Material, organic-inorganic hybrid material, and method for producing same

Abstract

[Problem] To provide a highly functional polymer derived from a biological resource. [Solution] The present invention provides a polymer having, as a basic unit, a polycyclic structure that includes a plurality of ring structures.

Description

Material, organic-inorganic hybrid material and method for producing the same

[0001] Some aspects of the present invention relate to materials that contain at least a molecular structure derived from a biological resource or a molecular structure similar to the molecular structure. In particular, the present invention relates to bioplastics, which are polymers that have the above-mentioned molecular structure as at least one repeating unit. Note that, in this specification, the term "bioplastics" refers to materials that do not originate from biological resources but contain at least one repeating unit with the same or similar molecular structure as that derived from a biological resource.

[0002] Furthermore, some aspects of the present invention relate to a material in which an element having a lower electronegativity than carbon, a cation of the element, or a compound containing the element is contained in a plastic, the above-mentioned material, or the above-mentioned polymer or bioplastic, and a method for producing the same.

[0003] Due to the problem of microplastic pollution and the like, bioplastic materials derived from biological resources such as plants have been attracting attention. For example, Patent Document 1 discloses a bioplastic that utilizes plant-derived hemicellulose.

[0004] Patent Document 2 discloses an example in which inorganic substances such as talc, wollastonite, calcium carbonate, barium sulfate, mica, and glass fiber are mixed with a polymer such as polypropylene using a twin-screw extruder.

[0005] JP 2020-132790 A JP 2001-288331 A

[0006] However, conventional bioplastics have a problem in that they do not have sufficient strength to withstand processing such as molding, drawing, or spinning.

[0007] Furthermore, conventional polymers containing inorganic substances have had problems such as the uniformity of the inorganic substance mixed inside the polymer being insufficient for desired performance, mechanical strength, flexibility, etc.

[0008] A material according to some embodiments of the present invention is a polymer having a plurality of structural units, wherein a first structural unit of the plurality of structural units has a first portion and a second portion, a portion of the first portion and a portion of the second portion are shared, the first portion is a six-membered ring, the six-membered ring includes a first oxygen atom, two first carbon atoms, two second carbon atoms, and one third carbon atom, the first oxygen atom and one first carbon atom of the two first carbon atoms form a first covalent bond, the first oxygen atom and one first carbon atom of the two first carbon atoms form a second covalent bond, the first carbon atom of one of the two first carbon atoms and one second carbon atom of the two second carbon atoms form a third covalent bond, and the other first carbon atom of the two first carbon atoms and one second carbon atom of the two second carbon atoms form a third covalent bond. a fourth covalent bond with the other second carbon atom, a fifth covalent bond with one second carbon atom of the two second carbon atoms and the one third carbon atom, a sixth covalent bond with the other second carbon atom of the two second carbon atoms and the one third carbon atom, the second portion is a first five-membered ring composed of the one first carbon atom, the one second carbon atom, a second oxygen atom, a third oxygen atom, and one fourth carbon atom, a seventh covalent bond with the one first carbon atom and the second oxygen atom, an eighth covalent bond with the one second carbon atom and the third oxygen atom, a ninth covalent bond with the second oxygen atom and the one fourth carbon atom, and a tenth covalent bond with the third oxygen atom and the one fourth carbon atom.

[0009] Typical examples of the first moiety include sugars such as xylose, glucose, mannose, galactose, fucose, and rhamnose, which have a six-membered ring structure composed of an oxygen atom and five carbon atoms. The second moiety has a five-membered ring structure containing two oxygen atoms and shares one covalent bond with the six-membered ring structure of the sugars described above. Typical examples of this include an acetal group or a ketal group.

[0010] In the above-described polymer, each of the plurality of structural units further has a third portion, and the third portion is a second five-membered ring composed of the other second carbon atom, the one third carbon atom, a fourth oxygen atom, a fifth oxygen atom, and one fifth carbon atom, wherein the other second carbon atom and the fourth oxygen atom form an eleventh covalent bond, the one third carbon atom and the fifth oxygen atom form a twelfth covalent bond, the fourth oxygen atom and the one fifth carbon atom form a thirteenth covalent bond, and the fifth oxygen atom and the one fifth carbon atom form a fourteenth covalent bond.

[0011] In the above polymer, the one fourth carbon atom is preferably bonded to the sixth carbon atom of the first carbonyl group directly or via a linking group.

[0012] In the above polymer, the fifth carbon atom is preferably bonded to the seventh carbon atom of the second carbonyl group directly or via a linking group.

[0013] In the above polymer, the sixth carbon atom preferably forms a fifteenth covalent bond with the sixth oxygen atom.

[0014] In the above polymer, the seventh carbon atom preferably forms a sixteenth covalent bond with the seventh oxygen atom.

[0015] In the above-described polymer, it is preferable that the second structural unit contained in the plurality of structural units has the same structure as the first structural unit, and that the sixth oxygen atom forms a seventeenth covalent bond with any atom constituting the second structural unit.

[0016] In the above-described polymer, it is preferable that the third structural unit contained in the plurality of structural units has the same structure as the first structural unit, and the seventh oxygen atom is bonded to any atom contained in the third structural unit directly or via a linking group.

[0017] In the above-described polymer, it is preferable that the third structural unit contained in the plurality of structural units has the same structure as the first structural unit, and the seventh oxygen atom forms an 18th covalent bond with the eighth oxygen atom contained in the third structural unit via a linking group.

[0018] In the above polymer, the linking group is preferably an alkylene group.

[0019] In the above polymer, it is preferable that at least one of the other first carbon atom and one fourth carbon atom is bonded to a substituent containing a hydrogen atom, an alkyl group, a hydroxy group or a hetero atom.

[0020] In the above polymer, it is preferable that at least one of the other first carbon atom and one fifth carbon atom is bonded to a hydrogen atom, an alkyl group, a hydroxy group or a substituent containing a hetero atom.

[0021] A material according to some embodiments of the present invention includes the above-described polymer and an electropositive atom, which is an atom of an element having a lower electronegativity than carbon, or a compound having such an electropositive atom.

[0022] In the above-described material, it is preferable that the electropositive atom is coordinated to at least one of the second oxygen atom and the third oxygen atom.

[0023] The above-mentioned material includes the above-mentioned polymer and an electropositive atom which is an atom of an element having a lower electronegativity than carbon, or a compound having the above-mentioned electropositive atom.

[0024] Examples of the polymer include polymers represented by the following general formulas (1) to (6).

[0025] ...(1)

[0026] ... (2)

[0027] ...(3)

[0028] ...(4)

[0029] ...(5)

[0030] ...(6)

[0031] In general formulas (1) to (6), m and n are integers of 1 or more and 2 or more, respectively; R001 and R002 are each independently a hydrogen atom, an organic group, a substituent containing a heteroatom, a hydroxy group, a thiol group, or an organic group containing a heteroatom; and R003 is an arylene group, an alkylene group, or an organic group containing a heteroatom.

[0032] A method for producing a solid according to some aspects of the present invention includes a step (a) of introducing a first gas or a plurality of first particles into a processing chamber while a processing object serving as a raw material for the solid is placed inside the processing chamber, and in the step (a), at least a portion of the first gas or at least a portion of the plurality of first particles penetrates into the processing object.

[0033] In the above-described method for producing a solid, the object to be processed preferably has a repeating structure of a plurality of base units.

[0034] In the above-described method for producing a solid, it is preferable that each of the plurality of basic units has at least one of a sugar skeleton, an ester group, an arylene group, an ether group, an acetal group, a ketal group, a carbonyl group, and an alkylene group.

[0035] In the above-described method for producing a solid, it is preferable that the first gas or the plurality of first particles are composed of at least a first compound containing atoms of a first element having an electronegativity of less than 2.5.

[0036] In the above-described method for producing a solid, the first element is preferably any one of a Group 1 element, a Group 2 element, a Group 3 element, a Group 4 element, a Group 5 element, a Group 6 element, a Group 7 element, a Group 8 element, a Group 9 element, a Group 10 element, a Group 11 element, a Group 12 element, a Group 13 element, and a Group 14 element other than carbon.

[0037] In the above-described method for producing a solid, the electronegativity of the first element is preferably 2.0 or less.

[0038] In the above-described method for producing a solid, the first element is preferably any one of aluminum, titanium, nickel, iron, copper, and zinc.

[0039] In the above-described method for producing a solid, the first compound preferably has an organic group or a substituent containing an organic group.

[0040] In the above-described method for producing a solid, it is preferable that the object to be treated is vibrated or rocked during at least a part of the period during which the step (a) is carried out.

[0041] The above-described method for producing a solid preferably further comprises, after the step (a), a step (b) of vibrating or shaking the object to be treated.

[0042] In the above-described method for producing a solid, it is preferable that after the step (a) or after performing at least one step after the step (a), the method further comprises a step (c) of introducing a second gas or a plurality of second particles into the processing chamber with the object to be processed placed inside the processing chamber.

[0043] In the above-described method for producing a solid, the second gas or the plurality of second particles is preferably composed of at least a second compound.

[0044] The above-described method for producing a solid makes it possible, for example, to uniformly diffuse a substance such as an inorganic substance into the interior of a plastic material, or to cause at least a portion of the atoms, units, or substituents constituting the plastic material to interact with atoms or substituents contained in the infiltrated substance, thereby making it possible to create organic-inorganic hybrid materials that have new functions or are high-quality plastic materials.

[0045] In some embodiments of the method for producing a material according to the present invention, for example, a gas or aerosol that interacts with or bonds to a substituent, unit, or atom constituting a member such as a plastic material is first brought into contact with the member, and at least a portion of the gas or aerosol penetrates into the member.

[0046] The atoms, units or substituents constituting at least a part of the gas or aerosol penetrated by the substance penetration method, which is a method of using a gas or aerosol to penetrate into the interior of a member as described above, cause coordination or electrostatic interaction with the atoms, units or substituents constituting the member to be treated.

[0047] It is also possible to form a covalent bond between an atom, unit, or substituent constituting the member to be treated and an atom, unit, or substituent constituting at least a part of the gas or aerosol that has been permeated into the member by the substance permeation method, depending on the combination of the member and the gas or aerosol.

[0048] In the substance penetration method, it is possible to penetrate in the next step a substance that reacts with the substance that was first penetrated into the treated body. Therefore, even if penetration of a substance into the treated body in one step results in low uniformity inside the treated body, it is possible to disperse another substance with high uniformity or dispersibility inside the treated body by, for example, penetrating the treated body in stages with multiple types of substance.

[0049] By dispersing another substance with high uniformity or dispersibility inside the object to be treated in this way, it is possible to impart to the object various performances or properties that lead to added value as a product, such as high mechanical strength, heat resistance, electrical conductivity, corrosion resistance, gas barrier properties, toughness, dielectric properties, or refractive index.

[0050] A typical example of the plastic material is polyester, which is obtained by condensation reaction of a polycarboxylic acid such as a dicarboxylic acid with a polyol, which is a compound having multiple hydroxy groups.

[0051] Specific examples of plastic materials include polyethylene terephthalate (PET) produced by copolymerizing terephthalic acid (TPA) and ethylene glycol (EG), polytrimethylene terephthalate (PTT) produced by copolymerizing terephthalic acid (TPA) and 1,3-propanediol (PDO), and polybutylene terephthalate (PBT) produced by copolymerizing terephthalic acid and 1,4-butanediol.

[0052] At least one of the raw materials, ethylene glycol, propanediol, and other polyols and polycarboxylic acids, may be derived not only from fossil resources but also from biological resources such as plants, including corn, sugarcane, and wood.

[0053] Polycarboxylic acids can also be produced from sugars, such as polysaccharide derivatives or monosaccharide derivatives obtained from corn or corn cobs, sugar cane, or wood.

[0054] Examples of polysaccharide derivatives include cellulose derivatives, starch derivatives, glucose condensate derivatives, sucrose derivatives, and xylose condensate derivatives. Cellulose derivatives include cellulose acetate, cellulose acetate propionate, cellulose benzoate, and fatty acid cellulose. Starch derivatives include starch acetate, starch acetate propionate, starch benzoate, and fatty acid starch. Glucose condensate derivatives include glucose acetate condensates, glucose acetate propionate condensates, glucose benzoate condensates, and fatty acid glucose condensates. Sucrose derivatives include sucrose acetate, sucrose acetate propionate, sucrose benzoate, and fatty acid sucrose. Xylose condensate derivatives include xylose acetate condensates, xylose acetate propionate condensates, xylose benzoate condensates, and fatty acid xylose condensates.

[0055] Examples of monosaccharide derivatives include glucose derivatives such as glucose acetate, glucose acetate propionate, glucose benzoate, and fatty acid glucose; and xylose derivatives such as xylose acetate, xylose acetate propionate, xylose benzoate, and fatty acid xylose.

[0056] The substituents on the carbon atoms of the polysaccharides or monosaccharides used as raw materials may be, for example, hydroxy groups, carbonyl groups, alkyl groups, acyl groups, substituents containing a carbonyl group, substituents containing a heteroatom, or substituents containing an alkyl group, but polysaccharides or monosaccharides in which each of the two directly bonded carbon atoms has a hydroxy group are preferred. It is more preferable to use polysaccharides or monosaccharides that have two or more covalent bonds between carbon atoms that have hydroxy groups. It is particularly preferable that two or more covalent bonds between carbon atoms that have hydroxy groups are contained in a cyclic structure.

[0057] By reacting such a sugar in which carbon atoms having hydroxy groups are bonded to each other with a carboxylic acid having a carboxyl group and a carbonyl group other than the carboxyl group, a carboxylic acid having a ketal structure or an acetal structure can be obtained.

[0058] By reacting a polysaccharide or monosaccharide having two or more covalent bonds between carbon atoms having hydroxy groups with a carboxylic acid having a carboxyl group and a carbonyl group other than the carboxyl group, a polycarboxylic acid having two or more ketal structures or acetal structures can be obtained.

[0059] By reacting a sugar or monosaccharide containing two or more covalent bonds between carbon atoms having hydroxy groups in a cyclic structure with a carboxylic acid having a carboxyl group and a carbonyl group other than the carboxyl group, it is possible to obtain a polycarboxylic acid in which two or more covalent bonds in the cyclic structure derived from the sugar are shared with a cyclic structure such as a five- or six-membered ring of a ketal structure or an acetal structure.

[0060] A polymer obtained by reacting such a polycyclic polycarboxylic acid with, for example, a polyol is expected to exhibit high mechanical strength or heat resistance.

[0061] A manufacturing method for producing a plastic material containing an inorganic compound according to some embodiments of the present invention includes a heating step of heating a plastic material placed in a chamber section, a vacuum step of evacuating the chamber section, an inorganic substance providing step of providing a gaseous inorganic substance at a first temperature into the chamber section, a shaking step of shaking the plastic material in the chamber section to produce a plastic material containing an inorganic compound, an exhaust step of evacuating the chamber section after the shaking step, an oxidation-reduction product providing step of providing at least one of an oxide and a reduction product into the chamber section at a second temperature lower than the first temperature after the exhaust step, and a shaking step of shaking the plastic material containing the inorganic compound in the chamber section.

[0062] Some of the methods for producing organic-inorganic hybrid materials according to the present invention include a heating step of heating a plastic material placed in a chamber, a vacuum step of evacuating the chamber, an inorganic substance providing step of providing a gaseous inorganic substance at a first temperature into the chamber, a shaking step of shaking the plastic material in the chamber to produce an organic-inorganic hybrid material, an evacuation step of evacuating the chamber after the shaking step, an oxidation-reduction product providing step of providing at least one of an oxide and a reduction product into the chamber at a second temperature lower than the first temperature after the evacuation step, and a shaking step of shaking the organic-inorganic hybrid material in the chamber.

[0063] According to some aspects of the present invention, it is possible to obtain a material that is excellent in, for example, mechanical strength or heat resistance.

[0064] FIG. 1 is a diagram illustrating an outline of the configuration of a substance permeation device. FIG. 2 is a diagram illustrating an implementation procedure for permeating a substance into a polymer. FIG. 3 is a diagram illustrating changes in the interior of a polymer when a substance is permeated into the polymer. FIG. 4 is a diagram illustrating changes in the interior of a polymer when a substance is permeated into the polymer. FIG. 5 is a diagram illustrating changes in the interior of a polymer when a substance is permeated into the polymer.

[0065] Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail with reference to drawings etc. as necessary, but the present invention is not limited to the present embodiment. The present invention can be modified in various ways without departing from the gist of the invention. In the drawings, the same elements are given the same reference numerals, and redundant explanations will be omitted. Furthermore, positional relationships such as up, down, left, and right will be based on the positional relationships shown in the drawings unless otherwise specified. Furthermore, the dimensional ratios of the drawings are not limited to those shown.

[0066] Fig. 1 is a cross-sectional schematic diagram of a substance penetration device 100 according to some embodiments of the present invention. The substance penetration device 100 is broadly composed of a material supply unit 10 and a chamber unit 20. The material supply unit 10 is configured to be able to introduce multiple types of materials into the chamber unit 20. In a typical example of this embodiment, as shown in Fig. 1, the device is configured to be able to introduce two or three types of materials into the chamber unit 20.

[0067] The material supply section 10 is composed of a primary tank 11 for the first material, a temperature adjustment section 19 that adjusts the temperature of the primary tank 11 for the first material, a buffer tank 15 for the first material that temporarily stores the first material sent out from the primary tank 11 for the first material until the first material is introduced into the chamber section 20, at least a part of a connecting pipe 12 that connects the buffer tank 15 for the first material and a nozzle 18 for introducing the first material into the chamber section 20, a tank 13 for the second material, a temperature adjustment section 19 that adjusts the temperature of the tank 13 for the second material, and at least a part of a connecting pipe 14 that connects the second material tank 13 and a nozzle 18 for introducing the second material into the chamber section 20.

[0068] Although not shown in FIG. 1, a buffer tank for the second material, similar to the buffer tank 15 for the first material, can be appropriately provided between the primary tank 13 for the second material and the nozzle 18 connected via the connecting pipe 14, depending on conditions such as the properties and boiling point of the second material, the degree of vacuum set in the chamber 20, etc.

[0069] The primary tank 11 for the first material contains, for example, a solid or liquid first material at room temperature, and by appropriately setting the temperature of the temperature adjustment unit 19, multiple particles such as gas or aerosol can be generated.

[0070] In addition, the buffer tank 15 for the first material may be provided with a temperature adjustment function such as a temperature adjustment unit 19, similar to the primary tank for the first material, and at least a part of the connecting pipe 12 may also be provided with a temperature adjustment function.

[0071] In the substance permeation device 100 according to this embodiment, the temperature adjustment unit 19 and the temperature adjustment function described above are typically configured to be able to set any temperature between about 50°C and 300°C, for example.

[0072] The delivery of the first material to the chamber portion 20 can be controlled using a temperature adjustment function such as the temperature adjustment portion 19 described above, but the introduction of the first material into the chamber portion 20 may also be controlled by providing a valve between the primary tank 11 for the first material and the buffer tank 15 for the first material, between the buffer tank 15 for the first material and the nozzle 18, or at least in the nozzle 18 itself.

[0073] By appropriately setting the opening diameter of the valve when it is opened or the timing of intermittent opening and closing of the valve, the directionality when the first material is introduced into the chamber portion 20 as a gas or multiple particles, the speed or temperature of the gas molecules or particles, etc. can be appropriately controlled.

[0074] The delivery of the second material from the primary tank 13 for the second material can also be carried out using the temperature adjustment function of the temperature adjustment unit 19 or the like, but for example, by providing a valve between the primary tank 13 for the second material and the nozzle 18 connected via the connecting pipe 14, or on the nozzle 18 itself, the introduction of the second material into the chamber 20 can be controlled. This valve can also be configured or controlled in the same way as the valve corresponding to the supply line for the first material.

[0075] The material of at least a part of at least one of the primary tank 11 for the first material, the buffer tank 15 for the first material, the connecting pipe 12, the primary tank 13 for the second material, and the connecting pipe 14 can be, for example, stainless steel, aluminum alloy, carbon steel, fiber-reinforced plastic, or the like, and is appropriately selected in consideration of the properties of the first material and the second material, the temperature set by the temperature adjustment unit 19, the introduction conditions into the chamber unit 20, and the like. The inside of the above-mentioned parts is preferably subjected to, for example, glass lining or fluorine lining.

[0076] Examples of compounds stored in the primary tank 11 for the first material include compounds containing elements with an electronegativity of less than 2.5. More specifically, compounds containing elements with an electronegativity of 2.0 or less are examples. When considering the efficiency of introduction into the chamber 20, compounds in which the above-mentioned elements are bonded to an organic group directly or via a heteroatom are preferred because they are relatively volatile. Specific examples of such compounds include so-called organometallic compounds such as organoaluminum and organozinc, organosilicon compounds, and so-called non-Werner complexes in which a carbonyl group or an allyl group is bonded to a transition metal element, which are relatively volatile and therefore preferred.

[0077] The primary tank 13 for the second material contains a gas for causing a reaction such as oxidation, reduction, nitridation or dehydration reaction, or a liquid or solid for generating the gas.

[0078] <Configuration of chamber section 20> The chamber section 20 has a storage container 26 that stores the object to be treated, a rotation mechanism 24 for rotating the storage container 26, a reduced pressure container 22 for reducing the pressure inside the storage container 26 to below atmospheric pressure, and a lid section 21 for maintaining the reduced pressure in the reduced pressure container 22 etc. or suppressing a pressure increase.

[0079] The lid 21, the reduced pressure vessel 22, the rotating vessel 24, and the storage vessel 26 are made of a metal material such as stainless steel or aluminum, and their shapes are preferably rectangular, cubic, cylindrical, or other shapes with an internal space, with the detailed shape and dimensions being appropriately selected based on the shape or properties of the object to be processed. It is preferable that the chamber 20 forms an angle θ with the floor, with the angle θ being particularly preferably 20° to 80°. This allows, for example, an operator to easily attach and detach the storage vessel 26. Another advantage is that it makes it easier to place the object to be processed in the storage vessel 26 or remove it from the storage vessel 26.

[0080] The storage container 26 may be detachable from the rotation mechanism 24, or may be fixed to the rotation container 24. When the storage container 26 is detachable from the rotation mechanism 24, it becomes easy for an operator to store objects to be treated in the storage container 26 removed from the chamber section 20 or to remove objects that have been treated.

[0081] For example, the storage container 26 may be fixed to the rotary container 24 with fasteners such as screws or bolts, or the storage container 26 and the rotary container 24 may be integrally formed.

[0082] The rotary vessel 24 is connected to a rotary motor MT and a shaft 25 that transmits the power of the rotary motor MT in order to rotate the storage vessel 26. The rotary motor MT and the rotary vessel 24 may be directly connected via the shaft 25, or may be indirectly connected via a gear or a belt and the shaft 25. The rotary vessel 24 can be rotated by the rotary motor MT at, for example, 5 rpm to 200 rpm. The rotation speed of the rotary vessel 24 can be kept constant or can be changed over time depending on the processing conditions of the object to be processed, etc.

[0083] In the substance permeation device 100, the shaft 25 passes through the reduced pressure vessel 22. A magnetic fluid seal (not shown) attached to the reduced pressure vessel 22 allows the shaft 25 to rotate even when the degree of reduced pressure inside the reduced pressure vessel 22 becomes high.

[0084] It is possible to infiltrate a material into the interior of the object to be treated without using the rotating vessel 24. In this case, it is preferable to rock or vibrate the object to be treated for at least a portion of the time period during which the first material or the second material is introduced into the chamber 20 in which the object to be treated is accommodated in the storage vessel 26. The vibration or rocking can be achieved, for example, by vibrating or rocking the storage vessel 26 or the object to be treated, or by changing the amount of gas or aerosol ejected onto the object to be treated at an as-needed or predetermined cycle.

[0085] A chamber heater 29 is attached to the bottom surface of the rotating vessel 24. This allows the heat from the chamber heater 29 to heat the storage vessel 26 via the rotating vessel 24. The chamber heater 29 makes it possible to adjust the temperature of the object to be processed in the storage vessel 26 to a temperature that corresponds to the processing conditions for the object, for example.

[0086] The chamber heater 29 may be attached to a location other than the bottom of the rotating vessel 24, such as the side of the rotating vessel 24, the storage vessel 26, the reduced pressure vessel 22, or the lid 21. Of course, the chamber heater 29 may be attached to two or more of the rotating vessel 24, the storage vessel 26, the reduced pressure vessel 22, or the lid 21, or to two or more locations on one of the rotating vessel 24, the storage vessel 26, the reduced pressure vessel 22, or the lid 21.

[0087] The decompression vessel 22 is a mechanism for creating a decompression condition inside the storage vessel 26, and is connected to a decompression pipe 27 which is connected to a vacuum pump VP.

[0088] The vacuum pump VP can set the pressure inside the container 26 to, for example, 10 −3 Pa to 100 Pa.

[0089] The degree of vacuum can be increased by arranging vacuum pumps VP in multiple stages or by combining multiple types of vacuum pumps. For example, first, the rotary pump is connected to the vacuum vessel 22 and operated, and when a certain degree of vacuum is reached, the connection with the vacuum vessel 22 is switched from the rotary pump to a turbomolecular pump, thereby achieving a higher degree of vacuum. The configuration and type of vacuum pump VP can be selected appropriately depending on the desired degree of vacuum within the chamber 20.

[0090] An exhaust gas removal unit GR is connected to the pressure reduction pipe 27. Any gas or aerosol of the first material introduced into the chamber 20 that is not used in treating the object to be treated or any surplus gas is captured or treated by the exhaust gas removal unit GR.

[0091] The lid 21 is intended to improve the airtightness inside the reduced pressure vessel 22, and a sealing member such as an O-ring is arranged on the lid 21 or on the reduced pressure vessel 22 that comes into contact with the lid 21. The connecting pipes 12 and 14 are attached to the lid 21, and it is preferable that the nozzle 18 connected to the connecting pipe 12 and the nozzle connected to the connecting pipe 14 are arranged so that they can reach the inside of the storage vessel 26 when the lid 21 is closed.

[0092] A connecting pipe 33 having a nozzle 38 is attached to the lid 21. A gas tank 31 is attached to the connecting pipe 33. The gas tank 31 can store, for example, an inert gas such as nitrogen, argon, or helium; a reducing gas such as hydrogen gas, carbon monoxide gas, or hydrocarbon gas; a nitriding gas such as ammonia; or an oxidizing gas such as oxygen gas, chlorine gas, ozone gas, or water vapor.

[0093] When the processing of the object to be processed under reduced pressure is completed, the gas stored in the gas tank 31 may be used to return the pressure inside the reduced pressure container 22 to atmospheric pressure.

[0094] Although Figure 1 does not depict timers, temperature sensors, computers, and other control devices, it is possible to provide appropriate control devices that control at least some of the functions of the substance penetration device 100, such as a temperature adjustment unit 19, a valve or monitoring device attached to the chamber heater 29, or the path of the supply line for the first material to the chamber portion 20, a valve or monitoring device attached to the path of the supply line for the second material to the chamber portion 20, or a valve or monitoring device provided in the path from the gas tank 31 to the chamber portion 20, a vacuum pump, and a rotating vessel 24.

[0095] FIG. 2 is a flowchart illustrating the substance penetration method, and the following description will be made with reference to this drawing.

[0096] A plastic material is placed in the container 26 as an object to be treated (S21). The temperature of the plastic material is preferably set lower than the chamber temperature. Furthermore, the internal temperature of the plastic material is preferably set lower than the surface temperature of the plastic material.

[0097] When the first material penetrates into the plastic material to be treated, the temperature inside the plastic material may tend to rise. Therefore, for example, when the plastic material to be treated is a plastic material with a low melting point, it is preferable to measure the temperature of the wall of the chamber 20 with a thermocouple or the like before the first material penetrates into the plastic material, and adjust the temperature of the plastic material to be lower than the temperature of the wall of the chamber 20 by, for example, placing the plastic material on a stage or the like through which a refrigerant or cold air is circulated.

[0098] After step S21, it is preferable to place the next plastic material in the container (S22) during a period in which there is no significant change in the temperatures of the above-mentioned parts since the temperature measurement.

[0099] If the storage container 26 is detachable, the plastic material to be treated is stored in the storage container 26 after the storage container 26 is removed from the rotating container 24, and if the storage container 26 is fixed, the plastic material is stored in the storage container 26 in the chamber section 20, for example.

[0100] Next, a pressure reduction operation (S23) of the chamber portion 20 is performed using a vacuum pump VP. The vacuum pump VP may be used to reduce the pressure inside the container 26 to, for example, 100 Pa or less. After performing S23, the supply of the first material to the chamber portion 20 is started (S24).

[0101] The supply of the first material to the chamber 20 (S24) is performed by, for example, heating the first material primary tank 11 by the heater 19 attached to the first material primary tank 11.

[0102] As a result, the first material, which is liquid at room temperature, becomes gaseous or aerosol, and the first material, which is solid at room temperature, becomes gaseous or aerosol by sublimation or the like, and is supplied to the container 26 containing the object to be treated.

[0103] During at least a portion of the period during which the first material thus converted into a gas or aerosol and the object to be treated are in contact with the container 26, the chamber 20 may be heated by, for example, the heater 29. For example, when the object to be treated is a plastic material, it is typically preferable to heat it to a temperature of 80°C to 150°C.

[0104] Before performing step S24, for example, an inert gas (nitrogen, argon, helium, etc.) may be introduced into the chamber 20.

[0105] This makes it possible, for example, when reacting or interacting with desired atoms or substituents that make up a plastic material, to suppress reaction or interaction with other substances during the process of the first material penetrating into the plastic material.

[0106] After the supply of the first material to the chamber 20 is stopped (S25), the rotation of the container 26 is started (S26), and then the rotation of the container 26 is stopped (S27).

[0107] Next, the pressure in the chamber 20 is reduced again (S28). This pressure reduction operation makes it possible to remove at least a portion of the first material that has been supplied to the chamber 20 and has not permeated the object to be treated, or that has adhered to the inside of the chamber 20.

[0108] By performing the operation of S28, when the second material described later is supplied to the chamber section 2, it is possible to remove the first material of the second material supplied to the chamber section 20 that has not penetrated into the object to be treated, or the excess first material that has adhered to the inside of the storage container 26, etc.

[0109] Thereafter, the supply of the second material to the chamber portion 2 is started (S29). As the second material, for example, a substance that reacts with the first material that has permeated into the plastic material that is the object to be treated can be used.

[0110] By operating S29, it becomes possible to introduce into the interior of the workpiece substances that are difficult to introduce directly or in one step, such as substances with low vapor pressure or substances that require high temperature or high vacuum to volatilize or aerosolize.

[0111] To give a specific example, metal oxides and inorganic metal salts have low vapor pressures and therefore require high temperatures or high vacuums to volatilize or aerosolize them. However, if, for example, the first material and the second material are respectively a metal element such as trimethylaluminum, an organometallic compound having an organic group on the metal element, and a substance that reacts with the organometallic compound such as water or oxygen, the organometallic compound is more easily volatilized than the corresponding metal oxide or inorganic salt, and therefore it is possible to use the substance penetration device 100 to cause the organometallic compound to penetrate into the interior of the object to be treated.

[0112] In addition, organometallic compounds generally have a lower degree of association than the corresponding metal oxides or inorganic salts, and even if they do form clusters, their size is small, which gives them the advantage of being easily diffused into the object to be treated.

[0113] By further supplying a second material that is reactive with the organometallic compound to the container 26, the first material and the second material react inside the object to be treated, making it possible to introduce metal oxides, inorganic salts, etc., which are difficult to introduce directly or in one step.

[0114] After S29, the supply of the second material to the chamber 20 (S30) is stopped, and then the rotation of the storage container 26 is started (S31) and stopped (S32). Furthermore, the pressure in the chamber 20 is reduced (S33), and then an inert gas is supplied to the chamber 20 (S34). This completes the series of plastic material processing steps (S35).

[0115] The decompression operation of S33 is carried out in the same manner as S28 described above, for example, to remove at least a portion of the second material that has not penetrated into the interior of the workpiece, the second material that is adhering to the inside of the storage container 26, or the second material that has not completed its reaction with the first material and remains unreacted.

[0116] In the above-described series of steps, depending on the combination of the object to be treated or the first material, it is possible to shorten the processing time by, for example, performing the steps so that at least a portion of the period from when the supply of the first material to the chamber section starts (S24) to when the supply of the first material to the chamber section stops (S25) or at least a portion of the period from when the chamber section 20 is depressurized (S23) to when S24 overlaps with at least a portion of the period from when the storage container 26 starts to rotate (S26) to when the storage container 26 stops to rotate (S27).

[0117] Similarly, the processing time can be shortened by overlapping at least a portion of the period from depressurizing the chamber portion 20 (S28) to starting to supply the second material to the chamber portion (S29) or at least a portion of the period from starting to supply the second material to the chamber portion (S29) to stopping to supply the second material to the chamber portion with at least a portion of the period from starting to rotate the storage container 26 (S31) to stopping to rotate the storage container 26 (S32).

[0118] <Examples of Plastic Materials Targeted by the Material Penetration Method> Specific examples of plastic materials targeted by the material penetration method include, as shown below, polyethylene terephthalate (PET) synthesized by copolymerizing terephthalic acid (TPA) and ethylene glycol (EG), polytrimethylene terephthalate (PTT) synthesized by copolymerizing terephthalic acid (TPA) and 1,3-propanediol (PDO), and polybutylene terephthalate (PBT) synthesized by copolymerizing terephthalic acid and 1,4-butanediol.

[0119]

[0120] At least one of the polyols such as ethylene glycol and propanediol and polycarboxylic acids, which are raw materials for synthesizing the above-mentioned plastic materials, may be derived not only from fossil resources but also from biological resources such as plants such as corn, sugarcane, and wood.

[0121] The plastic material to be subjected to the substance permeation method may have the following sugar skeleton.

[0122]

[0123] The polymer having the sugar skeleton is a polymer having a repeating structure whose basic unit is a cyclic structure containing an oxygen atom and a plurality of cyclic structures each sharing two covalent bonds contained in the cyclic structure.

[0124] In the above-mentioned basic unit, A and B have a six-membered ring containing one oxygen atom and a structure in which two covalent bonds of the six-membered ring are shared by ring structures each containing two oxygen atoms. The two ring structures each containing two oxygen atoms are both five-membered rings, and the two oxygen atoms in each of the two five-membered rings are directly bonded to carbon atoms constituting the above-mentioned six-membered ring.

[0125] Furthermore, in the basic unit, the two five-membered rings are each bonded to a carbon atom of a carboxyl group, and one of the two oxygen atoms of one of the carboxyl groups is bonded to an adjacent basic unit via a linking group, while one of the two oxygen atoms of the other carboxyl group is bonded to an adjacent basic unit via a linking group.

[0126] In the above-mentioned basic unit, C and D have a five-membered ring containing one oxygen atom and a structure in which two covalent bonds of the five-membered ring are shared by ring structures each containing two oxygen atoms. The two ring structures each containing two oxygen atoms are a six-membered ring and a five-membered ring, and one of the two oxygen atoms constituting the six-membered ring is directly bonded to a carbon atom constituting the central five-membered ring, and the other oxygen atom is bonded to a carbon atom constituting the central five-membered ring via one carbon atom.

[0127] In the above-mentioned basic units, the six-membered ring and the five-membered ring, each of which shares one covalent bond with the central five-membered ring, are each bonded to a carbon atom of a carboxyl group. One of the two oxygen atoms of one of the carboxyl groups is bonded to an adjacent basic unit, and one of the two oxygen atoms of the other carboxyl group is bonded to an adjacent basic unit via a linking group. A and B are particularly stable in the central six-membered ring of the polycyclic structure, resulting in good strength, elongation, and heat resistance. Furthermore, by material infiltration, these properties are further improved. On the other hand, C and D tend to have inferior strength, elongation, and heat resistance compared to A and B because the central five-membered ring of the polycyclic structure is less stable than the six-membered ring. However, by material infiltration, the strength, elongation, and heat resistance of the polymer itself are improved, making them suitable for use as a target material for material infiltration.

[0128] The outline of the synthesis procedure for tricyclic plastic materials having a sugar structure as a basic unit will be explained using D-xylose as an example of a monosaccharide.

[0129] A tricyclic polycarboxylic acid is synthesized by reacting D-xylose with glyoxylic acid, a carboxylic acid having a formyl group, and the carboxylic acid is further methyl-esterified to obtain the monomer xylose dimethylglyoxylate. This monomer is then reacted with ethylene glycol to obtain polyethylene diglyoxylate xylose.

[0130]

[0131] In the following, 1,6-hexanediol instead of ethylene glycol is reacted with xylose dimethylglyoxylate to obtain polyhexylene diglyoxylate.

[0132]

[0133] In the following, 1,3-propanediol instead of ethylene glycol is reacted with xylose dimethylglyoxylate to obtain polypropylene xylose diglyoxylate.

[0134]

[0135] As the sugar raw material, those having a structure represented by the following general formula can be used.

[0136] ... (7) (R ００４ is a hydrogen atom, an organic group, a substituent containing a heteroatom, a hydroxy group, a thiol group, or an organic group containing a heteroatom.

[0137] Specific examples include D-xylose, arabinose, and ribose represented by the following general formulas.

[0138] ... (8) Sugar, fucose or rhamnose.

[0139] Specific examples include deoxysugars represented by the following general formula, fucose, and rhamnose.

[0140] ...(9)

[0141] Specific examples include glucose, mannose, and galactose represented by the following general formula:

[0142] ...(10)

[0143] To synthesize the above-mentioned saccharide and a tricyclic monomer having a plurality of cyclic skeletons, for example, the above-mentioned saccharide is reacted with a carboxylic acid having a carbonyl group or a formyl group represented by the following general formula:

[0144] ... (11) (R ００５ is a hydrogen atom, an organic group, a substituent containing a heteroatom, a hydroxy group, a thiol group, or an organic group containing a heteroatom, and R ００６ is an arylene group, an alkylene group, or an organic group containing a heteroatom.

[0145] Examples of carboxylic acids having a carbonyl group or a formyl group include glyoxylic acid, pyruvic acid, 2-oxobutyric acid (2-ketobutyric acid), 6-oxoheptanoic acid, and 4-acetylbutyric acid.

[0146] When a saccharide represented by the general formula (11) is reacted with a carboxylic acid having a carbonyl group represented by the general formula (7), a polycyclic monomer represented by the following general formula can be obtained.

[0147] ... (12) (R ００４ is a hydrogen atom, an organic group, a substituent containing a heteroatom, a hydroxy group, a thiol group, or an organic group containing a heteroatom, and R ００５ is a hydrogen atom, an organic group, a substituent containing a heteroatom, a hydroxy group, a thiol group, or an organic group containing a heteroatom, and R ００６ is an arylene group, an alkylene group, or an organic group containing a heteroatom.

[0148] Furthermore, by reacting a polycarboxylic acid represented by the general formula (12) with a polyol, a polycyclic monomer represented by the following general formula can be obtained.

[0149] ... (13) (m and n are integers of 1 or more and 2 or more, respectively, and R ００４ is a hydrogen atom, an organic group, a substituent containing a heteroatom, a hydroxy group, a thiol group, or an organic group containing a heteroatom, and R ００５ is a hydrogen atom, an organic group, a substituent containing a heteroatom, a hydroxy group, a thiol group, or an organic group containing a heteroatom, and R ００６ is an arylene group, an alkylene group, or an organic group containing a heteroatom.

[0150] The above-mentioned plastic materials or polymers can be molded into molded bodies by injection molding, film molding, extrusion molding, photomolding, microwave molding, press molding, inflation molding, melt spinning, nonwoven fabric molding, etc., and the molded bodies can be used in the substance penetration method.

[0151] <Subject to be treated in substance penetration method> As the subject to be treated, for example, the above-mentioned plastic material or polymer can be used, but for example, other resins, polymers, inorganic substances, ores, or plastic materials can be appropriately selected depending on the desired application, physical properties, etc.

[0152] A typical example of a substance penetration device according to some aspects of the present invention is a plastic material, which may be in the form of, for example, a pellet having a diameter of 0.1 mm to 5 mm and a length of 0.1 mm to 5 mm, a fiber having a diameter of less than 0.5 mm and a length of 3 mm or more, a spherical particle having a diameter of 1 mm or more, or a powder having a diameter of 1 mm or less.

[0153] Examples of plastic materials include those derived from petroleum and those derived from biological resources such as plants.

[0154] In addition to the above-mentioned polyethylene terephthalate, examples of petroleum-derived plastic materials include PP (polypropylene), PC (polycarbonate), PMMA (polymethyl methacrylate), PS (polystyrene), COP (cycloolefin polymer), COC (cycloolefin copolymer), and the like.

[0155] Examples of plastic materials derived from biological resources include, in addition to the above-mentioned plastic materials containing sugar structures, polylactic acid (PLA), polybutylene succinate (PBS), hydroxyalkanoic acid (PHA), polyhydroxybutyric acid (PHB), PHBH (a copolymer polyester composed of R-3-hydroxybutanoic acid (3HB) and R-3-hydroxyhexanoic acid (3HH)), cellulose or a derivative thereof, and starch or a derivative thereof.

[0156] <Material to be Penetrated (First Material)> Examples of the first material include compounds containing elements with an electronegativity of less than 2.5. In this case, when the object to be treated is a substance mainly composed of carbon and nitrogen or oxygen, such as a general resin or plastic, these elements all have an electronegativity of 2.5 or more, so it is preferable that the elements contained in the first material with an electronegativity of less than 2.5 are relatively electrically positive. This has the advantage that molecules or particles of the first material can easily penetrate into the object to be treated. Specifically, examples of the first material include compounds containing elements belonging to Groups 1 to 13 and compounds containing elements of Group 14 other than carbon.

[0157] More specifically, examples of the first material include compounds containing metal elements such as aluminum compounds, iron compounds, titanium compounds, nickel compounds, copper compounds, zinc compounds, etc. Since elements in Group 14 other than carbon are also more electropositive than carbon, examples of the first material include compounds containing silicon, germanium, tin, and lead.

[0158] Examples of aluminum compounds include trimethylaluminum and aluminum chloride. Examples of iron compounds include ferrocene, bis(N,N'-diisopropylbutanamidinate)iron, and bis(N,N'-diisopropylpropionamidinate)iron. Examples of silicon compounds include triethylsilane and tris(dimethylamino)silane (TDMAS).

[0159] Among the above-mentioned compounds, compounds in which an atom of an element having an electronegativity of less than 2.5 is bonded to an organic group directly or via a heteroatom are particularly suitable because of their relatively high volatility. Compounds in which a carbon atom such as a carbonyl group or an allyl group is bonded to a transition metal element are relatively volatile and are therefore suitable for use as the first material.

[0160] <Material to be penetrated (second material)> The second material is appropriately selected in consideration of, for example, the combination with the first material, the object to be treated, the desired treatment for the object to be treated, etc. Examples of the second material include inert gases such as argon, helium, and nitrogen, halogen gases such as water (HO), oxygen, bromine, chlorine, and iodine, oxidizing gases such as oxygen and ozone (O), carburizing gases such as carbon monoxide and alcohols such as methanol and ethanol, nitriding gases such as ammonia, and reducing gases such as hydrogen and hydrocarbon gases.

[0161] The properties of the second material may be, for example, a solid that is sublimable, such as iodine, a liquid such as bromine, or a gas such as argon or helium, and are selected appropriately depending on the combination with the first material, the object to be treated, the desired treatment of the object to be treated, etc.

[0162] Example 1 is an example in which polyethylene terephthalate, a copolymer, was used as the material to be treated. The polyethylene terephthalate was obtained by processing polyethylene terephthalate powder into pellets using an extruder, a cooling stage, and a pelletizer.

[0163] 1 kg of these pellets was placed in the container 26 of the chamber 20 of the material permeation device 100. The temperature of the chamber 20 was set to a range from 80°C to 120°C.

[0164] The chamber portion 20 has a cylindrical structure, and is rotated around a line connecting the substantial center of a first main surface of the cylinder and the substantial center of a second main surface opposite the first main surface, as the rotation axis.

[0165] The rotation speed was set between 10 rpm and 100 rpm, and during at least a portion of the period during which the rotation was being carried out, the pressure inside the chamber 20 was reduced by the vacuum pump VP to a reduced pressure of 5 Pa inside the chamber 20.

[0166] As the first material, trimethylaluminum, which is liquid at room temperature, was stored in the first material primary tank 11. The liquid trimethylaluminum in the first material primary tank 11 was heated to 130°C, and vaporized trimethylaluminum was supplied into the chamber 20.

[0167] Vaporized trimethylaluminum was supplied until the degree of vacuum in the chamber 20 reached 500 Pa, and at that point the nozzle 18 of the connecting pipe 12 was closed.

[0168] This exposed the pellets placed in the container 26 to vaporized trimethylaluminum.

[0169] In the chamber 20, the pellets were subjected to agitation due to the rotation described above, or were mixed inside the chamber 20.

[0170] As a result, the vaporized trimethylaluminum penetrated into the pellet, the polyethylene terephthalate came into contact with the trimethylaluminum gas, and the aluminum atoms of the trimethylaluminum were coordinated to the carbonyl groups of the polyethylene terephthalate. The vaporized trimethylaluminum was supplied for 1,000 seconds. After that, the chamber 20 was vacuum pumped VP to remove the gas containing trimethylaluminum that had not interacted with the polyethylene terephthalate inside the chamber 20.

[0171] Thereafter, vaporized water (H2O) at 100-105°C as the second material was supplied into the chamber 20 until the degree of vacuum reached 250 Pa, and then the nozzle 18 connected to the connecting pipe 14 was closed.

[0172] During at least a part of the period during which vaporized water was supplied into chamber 20 via connecting pipe 14 and nozzle 18 connected to the connecting pipe, or after the end of the period, chamber 20 rotated about a line connecting the substantial center of the first main surface and the substantial center of the second main surface. In this example, the time for which vaporized water was supplied was 250 seconds.

[0173] By exposing the pellets placed inside the container 26 to steam while rotating them in this manner, it is possible to improve the uniformity of the penetration of steam into the pellets.

[0174] The water vapor that had permeated the interior of the pellet reacted with the trimethylaluminum that had previously been permeated into the interior of the pellet as the first material, to produce aluminum oxide and methane.

[0175] Thereafter, the pressure inside the chamber 20 was reduced again by the vacuum pump VP. This removed the methane generated by the reaction between trimethylaluminum and water vapor. Nitrogen or argon was then supplied into the chamber 20 to restore the pressure inside the chamber 20 to atmospheric pressure, the lid 21 was opened, and the pellets that had undergone the above-described series of processes were removed.

[0176] FIG. 3 shows a schematic diagram of the case where polyethylene terephthalate is treated with trimethylaluminum, an organometallic compound containing aluminum, an element having an electronegativity of less than 2.5, and water vapor.

[0177] In the structural formula of polyethylene terephthalate, n is an integer equal to or greater than 2. When vaporized trimethylaluminum is allowed to penetrate polyethylene terephthalate, the aluminum atoms of trimethylaluminum have low electronegativity and high affinity for oxygen atoms, and therefore interact with the oxygen atoms of the ester groups of polyethylene terephthalate, forming a structure in which they are coordinated to the ester groups.

[0178] When water vapor is applied to such a structure in which an electropositive aluminum atom is coordinated with an electropositive oxygen atom, the methyl group on the aluminum atom of trimethylaluminum is eliminated to form methane, and the aluminum atom is converted to a hydroxyl group.

[0179] The aluminum atom is bonded to the oxygen atom, which has a higher electronegativity, from the carbon atom. This makes the aluminum atom more electropositive, which is thought to strengthen the interaction between the aluminum atom and the ester group.

[0180] Furthermore, when the hydroxyl groups on the aluminum atoms are further heated or reduced pressure, the hydroxyl groups on the aluminum atoms undergo dehydration condensation with the hydroxyl groups on adjacent aluminum atoms, and the polyethylene terephthalate main chain changes to a crosslinked structure via the aluminum atoms and oxygen atoms, as shown in Figure 4. This structure improves the strength, hardness, heat resistance, refractive index, etc. of the plastic.

[0181] Example 2 is an example in which polybutylene terephthalate, a copolymer, was used as the material to be treated. The polybutylene terephthalate was obtained by processing polybutylene terephthalate powder into pellets using an extruder, a cooling stage, and a pelletizer.

[0182] In the same manner as in Example 1, a polybutylene terephthalate in a sintered state was treated with trimethylaluminum and water vapor.

[0183] Example 3 relates to the synthesis of polyethylene xylose diglyoxylate, a so-called bioplastic material produced from raw materials derived from biological resources, and the processing of polyethylene xylose diglyoxylate.

[0184] The synthesis of polyethylene diglyoxylate xylose was carried out as follows.

[0185] First step: D-xylose obtained by extraction from corn cobs and subsequent purification treatment and glyoxylic acid (aqueous solution) produced from corn-derived ethylene glycol were heated in the presence of sulfuric acid as a catalyst and dehydrated under reduced pressure to obtain a crude product (hereinafter referred to as "crude GX") mainly composed of GX as described above.

[0186] The above crude product was identified using analytical or analytical instruments such as thin layer chromatography (TLC), infrared spectroscopy (IR), gas chromatography (GC) and nuclear magnetic resonance (NMR).

[0187] Second step: Sulfuric acid and methanol were added to crude GX and the mixture was refluxed to react, followed by extraction with dichloromethane, washing with water, drying, and concentration to obtain a crude product (hereinafter referred to as "crude MX") mainly consisting of the methyl ester of GX (MX). The fact that crude MX was obtained was confirmed by analysis or analytical devices such as TLC, IR, GC, and NMR.

[0188] Third step: The purified MX product, ethylene glycol, and antimony (III) oxide were polymerized by heating and reducing the pressure, and then crystallized from hexafluoro-2-propanol (HFIP / IPA) to obtain a polymerized polyethylene diglyoxylate xylose.

[0189] More specifically, 63.0 g (0.420 mol) of D-xylose, 126.0 g (0.851 mol) of a 50% aqueous solution of glyoxylic acid, and 2.1 g of sulfuric acid were placed in a 500 ml recovery flask, and the mixture was concentrated by heating using an evaporator (bath temperature: 90°C; reduced pressure: 1.6 kPa; reaction time: 3 hours) to obtain 121.8 g of crude GX (crude yield: 100%).

[0190] 70.0 g of crude GX was added with 0.3 g of sulfuric acid and 120.0 g of methanol, and the mixture was refluxed for 2 hours. After reflux, sodium bicarbonate was added to the reaction mixture, which was then concentrated. The residue was extracted with dichloromethane and washed with water. The washed dichloromethane solution was dried over magnesium sulfate, and the filtered organic layer was concentrated to obtain 59.0 g of crude MX (yield 48%).

[0191] Crude MX (100 g, 35 mmol) was mixed with ethylene glycol (86 mmol, 2 equiv.), 5 mg of dibutyltin oxide, 10 mg of Irganox 1076, and 10 mg of triphenyl phosphite in a 300 ml round-bottom flask.

[0192] Next, this mixture was heated to 140°C while stirring in an oil bath. After 4 hours, 2 mg of dibutyltin oxide was added to the reaction mixture. The reaction mixture was then heated to 190°C to allow the polycondensation reaction to proceed. The reaction was stopped after 8 hours. The reaction mixture was cooled to room temperature and dissolved in a minimum amount of 1,1,1,3,3,3-hexafluoroisopropanol (250 mL). The resulting solution was added dropwise to methanol (1 L) to precipitate the polymer. The polymer was collected by filtration, washed with isopropyl alcohol and then diethyl ether, and dried in vacuum at 60°C for 24 hours to obtain polyethylene xylose diglyoxylate as a white powder. This white powder polyethylene xylose diglyoxylate was pelletized using an extruder, cooling stage, and pelletizer.

[0193] 1 kg of these pellets was treated with trimethylaluminum and water in the material permeation device 100. The specific treatment procedure was the same as that in Example 1, in which the polyethylene terephthalate was treated using the material permeation device.

[0194] In the structural formula of polyethylene xylose diglyoxylate, n is an integer equal to or greater than 2. When vaporized trimethylaluminum is permeated into polyethylene xylose diglyoxylate, as shown in Figure 5, the aluminum atoms of trimethylaluminum have low electronegativity and high affinity for oxygen atoms, and therefore interact with the oxygen atoms of the ester groups or acetal groups of polyethylene xylose diglyoxylate, forming a structure in which they are coordinated to the ester groups or acetal groups.

[0195] When water vapor is applied to such a structure in which an electropositive aluminum atom is coordinated with an electropositive oxygen atom, the methyl group on the aluminum atom of trimethylaluminum is eliminated to form methane, and the aluminum atom is converted to a hydroxyl group.

[0196] This results in a structure in which the aluminum atom is bonded from the carbon atom to the oxygen atom, which has a higher electronegativity, and this increases the positive charge on the aluminum atom, which is thought to strengthen the interaction between the aluminum atom and the ester group or acetal group.

[0197] Furthermore, when the hydroxyl groups on the aluminum atoms are further heated or reduced pressure, the hydroxyl groups on the aluminum atoms undergo dehydration condensation with the hydroxyl groups on adjacent aluminum atoms, and the polyethylene terephthalate main chain changes to a crosslinked structure via the aluminum atoms and oxygen atoms, as shown in Figure 6. This structure improves the strength, hardness, heat resistance, refractive index, etc. of the plastic.

[0198] The synthesis of polypropylene diglyoxylate xylose was similar to the synthesis of polyethylene diglyoxylate in Example 3 above, except that 1,3-propanediol was used in place of ethylene glycol.

[0199] Furthermore, similarly to the polyethylene diglyoxylic acid in Example 3, the product was made into pellets, and further treated with trimethylaluminum and water vapor using the substance permeation device 100 in the same manner as in Example 3 above.

[0200] Polyethylene dipyruvate xylose (5a) was synthesized in the same manner as in Example 3, except that pyruvic acid was used instead of glyoxylic acid.

[0201] ... (14) (m and n are integers of 1 and 2 or more, respectively.)

[0202] Further, polyethylene dioxobutyrate xylose (5b) represented by the following formula was synthesized in the same manner as in Example 3, except that glyoxylic acid was replaced with 2-oxobutyric acid.

[0203] ... (15) (m and n are integers of 1 and 2 or more, respectively.)

[0204] Further, polyethylene dioxoheptanoate xylose (5c) represented by the following formula was synthesized in the same manner as in Example 3, except that glyoxylic acid was replaced with 6-oxoheptanoic acid.

[0205] ... (16) (m and n are integers of 1 and 2 or more, respectively.)

[0206] The polymers 5a, 5b and 5c were pelletized in the same manner as in Example 3, and further treated with trimethylaluminum and water vapor using the substance permeation device 100 in the same manner as in Example 3.

[0207] Polyethylene diglyoxylate fucose (6a) represented by the following formula was synthesized in the same manner as in Example 3, except that D-xylose was replaced with fucose.

[0208] ... (17) (m and n are integers of 1 and 2 or more, respectively.)

[0209] Polyethylene pyruvate fucose (6b) represented by the following formula was synthesized in the same manner as in Example 3, except that D-xylose was changed to fucose and glyoxylic acid was changed to pyruvic acid.

[0210] ... (18) (m and n are integers of 1 and 2 or more, respectively.)

[0211] Further, polyethylene dioxobutyrate fucose (6c) represented by the following formula was synthesized in the same manner as in Example 3, except that D-xylose was changed to fucose and glyoxylic acid was changed to 2-oxobutyric acid.

[0212] ... (19) (m and n are integers of 1 and 2 or more, respectively.)

[0213] Furthermore, polyethyleneoxodifutanoate fucose (6d) represented by the following formula was synthesized in the same manner as in Example 3, except that D-xylose was changed to fucose and glyoxylic acid was changed to 6-oxoheptanoic acid.

[0214] ... (20) (m and n are integers of 1 and 2 or more, respectively.)

[0215] The polymers 6a, 6b, 6c and 6d were pelletized in the same manner as in Example 3, and further treated with trimethylaluminum and water vapor using the substance permeation device 100 in the same manner as in Example 3.

[0216] Polyethylene diglyoxylate glucose (7a) represented by the following formula was synthesized in the same manner as in Example 3, except that D-xylose was replaced with glucose.

[0217] ... (21) (m and n are integers of 1 and 2 or more, respectively.)

[0218] Polyethylene glucose dipyruvate (7b) represented by the following formula was synthesized in the same manner as in Example 3, except that D-xylose was changed to glucose and glyoxylic acid was changed to pyruvic acid.

[0219] ... (22) (m and n are integers of 1 and 2 or more, respectively.)

[0220] Furthermore, polyethylene dioxobutyric acid glucose (7c) represented by the following formula was synthesized in the same manner as in Example 3, except that D-xylose was changed to glucose and glyoxylic acid was changed to 2-oxobutyric acid.

[0221] ... (23) (m and n are integers of 1 and 2 or more, respectively.)

[0222] Furthermore, polyethylene dioxoheptanoic acid glucose (7d) represented by the following formula was synthesized in the same manner as in Example 3, except that D-xylose was changed to glucose and glyoxylic acid was changed to 6-oxoheptanoic acid.

[0223] ... (24) (m and n are integers of 1 and 2 or more, respectively.)

[0224] The polymers 7a, 7b, 7c and 7d were pelletized in the same manner as in Example 3, and further treated with trimethylaluminum and water vapor using the substance permeation device 100 in the same manner as in Example 3.

[0225] A normal sugar derivative, different from the sugar derivative not having a polycyclic base unit, was pelletized in the same manner as in the above-mentioned Examples, and then subjected to a permeation treatment using trimethylaluminum and water vapor.

[0226] The polymer or plastic materials and the materials into which substances were impregnated were measured for tensile properties such as tensile strength, bending properties such as flexural strength, Izod impact strength, deflection temperature under load, etc., and the results are shown in Table 1. As a comparative example, a material was prepared in which the sugar derivative of Example 8 was not impregnated with trimethylaluminum and water vapor.

[0227]

[0228] As can be seen from Table 1, polymers or plastics that have been treated with substance penetration have improved properties such as tensile properties, flexural properties, Izod impact strength, and deflection temperature under load compared to those that have not been treated.

[0229] In particular, for polymers or plastics whose basic unit has a polycyclic structure containing a sugar derivative, many of the properties such as tensile properties, flexural properties, Izod impact strength, and deflection temperature under load have been improved by substance infiltration.

[0230] Next, the pellets obtained in the above examples that had been subjected to the material impregnation treatment using trimethylaluminum and water vapor were subjected to a melt spinning process to produce yarn. A conventional melt spinning device was used for melt spinning, and a yarn was extruded as a 24-strand multifilament yarn. The temperature during melt spinning and the yarn take-up speed were adjusted to produce a yarn. The yarn was then drawn using a drawing machine. The physical properties of the yarn, including fineness, tensile strength, and elongation, were measured. Table 2 shows the results.

[0231] The sample of Example 1 that was not subjected to the polyethylene terephthalate permeation treatment, the sample of Example 2 that was not subjected to the polybutylene terephthalate permeation treatment, and the pellets of the comparative example that were not subjected to the permeation treatment exhibited poor spinning under the evaluation conditions, but the samples that were subjected to the permeation treatment were able to be spun.

[0232] In other words, this indicates that substance penetration has the effect of enabling molding and processing such as spinning of plastic materials.

[0233] The sugar derivative polymers having a polycyclic structure containing a sugar ring structure as a base unit related to Examples 3 to 7 could be spun regardless of whether or not they were subjected to permeation treatment. Furthermore, the sugar derivative polymers that had been subjected to permeation treatment were found to have good fiber properties, with small fineness, large tensile strength, and large elongation.

[0234] In other words, the polymer having a polycyclic structure as a basic unit according to the present invention can be molded or processed by itself, such as by spinning, but in addition, it was shown that the mechanical properties can be further improved by subjecting it to a substance infiltration treatment.

[0235]

[0236] DESCRIPTION OF SYMBOLS 11...primary tank for first material, 12...primary tank for second material, 15...buffer tank for first material, 18...nozzle, 19...heater, 20...chamber section, 21...lid section, 22...reduced pressure vessel, 24...rotary vessel, 26...storage vessel, 29...chamber heater, 31...gas tank, MT...rotary motor, GR...exhaust gas removal section, VP...vacuum pump, 100...inorganic substance permeation device

Claims

1. A method for producing a plastic material containing an inorganic compound, comprising: a heating step for heating a plastic material placed in a chamber; a vacuum step for creating a vacuum in the chamber; an inorganic substance providing step for providing a gaseous inorganic substance at a first temperature into the chamber; a shaking step for shaking the plastic material in the chamber to produce a plastic material containing an inorganic compound; an exhaust step for evacuating the chamber after the shaking step; an oxidation / reduction product providing step for providing at least one of an oxide and a reduction product at a second temperature lower than the first temperature into the chamber after the exhaust step; and a shaking step for shaking the plastic material containing the inorganic compound in the chamber.

2. A method for producing an organic-inorganic hybrid material, comprising: a heating step for heating a plastic material placed in a chamber; a vacuum step for creating a vacuum in the chamber; an inorganic substance providing step for providing a gaseous inorganic substance at a first temperature into the chamber; a rocking step for rocking the plastic material in the chamber to produce an organic-inorganic hybrid material; an exhaust step for evacuating the chamber after the rocking step; an oxidation-reduction product providing step for providing at least one of an oxide and a reduction product at a second temperature lower than the first temperature into the chamber after the exhaust step; and a rocking step for rocking the organic-inorganic hybrid material in the chamber.

3. A method for producing a solid, comprising: a step (a) of introducing a first gas or a plurality of first particles into a processing chamber while a workpiece that is a raw material for the solid is placed inside the processing chamber, wherein in the step (a), at least a portion of the first gas or at least a portion of the plurality of first particles penetrates into the interior of the workpiece.

4. The method for producing a solid according to claim 3, wherein the object to be processed has a repeating structure of a plurality of basic units.

5. The method for producing a solid according to claim 4, wherein each of the plurality of basic units has at least one of a sugar skeleton, an ester group, an arylene group, an ether group, an acetal group, a ketal group, a carbonyl group, and an alkylene group.

6. The method for producing a solid according to claim 3, wherein the first gas or the plurality of first particles is at least composed of a first compound containing atoms of a first element having an electronegativity of less than 2.

5.

7. A method for producing a solid according to claim 6, wherein the first element is any one of a Group 1 element, a Group 2 element, a Group 3 atom, a Group 4 element, a Group 5 element, a Group 6 element, a Group 7 element, a Group 8 element, a Group 9 element, a Group 10 element, a Group 11 element, a Group 12 element, a Group 13 element, and an element in Group 14 other than carbon.

8. The method for producing a solid according to claim 6, wherein the electronegativity of the first element is 2.0 or less.

9. The method for producing a solid according to claim 6, wherein the first element is any one of aluminum, titanium, nickel, iron, copper and zinc.

10. The method for producing a solid according to claim 6, wherein the first compound has an organic group or a substituent containing an organic group.

11. The method for producing a solid according to claim 3, wherein the object is vibrated or rocked during at least a portion of the period during which step (a) is carried out.

12. The method for producing a solid according to claim 3, further comprising the step (b) of vibrating or rocking the object to be treated after the step (a).

13. The method for producing a solid as described in claim 3, further comprising, after step (a) or after performing at least one step after step (a), a step (c) of introducing a second gas or a plurality of second particles into the treatment chamber with the object to be treated placed inside the treatment chamber.

14. The method for producing a solid according to claim 13, wherein the second gas or the plurality of second particles is composed of at least a second compound.

15. The method for producing a solid according to claim 14, wherein at least a portion of the first compound introduced into the object to be treated via at least the step (a) reacts with at least a portion of the second compound and is converted into a third compound.

16. A polymer having a plurality of structural units, wherein a first structural unit of the plurality of structural units has a first portion and a second portion, a portion of the first portion and a portion of the second portion are shared, the first portion is a six-membered ring, the six-membered ring includes a first oxygen atom, two first carbon atoms, two second carbon atoms and one third carbon atom, the first oxygen atom and one first carbon atom of the two first carbon atoms form a first covalent bond, the first oxygen atom and the other first carbon atom of the two first carbon atoms form a second covalent bond, the first carbon atom of one of the two first carbon atoms and one second carbon atom of the two second carbon atoms form a third covalent bond, the other first carbon atom of the two first carbon atoms and the other second carbon atom of the two second carbon atoms form a fourth covalent bond, and the second carbon atom of one of the two second carbon atoms and the one third carbon atom form a fifth covalent bond, a sixth covalent bond is formed between the other second carbon atom of the two second carbon atoms and the one third carbon atom; the second portion is a first five-membered ring composed of the one first carbon atom, the one second carbon atom, a second oxygen atom, a third oxygen atom, and one fourth carbon atom; a seventh covalent bond is formed between the one first carbon atom and the second oxygen atom; an eighth covalent bond is formed between the one second carbon atom and the third oxygen atom; a ninth covalent bond is formed between the second oxygen atom and the one fourth carbon atom; and a tenth covalent bond is formed between the third oxygen atom and the one fourth carbon atom.

17. The polymer described in claim 16, wherein each of the plurality of structural units further has a third portion, the third portion being a second five-membered ring composed of the other second carbon atom, the one third carbon atom, a fourth oxygen atom, a fifth oxygen atom and a one fifth carbon atom, the other second carbon atom and the one third carbon atom forming a tenth covalent bond, the other second carbon atom and the one third carbon atom forming an eleventh covalent bond, the one third carbon atom and the fifth oxygen atom forming a twelfth covalent bond, the fourth oxygen atom and the one fifth carbon atom forming a thirteenth covalent bond, and the fifth oxygen atom and the one fifth carbon atom forming a fourteenth covalent bond.

18. The polymer of claim 16, wherein the one fourth carbon atom is bonded directly or through a linking group to the sixth carbon atom of the first carbonyl group.

19. The polymer of claim 17, wherein the fifth carbon atom is bonded directly or through a linking group to the seventh carbon atom of a second carbonyl group.

20. The polymer of claim 18, wherein the sixth carbon atom forms a fifteenth covalent bond with a sixth oxygen atom.

21. The polymer of claim 19, wherein the seventh carbon atom forms a sixteenth covalent bond with a seventh oxygen atom.

22. The polymer described in claim 20, wherein a second structural unit included in the plurality of structural units has the same structure as the first structural unit, and the sixth oxygen atom forms a seventeenth covalent bond with any atom constituting the second structural unit.

23. The polymer described in claim 21, wherein a third structural unit included in the plurality of structural units has the same structure as the first structural unit, and the seventh oxygen atom is bonded to any atom included in the third structural unit directly or via a linking group.

24. The polymer described in claim 21, wherein a third structural unit included in the plurality of structural units has the same structure as the first structural unit, and the seventh oxygen atom forms an 18th covalent bond with an eighth oxygen atom included in the third structural unit via a linking group.

25. The polymer of claim 24, wherein the linking group is an alkylene group.

26. The polymer according to claim 16, wherein at least one of the other first carbon atom and the one fourth carbon atom is bonded to a substituent containing a hydrogen atom, an alkyl group, a hydroxyl group, or a heteroatom.

27. The polymer according to claim 17, wherein at least one of the other first carbon atom and the one fifth carbon atom is bonded to a substituent containing a hydrogen atom, an alkyl group, a hydroxyl group, or a heteroatom.

28. A material comprising the polymer according to claim 16 and an electropositive atom which is an atom of an element having a lower electronegativity than carbon, or a compound having said electropositive atom.

29. The material of claim 28, wherein the electropositive atom is coordinated to at least one of the second oxygen atom and the third oxygen atom.

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