) tends to be further reduced.
- a method of treatment with the above-mentioned solvent there is a method of mixing a solvent and a polymerization reaction product, and it is possible to appropriately stir or heat as necessary.
- the temperature at the time of treatment with a solvent is preferably 20 to 220 ° C, more preferably 50 to 200 ° C. In such a range, for example, by-product salt can be easily removed, and the treatment can be performed at a relatively low pressure, which is preferable.
- the water when water is used as the solvent, the water is preferably distilled water or deionized water, but if necessary, formic acid, acetic acid, propionic acid, butyric acid, chloroacetic acid, dichloroacetic acid, acrylic acid, crotonic acid, Organic acidic compounds such as benzoic acid, salicylic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, fumaric acid, and their alkali metal salts, alkaline earth metal salts, sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid, silicic acid, etc. It is also possible to use an aqueous solution containing a compound and ammonium ions.
- Cyclic PPS (a)
- the cyclic PPS contained in the cyclic PPS (a) used in the production method (A1) of PPS (A) has a repeating unit of formula, — (Ph—S) — (Ph is a phenylene group) as a main structural unit.
- it is a cyclic compound represented by the following general formula (II) containing 80 mol% or more of the repeating unit.
- the cyclic PPS (a) contains at least 50% by weight of the cyclic PPS of the general formula (II), preferably 70% by weight or more, more preferably 80% by weight or more, and further preferably 90% by weight. What contains the above is preferable.
- the upper limit of the weight fraction of the cyclic PPS contained in the cyclic PPS (a) is not particularly limited, but 98% by weight or less, preferably 95% by weight or less can be exemplified as a preferred range.
- the higher the weight fraction of cyclic PPS in cyclic PPS (a) the higher the molecular weight of PPS obtained after heating.
- the weight fraction of cyclic PPS in cyclic PPS (a) exceeds the above-described upper limit value, the melt solution temperature tends to increase.
- the conversion of the cyclic PPS to PPS by heating is preferably performed at a temperature equal to or higher than the temperature at which the cyclic PPS melts.
- the melt temperature of the cyclic PPS increases.
- the conversion of cyclic PPS to PPS can be performed at a lower temperature.
- the cyclic PPS may be either a single compound having a single repeat number or a mixture of cyclic compounds having different repeat numbers, but a mixture of cyclic compounds having different repeat numbers is a single repeat.
- the melting solution temperature tends to be lower than that of a single compound having a number, and the use of a mixture of cyclic compounds having different numbers of repetitions is preferable because the temperature at the time of conversion to PPS can be lowered.
- components other than cyclic PPS in cyclic PPS (a) are PPS oligomers.
- the PPS oligomer is a linear homo-oligomer or co-oligomer having a repeating unit of the formula, — (Ph—S) —, as a main constituent unit, and preferably containing 80 mol% or more of the repeating unit.
- the molecular weight of the PPS oligomer include those having a molecular weight lower than that of PPS. Specifically, the number average molecular weight is preferably less than 5,000.
- Sulfide Compound The sulfide compound used in the production method (A1) of PPS (A) is a sulfide compound having a reactive functional group represented by the following general formula (III).
- At least one of X and Y in the formula (III) is a reactivity selected from an amino group, a carboxyl group, a hydroxyl group, a mercapto group, an isocyanato group, a silanol group, an acid anhydride group, an epoxy group, or a derivative thereof.
- a functional group preferably a reactive functional group selected from an amino group, a carboxyl group, and a hydroxyl group.
- the other functional group is not particularly limited, and examples thereof include a hydrogen group or a halogeno group.
- the repeating number p in the sulfide compound represents an integer of 0 to 20.
- p is preferably an integer of 0 to 15, more preferably 0 to 10.
- the repeating number p is in the above preferred range, the solubility with the cyclic PPS and the low viscosity property are not impaired.
- the mixture of the sulfide compound which has different repeating number p can also be used.
- sulfide compounds include bis (2-aminophenyl) sulfide, bis (3-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (2-carboxyphenyl) sulfide, bis (3 -Carboxyphenyl) sulfide, bis (4-carboxyphenyl) sulfide, bis (2-hydroxyphenyl) sulfide, bis (3-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy-3- Methylphenyl) sulfide, 5,5′-thiodisalicylic acid, 2,2 ′, 4,4′-tetrahydroxydiphenylsulfide and the like, and oligomers thereof are also included.
- bis (4-aminophenyl) sulfide, bis (4-carboxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfide, and oligomers thereof are more preferably used from the viewpoint of reactivity and crystallinity. . Moreover, these sulfide compounds may be used alone or in combination of two or more.
- Sulfiding agent The sulfidizing agent used in the production method (A2) of PPS (A) may be any as long as it can introduce a sulfide bond into a dihalogenated aromatic compound.
- an alkali metal sulfide examples include alkali metal hydrosulfides and hydrogen sulfide.
- alkali metal sulfide examples include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and a mixture of two or more thereof, among which lithium sulfide and / or sodium sulfide are preferable.
- Sodium sulfide is more preferably used.
- These alkali metal sulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides.
- the aqueous mixture refers to an aqueous solution, a mixture of an aqueous solution and a solid component, or a mixture of water and a solid component. Since generally available inexpensive alkali metal sulfides are hydrates or aqueous mixtures, it is preferable to use such forms of alkali metal sulfides.
- alkali metal hydrosulfide examples include, for example, lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide and a mixture of two or more thereof, among them lithium hydrosulfide and Sodium hydrosulfide is preferred, and sodium hydrosulfide is more preferably used.
- alkali metal sulfides prepared from a reaction system from alkali metal hydrosulfides and alkali metal hydroxides can be used.
- an alkali metal sulfide prepared by previously contacting an alkali metal hydrosulfide and an alkali metal hydroxide can also be used.
- These alkali metal hydrosulfides and alkali metal hydroxides can be used as hydrates or aqueous mixtures, or in the form of anhydrides. From the viewpoint of availability and cost of hydrates or aqueous mixtures. preferable.
- alkali metal sulfides prepared in the reaction system from alkali metal hydroxides such as lithium hydroxide and sodium hydroxide and hydrogen sulfide can also be used.
- alkali metal sulfides prepared by previously contacting alkali metal hydroxides such as lithium hydroxide and sodium hydroxide with hydrogen sulfide can also be used.
- Hydrogen sulfide can be used in any form of gas, liquid, and aqueous solution.
- alkali metal hydroxide and / or an alkaline earth metal hydroxide in combination with the sulfidizing agent.
- alkali metal hydroxide include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and a mixture of two or more thereof.
- metal hydroxide include, for example, calcium hydroxide, strontium hydroxide, barium hydroxide, and sodium hydroxide is preferably used.
- an alkali metal hydrosulfide is used as the sulfidizing agent, it is particularly preferable to use an alkali metal hydroxide at the same time, but the amount used is from 0.95 mol to 1 per mol of the alkali metal hydrosulfide. A range of .50 mol, preferably 1.00 mol to 1.25 mol, more preferably 1.005 mol to 1.200 mol can be exemplified.
- hydrogen sulfide is used as the sulfiding agent, it is particularly preferable to use an alkali metal hydroxide at the same time. The amount of the alkali metal hydroxide used in this case is 2.0 to 3.0 with respect to 1 mole of hydrogen sulfide.
- Dihalogenated aromatic compound used in the production method (A2) of PPS (A) includes p-dichlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dibromobenzene.
- Dihalogenated benzenes such as o-dibromobenzene, m-dibromobenzene, 1-bromo-4-chlorobenzene, 1-bromo-3-chlorobenzene, and 1-methoxy-2,5-dichlorobenzene, 1-methyl-2
- Dihalogenated aromatics containing substituents other than halogen such as 5-dichlorobenzene, 1,4-dimethyl-2,5-dichlorobenzene, 1,3-dimethyl-2,5-dichlorobenzene, 3,5-dichlorobenzoic acid Group compounds and the like.
- a halogenated aromatic compound mainly composed of p-dihalogenated benzene represented by p-dichlorobenzene is preferable. Particularly preferably, it contains 80 to 100 mol% of p-dichlorobenzene, and more preferably 90 to 100 mol%. It is also possible to use two or more different dihalogenated aromatic compounds in combination.
- N-alkylpyrrolidones such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and N-cyclohexyl-2-pyrrolidone
- caprolactams such as N-methyl- ⁇ -caprolactam
- 1, Aprotic organic solvents typified by 3-dimethyl-2-imidazolidinone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, etc., and mixtures thereof have high reaction stability.
- N-alkylpyrrolidones such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and N-cyclohexyl-2-pyrrolidone
- caprolactams such as N-methyl- ⁇ -caprolactam
- 1, Aprotic organic solvents typified by 3-dimethyl-2-imidazolidinone, N, N-dimethylacetamide, N, N-
- the monohalogenated compound used in the production method (A2) of PPS (A) is a monohalogenated compound having a reactive functional group W represented by the following general formula (IV). Any functional group may be used, but the reactive functional group W is selected from an amino group, a carboxyl group, a hydroxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, an alkoxysilane group, or a derivative thereof. In particular, those having an amino group, a carboxyl group, or a hydroxyl group as a functional group are more preferred.
- V in the general formula (IV) represents halogen
- monohalogenated compounds include 2-chlorobenzoic acid, 3-chlorobenzoic acid, 4-chlorobenzoic acid, 2-amino-4-chlorobenzoic acid, 4-chloro-3-nitrobenzoic acid.
- monohalogenated compounds such as 4′-chlorobenzophenone-2-carboxylic acid, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol Can do.
- 4-chlorobenzoic acid, 4-chloroaniline, and 4-chlorophenol are more preferable from the viewpoint of reactivity during polymerization and versatility.
- Epoxy resin The preferable aspect of an epoxy resin in the case of using a bifunctional epoxy resin as a bifunctional coupling agent is explained in full detail.
- the term epoxy resin is used in two meanings: a prepolymer before curing, and a cured product obtained by reacting a prepolymer with a composition in which a curing agent and other components are blended.
- the epoxy resin in the invention refers to a prepolymer before curing having an epoxy group in the molecule.
- Epoxy resins can react with various nucleophiles to form chemical bonds.
- nucleophiles include amines, carboxylic acids, alcohols, aromatic alcohols, thiols, isocyanates, silanols, and acid anhydrides. Etc. When the epoxy resin reacts with these nucleophiles, the epoxy group is opened and a secondary alcohol is produced.
- the number average molecular weight of the epoxy resin is not particularly limited. However, since the epoxy resin is required to have heat resistance, it is preferably 300 or more, more preferably 500 or more, and further preferably 700 or more.
- the upper limit of the number average molecular weight is preferably 3,000 or less, and more preferably 2,000 or less. When the upper limit of the number average molecular weight is within the above preferred range, the miscibility with PPS and polyester does not decrease and the proportion of epoxy resin that does not contribute to the block copolymerization reaction does not increase.
- the number average molecular weight of the epoxy resin is a value calculated in terms of polystyrene by GPC analysis.
- the epoxy resin of the present invention preferably contains a halogen atom in the molecule. Since halogen atoms have a larger atomic weight than carbon atoms, nitrogen atoms, and oxygen atoms, the molecular weight of the epoxy resin is increased, and sublimation and evaporation can be suppressed when a block copolymer is produced. In addition, when compared with epoxy resins having the same molecular weight, the epoxy resin containing halogen atoms has a shorter molecular chain, so the reactivity with the reactive functional group of PPS and thermoplastic resin is improved, and the block copolymerization reaction is improved. The reaction rate is improved.
- the flame retardancy of the PPS-thermoplastic resin block copolymer can be improved by utilizing the self-extinguishing property of the halogen atom.
- the number of halogen atoms contained in one molecule of epoxy resin is not particularly limited, and an epoxy resin containing one or more halogen atoms in the molecule can be used.
- the range of the epoxy equivalent of the epoxy resin of the present invention can be appropriately set according to the terminal equivalent amount of PPS or polyester to be reacted.
- the epoxy equivalent is the mass of a resin containing 1 equivalent of an epoxy group, and its unit is expressed in g / ep. Since the heat resistance of an epoxy resin will become low when an epoxy equivalent is too small, it is preferable that it is 200 g / ep or more.
- the upper limit of the epoxy equivalent is preferably 3,000 g / ep or less. When the upper limit of the epoxy equivalent is within the above preferable range, the viscosity of the resin does not become too high and the miscibility with PPS or polyester does not decrease.
- the epoxy resin used in the present invention is not particularly limited as long as it has heat resistance and is bifunctional, and examples thereof include glycidyl ether type, glycidyl ester type, and olefin oxidation type (alicyclic type).
- examples of glycidyl ether type epoxy resins include bisphenol A type, bisphenol F type, bisphenol S type, hydrogenated bisphenol A type, hydrogenated bisphenol F type, biphenyl type, naphthalene type, aliphatic dihydric alcohols and aromatic divalents.
- Examples thereof include epoxy resins obtained by reacting alcohol with epichlorohydrin or ⁇ -methylepichlorohydrin, prepolymers obtained by polymerizing them, and various isomers, alkyls, and halogen-substituted products.
- Examples of the glycidyl ester type epoxy resin include dicarboxylic acids such as phthalic acid, hexahydrophthalic acid, and dimer acid, an epoxy resin obtained by reacting epichlorohydrin or ⁇ -methylepichlorohydrin, and a prepolymer obtained by polymerizing them. And various isomers, alkyl, and halogen-substituted isomers.
- Olefin-oxidized epoxy resins include conjugated or non-conjugated linear dienes, epoxidized polyolefins such as conjugated or non-conjugated cyclic dienes, prepolymers obtained by polymerizing them, and various isomers, alkyls, halogen-substituted products, etc. Is mentioned. Furthermore, an epoxy-containing olefin copolymer containing an ⁇ -olefin and an ⁇ , ⁇ -unsaturated carboxylic acid glycidyl ester as a copolymerization component may also be mentioned.
- epoxy resin examples include, for example, chlorinated bisphenol A diglycidyl ether, brominated bisphenol A diglycidyl ether, chlorinated bisphenol F diglycidyl ether, brominated bisphenol F diglycidyl ether, bisphenol A diglycidyl ether prepolymer, Chlorinated bisphenol A diglycidyl ether prepolymer, brominated bisphenol A diglycidyl ether prepolymer, chlorinated bisphenol F diglycidyl ether prepolymer, brominated bisphenol F diglycidyl ether prepolymer, and the like can be suitably used.
- brominated bisphenol A diglycidyl ether brominated bisphenol F diglycidyl ether, bisphenol A diglycidyl ether prepolymer, brominated bisphenol A diglycidyl ether prepolymer, or the like. It is more preferable to use brominated bisphenol A diglycidyl ether or brominated bisphenol A diglycidyl ether prepolymer because the effect of improving the flame retardancy of the block copolymer is exhibited.
- These epoxy resins may be used alone or in combination of two or more.
- thermoplastic PPS-thermoplastic resin block copolymer (hereinafter simply referred to as an “epoxy-linked block copolymer” in which a PPS unit represented and a thermoplastic resin unit are bonded via a linking group containing a secondary alcohol. Is sometimes obtained).
- thermoplasticity of the block copolymer means that the block copolymer melts and deforms when 30 mg of the copolymer is heated at 300 ° C. for 30 seconds.
- the connecting group contained in the epoxy-linked block copolymer is characterized by containing a secondary alcohol.
- the linking group is a structure in which a PPS unit and a thermoplastic resin unit are linked to form a block copolymer of PPS and a thermoplastic resin, and can be represented by the following general formula (V).
- the structure of R is not particularly limited, and may be any group such as various alkylene groups and aryl groups, and R may include a substituent.
- R may include a substituent.
- a halogen atom is included in the structure of R, the flame retardancy of the block copolymer is improved, which is preferable.
- the linking group since the linking group uses an epoxy resin as a precursor, a secondary alcohol is generated when the epoxy group reacts with PPS or a thermoplastic resin.
- the secondary alcohol when the secondary alcohol is contained, the hydrophilicity of the block copolymer is improved, and the adhesiveness with the additive is improved.
- the presence of a secondary alcohol can be confirmed by analyzing it by a technique such as infrared spectroscopy (IR) or nuclear magnetic resonance (NMR).
- the PPS unit and the linking group are preferably bonded via a structure selected from the group consisting of secondary amine, ester, ether, sulfide, amide and siloxane.
- the reactive functional group of PPS (A) is an amino group, a carboxyl group, a hydroxyl group, a mercapto group, an isocyanato group, a silanol group, an acid anhydride group, or an epoxy group
- the PPS unit and the linking group are from the above group. Bonding will occur through the structure of choice.
- the fact that the PPS unit and the linking group are bonded via a structure selected from the group consisting of secondary amines, esters, ethers, sulfides, amides and siloxanes means that the PPS-thermoplastic resin block copolymer is It can be confirmed by analyzing by various methods such as infrared spectroscopy (IR), nuclear magnetic resonance (NMR), mass spectrometry, energy dispersive X-ray spectroscopy (EDX).
- IR infrared spectroscopy
- NMR nuclear magnetic resonance
- EDX energy dispersive X-ray spectroscopy
- the PPS unit and the thermoplastic resin unit may be connected not only via the above-mentioned linking group, but also terminal structures derived from repetition of each unit may be directly connected.
- a plurality of PPS units and thermoplastic resin units may be present in one molecule of the block copolymer. That is, not only a diblock copolymer or a triblock copolymer but also a multiblock copolymer of tetrablock or more may be used.
- the number average molecular weight of the epoxy-linked block copolymer varies depending on the structure of the thermoplastic resin forming the block copolymer, it cannot be specified unconditionally, but it can be exemplified as 10,000 or more. It is preferable that it is above, and it is more preferable that it is 20,000 or more. Moreover, as the upper limit, it can be illustrated that it is 2,000,000 or less, preferably 1,000,000 or less, and more preferably 500,000 or less. When the number average molecular weight of a block copolymer exists in the said range, the physical property of a block copolymer becomes favorable. It is also a preferred form that the block copolymer of the present invention exhibits a unimodal molecular weight distribution.
- the number average molecular weight is a value calculated in terms of polystyrene by gel permeation chromatography (GPC).
- the present invention will be specifically described below. The present invention is not limited to these examples.
- A. Measurement of molecular weight As for the molecular weight of PPS, the number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated in terms of polystyrene by gel permeation chromatography (GPC) which is a kind of size exclusion chromatography (SEC). The GPC measurement conditions are described below.
- HFIP 1,1,1,3,3,3-hexafluoroisopropanol
- Measurement of Alkali Weight Loss of Polyester The alkali weight loss rate when the PPS-polyester block copolymer was hydrolyzed with an aqueous alkali solution was calculated by the following equation.
- Alkali weight loss (% by weight) ⁇ (weight before alkali hydrolysis (g)) ⁇ (weight after alkali hydrolysis (g)) ⁇ / (weight before alkali hydrolysis (g)) ⁇ 100
- E. Measurement of Film Thickness The average value of the cross-sectional thicknesses at 10 arbitrary positions of the porous body observed with a scanning electron microscope was taken as the film thickness.
- Porosity (%) ⁇ (apparent volume ⁇ actual volume) / apparent volume ⁇ ⁇ 100
- the apparent volume and the actual volume were calculated by the following equations.
- Measurement of Tensile Strength As a tensile strength measurement method, a Tensilon tensile tester (UTM-4L manufactured by Toyo Baldwin) was used. A strip-shaped sample having a length of 50 mm and a width of 10 mm was cut out from the PPS porous body, and the tensile strength was measured at an elongation rate of 300 mm / min in an atmosphere of 25 ° C. and a humidity of 65%. I.
- the water permeation flow rate is measured by fixing a sheet-like PPS porous body (diameter 40 mm, thickness 50 ⁇ m) between stainless steel cells for vacuum filtration and performing the vacuum filtration test of JIS K 3831 (1990). Conducted in compliance. Using 500 mL of ion exchange water as a test solution, the time when the entire amount of ion exchange water passed through the cell at a gauge pressure of ⁇ 10 kPa was measured, and the flow rate of ion exchange water was calculated. Here, it measured 3 times by the separate PPS porous body produced from the same level, The average value was made into the permeation
- Weight retention rate analysis of the epoxy resin was performed using a TG-DTA apparatus manufactured by Seiko Instruments Inc., heated to 300 ° C. at 90 ° C./min, and then held at 300 ° C. for 10 minutes. And the weight after a measurement was measured and the weight retention was computed by following Formula.
- Weight retention (% by weight) weight after measurement (g) / weight before measurement (g) ⁇ 100 [Reference Example 1] Preparation of cyclic PPS A stainless steel autoclave equipped with a stirrer was prepared by using 14.03 g (0.120 mol) of a 48 wt% aqueous solution of sodium hydrosulfide and 96% sodium hydroxide48. 12.50 g (0.144 mol) of a weight% aqueous solution, 615.0 g (6.20 mol) of N-methyl-2-pyrrolidone (NMP), and 18.08 g (0.123) of p-dichlorobenzene (p-DCB) Mole). The reaction vessel was sufficiently purged with nitrogen, and then sealed under nitrogen gas.
- NMP N-methyl-2-pyrrolidone
- p-DCB p-dichlorobenzene
- the temperature was raised from room temperature to 200 ° C. over about 1 hour.
- the pressure in the reaction vessel was 0.35 MPa as a gauge pressure.
- the temperature was raised from 200 ° C. to 270 ° C. over about 30 minutes.
- the pressure in the reaction vessel at this stage was 1.05 MPa as a gauge pressure.
- the content obtained was analyzed by gas chromatography and high performance liquid chromatography. As a result, the consumption rate of monomer p-DCB was 93%, and the sulfur content in the reaction mixture was all converted to cyclic PPS. The formula PPS production rate was found to be 18.5%.
- this white powder has p-phenylene sulfide unit as the main constituent unit based on mass spectrum analysis of the components separated by high performance liquid chromatography (apparatus: Hitachi M-1200H) and molecular weight information by MALDI-TOF-MS.
- the cyclic PPS mixture containing about 98% by weight of a cyclic compound having 4 to 13 repeating units and suitable for use in the production of PPS (A) in the present invention was found.
- the cyclic PPS mixture was completely dissolved in 1-chloronaphthalene at room temperature, and the weight average molecular weight was 900.
- the melt was discharged in a strand form, cooled, and immediately cut to obtain polyethylene terephthalate pellets.
- the intrinsic viscosity of the obtained polyethylene terephthalate it was 0.69 dL / g.
- Example 1 In a test tube equipped with a stirrer, a vacuum stirrer, and a nitrogen blowing tube, 50 parts by weight of amino group-terminated PPS obtained by the method described in Reference Example 2, 50 parts by weight of polyethylene terephthalate obtained by the method described in Reference Example 4, Then, 7 parts by weight of a brominated bisphenol A diglycidyl ether (manufactured by Sigma Aldrich, epoxy equivalent 350-450, weight retention 95.3% by weight), which is a bifunctional epoxy resin, was measured as an epoxy resin, and the inside of the test tube was sealed. And replaced with nitrogen. Subsequently, the test tube was placed in a 300 ° C. oil bath and allowed to stand for 5 minutes to melt the resin, followed by stirring. Stirring was stopped 5 minutes after the start of stirring, and the product was recovered by quenching the test tube.
- a brominated bisphenol A diglycidyl ether manufactured by Sigma Aldrich, epoxy equivalent 350-450, weight retention 95.3% by weight
- the chromatogram of the product is unimodal, the number average molecular weight is 42,000, and the weight average molecular weight is 83,000.
- the molecular weight of the PPS used in the reaction can be increased by block copolymerization. confirmed.
- the resulting PPS-polyethylene terephthalate block copolymer was freeze-ground and extracted with 1,1,1,3,3,3-hexafluoroisopropanol (HFIP). As a result, it was contained in the block copolymer.
- the unreacted polyethylene terephthalate was 30% by weight based on the added polyethylene terephthalate.
- the obtained PPS-polyethylene terephthalate copolymer was melt-pressed to produce a film (thickness: 50 ⁇ m).
- the polyethylene terephthalate is hydrolyzed and removed by immersing it in a 7M sodium hydroxide aqueous solution at 80 ° C. for 4 hours, washed with ion exchange water three times, and vacuum dried at 100 ° C. for 3 hours to obtain a PPS porous body. It was.
- the molecular weight of the PPS porous material was measured by GPC, the number average molecular weight was 16,000 and the weight average molecular weight was 26,000.
- the macro form before and after the hydrolysis treatment did not change, and the weight reduction rate of the block copolymer by the hydrolysis treatment was 46% by weight.
- Example 2 A block copolymer was obtained in the same manner as in Example 1 except that the carboxyl group-terminated PPS obtained by the method described in Reference Example 3 was used. As a result of GPC measurement, the chromatogram of the product was unimodal, the number average molecular weight was 37,000, and the weight average molecular weight was 72,000. Further, as a result of extracting the obtained block copolymer with HFIP, the unreacted polyethylene terephthalate contained in the block copolymer was 38% by weight with respect to the added polyethylene terephthalate. Next, when it was made porous by hydrolysis treatment in the same manner as in Example 1, the macro form before and after the treatment did not change, and the weight reduction rate of the block copolymer by the hydrolysis treatment was 38% by weight. there were.
- the PPS porous body had an average pore diameter of 0.22 ⁇ m and a porosity of 48%. Table 1 shows the tensile strength and water permeation flow rate of the obtained PPS porous body.
- Example 3 A block copolymer was obtained in the same manner as in Example 1 except that 35 parts by weight of amino group-terminated PPS, 65 parts by weight of polyethylene terephthalate, and 7 parts by weight of brominated bisphenol A diglycidyl ether were used. Moreover, as a result of extracting the obtained block copolymer with HFIP, the unreacted polyethylene terephthalate contained in a block copolymer was 43 weight% with respect to the added polyethylene terephthalate. Next, when it was made porous by hydrolytic treatment in the same manner as in Example 1, the macroscopic form before and after the hydrolytic treatment did not change, and the weight reduction rate of the block copolymer by the hydrolytic treatment was 48 wt. %Met.
- the PPS porous body had an average pore diameter of 0.38 ⁇ m and a porosity of 62%. Table 1 shows the tensile strength and water permeation flow rate of the obtained PPS porous body.
- Example 4 A block copolymer was obtained in the same manner as in Example 1 except that 65 parts by weight of amino group-terminated PPS, 35 parts by weight of polyethylene terephthalate, and 7 parts by weight of brominated bisphenol A diglycidyl ether were used. Further, as a result of extracting the obtained block copolymer with HFIP, the unreacted polyethylene terephthalate contained in the block copolymer was 26% by weight based on the added polyethylene terephthalate. Next, when it was made porous by hydrolytic treatment in the same manner as in Example 1, the macro form before and after the hydrolytic treatment did not change, and the weight reduction rate of the block copolymer by the hydrolytic treatment was 27 wt. %Met.
- the PPS porous body had an average pore diameter of 0.20 ⁇ m and a porosity of 39%. Table 1 shows the tensile strength and water permeation flow rate of the obtained PPS porous body.
- the obtained film was cut into a circular shape having a diameter of 5 cm and immersed in 100 ml of N-methyl-2-pyrrolidone at 100 ° C. for 12 hours to dissolve and remove the cyclic PPS oligomer.
- the resultant was washed with 20 ml of N-methyl-2-pyrrolidone and subsequently washed three times with ion-exchanged water, and then vacuum-dried at 100 ° C. for 3 hours to prepare a PPS porous film.
- the surface of the PPS porous body was observed at a magnification of 1,300 with a scanning electron microscope, only a uniform porous region was observed, and substantially no non-porous region was present.
- the PPS porous body had an average pore diameter of 0.002 ⁇ m and a porosity of 50%.
- Table 1 shows the tensile strength and water permeation flow rate of the obtained PPS porous body. Although the water permeation flow rate was high, the tensile strength was low.
- PPS Transparative Example 2
- a nitrogen-substituted autoclave was charged with 17 parts by weight of commercially available PPS (Tolerina (registered trademark) E2088) manufactured by Toray, 10 parts by weight of diethylene glycol, and 73 parts by weight of N-methyl-2-pyrrolidone, and pressurized at 250 ° C. Dissolved under conditions. This solution was discharged at 235 ° C. using a slit-type die, passed 22 mm through the air, and then led into a coagulation bath of NMP 60% by weight to obtain a PPS film.
- Tolerina registered trademark
- the weight reduction rate in the alkali treatment was 0% by weight, and the macroscopic form before and after the hydrolysis treatment was not changed. Therefore, the PPS-polyethylene terephthalate block copolymer before the hydrolysis had PPS as a sea component, Polyethylene terephthalate has a sea-island structure of island components, and polyethylene terephthalate was not decomposed and removed even after alkali treatment.
- Table 1 shows the tensile strength and water permeation flow rate of the obtained PPS porous body.
- the polyphenylene sulfide porous body of the present invention can be used in various fields as a functional material excellent in heat resistance, chemical resistance, mechanical properties, and permeation performance.
- it can be widely studied for applications such as separation membranes, battery separators, bag filters, lightweight structural materials, dialysis membranes, catalyst carriers, heat insulating materials, heat insulating materials, buffer materials, adsorbing materials, and low dielectric constant materials. it can.
- various performances can be achieved by combining with other materials.
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Abstract
Description
表面に、多孔構造からなる多孔領域と、実質的に多孔構造を有しない無孔領域とを有するポリフェニレンスルフィド多孔質体、である。
末端に反応性官能基を有するポリフェニレンスルフィド(A)と、熱可塑性樹脂(B)と、二官能連結剤(C)とを反応させるポリフェニレンスルフィド-熱可塑性樹脂ブロック共重合体の製造方法、である。
前記ポリフェニレンスルフィド-熱可塑性樹脂ブロック共重合体または前記製造方法で得られるポリフェニレンスルフィド-熱可塑性樹脂ブロック共重合体から、熱可塑性樹脂成分を分解除去するポリフェニレンスルフィド多孔質体の製造方法、である。
(1)PPS多孔質体
本発明におけるPPS多孔質体は、表面に、多孔構造からなる多孔領域と、実質的に多孔構造を有しない無孔領域とを有するものである。
なお、空孔が表面に均一な頻度で存在する多孔質体の場合、すべて無孔領域(多孔領域の平均面積率0%)、またはすべて多孔領域(多孔領域の平均面積率100%)となるため、本発明のPPS多孔質体とは区別される。
ここで、見かけの体積とは空孔を含めたPPS多孔質体全体の体積のことである。また、実際の体積とは、PPS多孔質体のうち樹脂成分が占有する体積のことであり、以下の式により求める。
PPS多孔質体の空孔率が上記好ましい範囲であると、流体が多孔質体を透過するときの圧力損失が小さくなり、透過性能を向上させることができる。また、物質の吸着や脱着効率を高めたり、他素材と複合化する際に充填効率を高めたりすることができる。一方、引張、圧縮、曲げなどの機械強度が損なわれることはない。空孔率は20%以上がより好ましく、30%以上がさらに好ましい。また、空孔率は70%以下がより好ましく、65%以下がさらに好ましい。
(2)PPS-熱可塑性樹脂ブロック共重合体の製造方法およびPPS多孔質体の製造方法
本発明のPPS-熱可塑性樹脂ブロック共重合体は、少なくとも末端に反応性官能基を有するポリフェニレンスルフィド(A)と、熱可塑性樹脂(B)と、二官能連結剤(C)を反応させることによって製造することが可能であり、また、当該ブロック共重合体から熱可塑性樹脂(B)の成分を除去することによってPPS多孔質体を製造することが可能である。
また、PPS末端の反応性官能基とは、連結剤と反応して化学結合を形成することができる官能基のことを指す。PPS末端の反応性官能基としては、アミノ基、カルボキシル基、ヒドロキシル基、メルカプト基、イソシアナト基、シラノール基、酸無水物基、エポキシ基およびこれらの誘導体からなる群より選ばれる官能基であることが好ましい。PPSの末端構造がこのような反応性官能基であれば連結剤との反応性が高く、PPSと熱可塑性樹脂とのブロック共重合化反応を短時間かつ高効率に進行させることができる。ここで、反応性官能基がPPSの末端のみに有することにより、PPSの側鎖に反応性官能基を有する場合に比べ、連結剤と化学結合を形成する箇所が限定されて架橋反応が抑制されるため、熱可塑性を有するPPS-熱可塑性樹脂ブロック共重合体を製造することができる。上記の反応性官能基の中で、アミノ基、カルボキシル基、ヒドロキシル基、メルカプト基から選ばれる官能基であることが特に好ましく例示できる。
PPSを溶融状態で反応させる場合は280~300℃、また、溶液状態で反応させる場合では200~250℃で反応させることができる。そのため、連結剤の耐熱性が低い場合、高温での反応時に連結剤が昇華や蒸発、熱分解して反応に寄与しない連結剤の割合が増加して、ブロック共重合化反応の反応率が低下する。連結剤が耐熱性を有することにより、ブロック共重合化反応の反応率を向上させることができる。
(3)PPS(A)の製造方法
上記のPPS(A)の製造方法の一例として、環式PPS(a)を、反応性官能基を有するスルフィド化合物の存在下に加熱するPPS(A)の製造方法(A1)、および、少なくともスルフィド化剤、ジハロゲン化芳香族化合物、有機極性溶媒、および反応性官能基を有するモノハロゲン化化合物を含む混合物を加熱するPPS(A)の製造方法(A2)が挙げられる。以下、これらのPPS(A)の製造方法につき詳細を記す。
(3-1)PPS(A)の製造方法(A1)
PPS(A)の第1の好ましい製造方法として、環式PPS(a)を、反応性官能基を有するスルフィド化合物の存在下に加熱する方法が挙げられる。
(3-2)PPS(A)の製造方法(A2)
PPS(A)の第2の好ましい製造方法として、少なくともスルフィド化剤、ジハロゲン化芳香族化合物、有機極性溶媒、および反応性官能基を有するモノハロゲン化化合物を含む混合物を加熱する製造方法(A2)が挙げられる。
(3-3)環式PPS(a)
PPS(A)の製造方法(A1)に用いられる環式PPS(a)に含まれる環式PPSは、式、-(Ph-S)-の繰り返し単位(Phはフェニレン基)を主要構成単位とし、好ましくは当該繰り返し単位を80モル%以上含有する下記一般式(II)で表される環式化合物である。環式PPS(a)としては、一般式(II)の環式PPSを少なくとも50重量%以上含むものであり、好ましくは70重量%以上、より好ましくは80重量%以上、さらに好ましくは90重量%以上含むものが好ましい。
(3-4)スルフィド化合物
PPS(A)の製造方法(A1)に用いられるスルフィド化合物とは、下記一般式(III)で表される反応性官能基を有するスルフィド化合物である。
(3-5)スルフィド化剤
PPS(A)の製造方法(A2)に用いられるスルフィド化剤とは、ジハロゲン化芳香族化合物にスルフィド結合を導入できるものであればよく、例えばアルカリ金属硫化物、アルカリ金属水硫化物、および硫化水素が挙げられる。
(3-6)ジハロゲン化芳香族化合物
PPS(A)の製造方法(A2)に用いられるジハロゲン化芳香族化合物としては、p-ジクロロベンゼン、o-ジクロロベンゼン、m-ジクロロベンゼン、p-ジブロモベンゼン、o-ジブロモベンゼン、m-ジブロモベンゼン、1-ブロモ-4-クロロベンゼン、1-ブロモ-3-クロロベンゼンなどのジハロゲン化ベンゼン、および1-メトキシ-2,5-ジクロロベンゼン、1-メチル-2,5-ジクロロベンゼン、1,4-ジメチル-2,5-ジクロロベンゼン、1、3-ジメチル-2,5-ジクロロベンゼン、3,5-ジクロロ安息香酸などのハロゲン以外の置換基を含むジハロゲン化芳香族化合物などを挙げることができる。なかでも、p-ジクロロベンゼンに代表されるp-ジハロゲン化ベンゼンを主成分とするハロゲン化芳香族化合物が好ましい。特に好ましくは、p-ジクロロベンゼンを80~100モル%含むものであり、さらに好ましくは90~100モル%含むものである。また、異なる2種類以上のジハロゲン化芳香族化合物を組み合わせて用いることも可能である。
(3-7)有機極性溶媒
PPS(A)の製造方法(A2)に用いられる有機極性溶媒として、有機アミド溶媒が好ましく例示できる。具体例としては、N-メチル-2-ピロリドン、N-エチル-2-ピロリドン、N-シクロヘキシル-2-ピロリドンなどのN-アルキルピロリドン類、N-メチル-ε-カプロラクタムなどのカプロラクタム類、1,3-ジメチル-2-イミダゾリジノン、N、N-ジメチルアセトアミド、N、N-ジメチルホルムアミド、ヘキサメチルリン酸トリアミドなどに代表されるアプロチック有機溶媒、およびこれらの混合物などが反応の安定性が高いために好ましく使用される。これらのなかでもN-メチル-2-ピロリドン、1、3-ジメチル-2-イミダゾリジノンが好ましく、N-メチル-2-ピロリドンがより好ましく用いられる。
(3-8)モノハロゲン化化合物
PPS(A)の製造方法(A2)に用いられるモノハロゲン化化合物は、下記一般式(IV)で表される反応性官能基Wを有するモノハロゲン化化合物であればいかなるものでもよいが、反応性官能基Wとしてアミノ基、カルボキシル基、ヒドロキシル基、酸無水物基、イソシアネート基、エポキシ基、シラノール基、アルコキシシラン基、もしくはそれらの誘導体から選ばれる官能基を有するものが好ましく、なかでもアミノ基、カルボキシル基、ヒドロキシル基を官能基として有するものがより好ましい。
このようなモノハロゲン化化合物の具体例としては、2-クロロ安息香酸、3-クロロ安息香酸、4-クロロ安息香酸、2-アミノ-4-クロロ安息香酸、4-クロロ-3-ニトロ安息香酸、4’-クロロベンゾフェノン-2-カルボン酸、2-クロロアニリン、3-クロロアニリン、4-クロロアニリン、2-クロロフェノール、3-クロロフェノール、4-クロロフェノールなどのモノハロゲン化化合物を挙げることができる。これらのなかでも重合時の反応性や汎用性などの観点から4-クロロ安息香酸、4-クロロアニリン、4-クロロフェノールがより好ましく例示できる。また、これらのモノハロゲン化化合物は1種類単独で用いてもよいし、2種類以上を組み合わせて用いてもできる。
(4)エポキシ樹脂
二官能連結剤として二官能エポキシ樹脂を用いる場合における、エポキシ樹脂の好ましい態様について詳述する。なお、一般的にエポキシ樹脂という用語は、硬化前のプレポリマー、およびプレポリマーに硬化剤や他の成分を配合した組成物を反応させて得られる硬化物の2つの意味で用いられるが、本発明におけるエポキシ樹脂とは、分子内にエポキシ基を有する硬化前のプレポリマーのことを指す。
(5)ポリフェニレンスルフィド-熱可塑性樹脂ブロック共重合体
二官能連結剤として二官能エポキシ樹脂を用いる場合、本発明のPPS-熱可塑性樹脂ブロック共重合体を製造方法により、下記一般式(I)で表されるPPS単位と、熱可塑性樹脂単位とが第二級アルコールを含む連結基を介して結合した熱可塑性のPPS-熱可塑性樹脂ブロック共重合体(以下、単に「エポキシ連結のブロック共重合体」という場合がある)が得られる。ここでブロック共重合体の熱可塑性とは、共重合体30mgを300℃で30秒間加熱したときにブロック共重合体が溶融して流動変形することを意味する。
A.分子量の測定
PPSの分子量はサイズ排除クロマトグラフィー(SEC)の一種であるゲルパーミエーションクロマトグラフィー(GPC)により、ポリスチレン換算で数平均分子量(Mn)と重量平均分子量(Mw)を算出した。GPCの測定条件を以下に記す。
カラム名:センシュー科学 GPC3506
溶離液:1-クロロナフタレン
検出器:示差屈折率検出器
カラム温度:210℃
プレ恒温槽温度:250℃
ポンプ恒温槽温度:50℃
検出器温度:210℃
流量:1.0mL/min
試料注入量:300μL(スラリー状:約0.2重量%)
B.ポリエステルの抽出率の分析
ポリエステルの抽出は、ブロック共重合体の反応生成物1.00gを溶融プレスして厚さ100μm以下のフィルム状とした後、凍結粉砕して粉末状とした。続いて、1,1,1,3,3,3-ヘキサフルオロイソプロパノール(HFIP)を30g加え、50℃のオイルバスを用いて3時間還流することにより、ブロック共重合体中に残存する未反応のポリエステルをHFIP中に溶出させた。3時間の加熱撹拌後、平均目開き0.45μmのメンブレンフィルタを用いてろ過を行い、HFIP可溶成分と不溶成分を分離回収した。不溶成分を80℃で一晩真空乾燥した。得られた各乾燥固体の重量を測定し、抽出前後の重量から以下の式によりポリエステルの抽出率を算出した。
C.ポリエステルのアルカリ減量率の測定
PPS-ポリエステルブロック共重合体をアルカリ水溶液で加水分解処理したときのアルカリ減量率は次式により算出した。
D.走査型電子顕微鏡の観察
プレスフィルムの表面および断面の観察は、走査型電子顕微鏡(日立ハイテクノロジーズ製S-5500)を用い、白金パラジウムでスパッタリング処理した試料を観察した。
E.膜厚の測定
走査型電子顕微鏡によって観察した多孔質体の任意の10ヶ所の断面厚さの平均値を膜厚とした。
F.平均孔径の測定
PPS多孔質体をクロスセクションポリッシャー法(CP法)により形成させた任意の断面10点を倍率10万倍の走査型電子顕微鏡で観察した際、各々の観察画像における空孔の直径を測定し、その平均値を平均孔径とした。
G.空孔率の測定
直径20mm、厚さ50μmの円盤状のPPS多孔質体を作製し、次式により空孔率を算出した。
ここで、見かけの体積および実際の体積は次式により算出した。
実際の体積(m3)=多孔質体の重量(g)/材質の比重(g・m-3)
H.引張強度の測定
引張強度測定法としては、テンシロン引張試験機(東洋ボールドウィン製UTM-4L)を用いた。PPS多孔質体から長さ50mm、幅10mmの短冊状のサンプルを切り出し、25℃湿度65%の雰囲気下で引張速度300mm/分で引張強度を測定した。
I.水の透過流量の測定
水の透過流量は、シート状のPPS多孔質体(直径40mm、厚み50μm)を減圧ろ過用のステンレスセルに挟んで固定し、JIS K 3831(1990)の減圧ろ過試験に準拠して実施した。試験液としてイオン交換水500mLを用い、ゲージ圧-10kPaにてイオン交換水の全量がセルを通過したときの時間を計測し、イオン交換水の流量を算出した。ここで、同一の水準から作製した別々のPPS多孔質体にて3回測定し、その平均値をPPS多孔質体の水の透過流量とした。
J.エポキシ樹脂の重量保持率の分析
エポキシ樹脂の重量保持率の分析は、セイコーインスツル製TG-DTA装置を用い、90℃/分で300℃まで昇温後、300℃で10分間保持した。そして測定後の重量を測定し、次式により重量保持率を算出した。
[参考例1]環式PPSの調製
撹拌機を具備したステンレス製オートクレーブに、水硫化ナトリウムの48重量%水溶液を14.03g(0.120モル)、96%水酸化ナトリウムを用いて調製した48重量%水溶液12.50g(0.144モル)、N-メチル-2-ピロリドン(NMP)615.0g(6.20モル)、及びp-ジクロロベンゼン(p-DCB)18.08g(0.123モル)を仕込んだ。反応容器内を十分に窒素置換した後、窒素ガス下に密封した。
[参考例2]アミノ基末端PPSの製造方法
参考例1に示した方法により得られる環式PPS混合物20gに、PPS単位1モルに対し、ビス(4-アミノフェニル)スルフィドを0.80g(2.0モル%)混合した粉末を、ガラス製アンプルに仕込み、アンプル内を窒素で置換した。320℃に温調した電気炉内にアンプルを設置し120分間加熱した後、アンプルを取り出し室温まで冷却し黒色固体を得た。生成物は1-クロロナフタレンに250℃で全溶であった。HPLC測定の結果、環式PPSのPPSへの転化率は97.0%であることが分かった。
[参考例3]カルボキシル基末端PPSの製造方法
ビス(4-カルボキシフェニル)スルフィドを0.5モル%、反応時間を120分とした以外は参考例2と同様に実施し、黒色固体を得た。生成物は1-クロロナフタレンに250℃で全溶であった。HPLC測定の結果、環式PPSのPPSへの転化率は96.2%であることが分かった。GPC測定の結果、環式PPSに由来するピークと生成したPPSのピークが確認でき、得られたPPSの数平均分子量は17,000、重量平均分子量は35,000、分散度は2.06であることが分かった。また、PPS構造単位1モル当たりに対するカルボキシル基含有量は0.37モル%であった。
[参考例4]ポリエチレンテレフタレートの製造方法
テレフタル酸ジメチル100重量部とエチレングリコール60重量部、得られるポリマー100gに対してマグネシウム原子換算で0.05mmolの酢酸マグネシウムを、150℃、窒素雰囲気下で溶融後、撹拌しながら240℃まで4時間かけて昇温し、メタノールを留出させ、エステル交換反応を行い、ビス(ヒドロキシエチル)テレフタレート(BHT)を得た。
[実施例1]
撹拌機、バキュームスターラー、窒素吹き込み管を具備した試験管に、参考例2記載の方法により得られるアミノ基末端PPSを50重量部、参考例4記載の方法により得られるポリエチレンテレフタレートを50重量部、そしてエポキシ樹脂として二官能エポキシ樹脂であるブロモ化ビスフェノールAジグリシジルエーテル(シグマアルドリッチ製、エポキシ当量350~450、重量保持率95.3重量%)7重量部を量り取り、試験管内を密封した後、窒素置換した。続いて、試験管を300℃のオイルバス中に入れ、5分間静置して樹脂を溶融した後、攪拌した。攪拌開始5分後に攪拌を停止し、試験管を急冷させることにより生成物を回収した。
[実施例2]
参考例3記載の方法により得られるカルボキシル基末端PPSを用いた以外は実施例1と同様の方法でブロック共重合体を得た。GPC測定の結果、生成物のクロマトグラムは単峰性であり数平均分子量は37,000、重量平均分子量は72,000であった。また、得られたブロック共重合体をHFIPにて抽出処理した結果、ブロック共重合体中に含まれる未反応のポリエチレンテレフタレートは添加したポリエチレンテレフタレートに対して38重量%であった。次に実施例1と同様の方法で加水分解処理して多孔化したところ、処理前後のマクロな形態が変化しておらず、加水分解処理によるブロック共重合体の重量減少率は38重量%であった。
[実施例3]
アミノ基末端PPSを35重量部、ポリエチレンテレフタレート65重量部、ブロモ化ビスフェノールAジグリシジルエーテルを7重量部とした以外は実施例1と同様の方法でブロック共重合体を得た。また、得られたブロック共重合体をHFIPにて抽出処理した結果、ブロック共重合体中に含まれる未反応のポリエチレンテレフタレートは添加したポリエチレンテレフタレートに対して43重量%であった。次に実施例1と同様の方法で加水分解処理して多孔化したところ、加水分解処理前後のマクロな形態が変化しておらず、加水分解処理によるブロック共重合体の重量減少率は48重量%であった。
[実施例4]
アミノ基末端PPSを65重量部、ポリエチレンテレフタレート35重量部、ブロモ化ビスフェノールAジグリシジルエーテルを7重量部とした以外は実施例1と同様の方法でブロック共重合体を得た。また、得られたブロック共重合体をHFIPにて抽出処理した結果、ブロック共重合体中に含まれる未反応のポリエチレンテレフタレートは添加したポリエチレンテレフタレートに対して26重量%であった。次に実施例1と同様の方法で加水分解処理して多孔化したところ、加水分解処理前後のマクロな形態が変化しておらず、加水分解処理によるブロック共重合体の重量減少率は27重量%であった。
[比較例1]
市販のPPS(東レ製“トレリナ(登録商標)E2088”)と、参考例1で調製した環式PPSオリゴマーをそれぞれ50重量部ずつ混合し、リップ間隔0.2mmに調整したT-ダイ付き二軸溶融混練機HK-25D(パーカーコーポレーション製)に供し、300℃で溶融製膜を実施した。ドラム温度を60℃とし、巻き取り速度を調整することにより、厚さ150μmのPPSポリマー/環状PPSオリゴマー混合物フィルムを作製した。得られたフィルムを直径5cmの円形状に切り出し、100℃のN-メチル-2-ピロリドン100mlに12時間浸漬し、環状PPSオリゴマーを溶解除去した。N-メチル-2-ピロリドン20mlで洗浄し、続いてイオン交換水で3回洗浄を繰り返した後、100℃で3時間真空乾燥してPPS多孔質フィルムを作製した。走査型電子顕微鏡にてPPS多孔質体の表面を倍率1,300倍で観察したところ、均一な多孔領域のみ観察され、実質的に無孔領域は存在しなかった。また、PPS多孔質体の平均孔径は0.002μm、空孔率は50%であった。得られたPPS多孔質体の引張強度および水の透過流量を表1に示す。水の透過流量は高いものの、引張強度が低かった。
[比較例2]
窒素置換したオートクレーブに市販のPPS(東レ製“トレリナ(登録商標)E2088”)を17重量部、ジエチレングリコールを10重量部、N-メチル-2-ピロリドンを73重量部投入し、250℃の加圧条件下で溶解した。この溶液をスリット型の口金を用いて235℃で吐出し、空気中を22mm通過した後、NMP60重量%の凝固浴中に導きPPSフィルムを得た。
[比較例3]
二官能エポキシ樹脂を添加しなかった以外は実施例1と同様の方法でPPS/ポリエチレンテレフタレートブレンドのプレスフィルムを作製し、アルカリ加水分解処理を行った。アルカリ処理における重量減少率は0重量%であり、また、加水分解処理前後のマクロな形態が変化していなかったことから、加水分解前のPPS-ポリエチレンテレフタレートブロック共重合体はPPSが海成分、ポリエチレンテレフタレートが島成分の海島構造であり、アルカリ処理後においてもポリエチレンテレフタレートが分解除去されなかった。
2 無孔領域
Claims (17)
- 表面に、多孔構造からなる多孔領域と、実質的に多孔構造を有しない無孔領域とを有するポリフェニレンスルフィド多孔質体。
- 表面における前記多孔領域の平均面積率が10~80%である請求項1に記載のポリフェニレンスルフィド多孔質体。
- 前記無孔領域が表面で連続している請求項1または請求項2に記載のポリフェニレンスルフィド多孔質体。
- 空孔率が10~80%である請求項1~請求項3のいずれかに記載のポリフェニレンスルフィド多孔質体。
- 数平均分子量(Mn)が6,000~100,000のポリフェニレンスルフィドにより構成されてなる請求項1~請求項4のいずれかに記載のポリフェニレンスルフィド多孔質体。
- 少なくとも末端に反応性官能基を有するポリフェニレンスルフィド(A)と、熱可塑性樹脂(B)と、二官能連結剤(C)とを反応させるポリフェニレンスルフィド-熱可塑性樹脂ブロック共重合体の製造方法。
- ポリフェニレンスルフィド(A)の前記反応性官能基がアミノ基、カルボキシル基、ヒドロキシル基、メルカプト基、イソシアナト基、シラノール基、酸無水物基、エポキシ基およびこれらの誘導体からなる群より選ばれる基である請求項6に記載のポリフェニレンスルフィド-熱可塑性樹脂ブロック共重合体の製造方法。
- 前記二官能連結剤(C)がエポキシ樹脂である請求項6または請求項7に記載のポリフェニレンスルフィド-熱可塑性樹脂ブロック共重合体の製造方法。
- 前記二官能連結剤(C)がハロゲン原子を含むものである請求項6~請求項8のいずれかに記載のポリフェニレンスルフィド-熱可塑性樹脂ブロック共重合体の製造方法。
- 前記エポキシ樹脂の数平均分子量が300以上である請求項8または請求項9に記載のポリフェニレンスルフィド-熱可塑性樹脂ブロック共重合体の製造方法。
- 前記エポキシ樹脂のエポキシ当量が200g/ep以上である請求項8~請求項10のいずれかに記載のポリフェニレンスルフィド-熱可塑性樹脂ブロック共重合体の製造方法。
- ポリフェニレンスルフィド単位と熱可塑性樹脂単位とが第二級アルコールを含む連結基を介して結合しているポリフェニレンスルフィド-熱可塑性樹脂ブロック共重合体。
- 前記ポリフェニレンスルフィド単位と前記連結基が、第二級アミン、エステル、エーテル、スルフィド、アミドおよびシロキサンからなる群から選ばれる構造を介して結合している請求項12に記載のポリフェニレンスルフィド-熱可塑性樹脂ブロック共重合体。
- 前記連結基がハロゲン原子を含む請求項12または請求項13に記載のポリフェニレンスルフィド-熱可塑性樹脂ブロック共重合体。
- 前記ポリフェニレンスルフィド単位の数平均分子量(Mn)が6,000以上かつ100,000以下の範囲である請求項12~請求項14のいずれかに記載のポリフェニレンスルフィド-熱可塑性樹脂ブロック共重合体。
- 数平均分子量(Mn)が10,000以上かつ2,000,000以下の範囲である請求項12~請求項15のいずれかに記載のポリフェニレンスルフィド-熱可塑性樹脂ブロック共重合体。
- 請求項12~請求項16のいずれかに記載のポリフェニレンスルフィド-熱可塑性樹脂ブロック共重合体または請求項6~請求項11のいずれかに記載の製造方法で得られるポリフェニレンスルフィド-熱可塑性樹脂ブロック共重合体から、熱可塑性樹脂成分を分解除去するポリフェニレンスルフィド多孔質体の製造方法。
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EP18176826.8A EP3395858A1 (en) | 2014-03-18 | 2015-03-11 | Polyphenylene sulfide porous body and production method thereof, polyphenylene sulfide-thermoplastic resin block copolymer and production method thereof |
AU2015232637A AU2015232637B2 (en) | 2014-03-18 | 2015-03-11 | Polyphenylene sulfide porous body and production method thereof, polyphenylene sulfide-thermoplastic resin block copolymer and production method thereof |
US15/126,519 US20170081493A1 (en) | 2014-03-18 | 2015-03-11 | Polyphenylene sulfide porous body and production method thereof, polyphenylene sulfide-thermoplastic resin block copolymer and production method thereof |
JP2015515335A JP6319306B2 (ja) | 2014-03-18 | 2015-03-11 | ポリフェニレンスルフィド多孔質体およびその製造方法、ポリフェニレンスルフィド−熱可塑性樹脂ブロック共重合体およびその製造方法 |
EP15764956.7A EP3121215A4 (en) | 2014-03-18 | 2015-03-11 | Polyphenylene sulfide porous body and production method thereof, polyphenylene sulfide-thermoplastic resin block copolymer and production method thereof |
CN201580011372.7A CN106062038A (zh) | 2014-03-18 | 2015-03-11 | 聚苯硫醚多孔质体及其制造方法、聚苯硫醚‑热塑性树脂嵌段共聚物及其制造方法 |
KR1020167023476A KR20160134659A (ko) | 2014-03-18 | 2015-03-11 | 폴리페닐렌술피드 다공질체 및 그의 제조 방법, 폴리페닐렌술피드-열 가소성 수지 블록 공중합체 및 그의 제조 방법 |
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KR20210035192A (ko) | 2018-07-30 | 2021-03-31 | 도레이 카부시키가이샤 | 분리막 및 분리막의 제조 방법 |
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KR20220055828A (ko) * | 2020-10-27 | 2022-05-04 | 에이치디씨폴리올 주식회사 | 폴리아릴렌 설파이드 수지 및 이의 제조방법 |
CN116575142B (zh) * | 2023-07-14 | 2023-09-22 | 江苏恒力化纤股份有限公司 | 一种多孔隙服装用聚苯硫醚纤维的制备方法 |
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EP3121215A4 (en) | 2017-12-20 |
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