Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J11/00—Recovery or working-up of waste materials
  • C08J11/04—Recovery or working-up of waste materials of polymers
  • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/14—Esterification
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
  • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
  • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2810/00—Chemical modification of a polymer
  • C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

• Recyclable polymer manufacturing method thereof, and recycling method
• the present invention relates to a novel polymer material that can be repeatedly used by decomposition and resynthesis, and a novel decomposition and repolymerization method using the material, and a method using the material.
• polymer materials are a symbolic example, and have produced useful resins such as polyethylene, polypropylene, plastic materials such as polystyrene-pinyl chloride, and rubber such as polyisoprene-polybutene.
• resin materials having extremely excellent properties such as polyimide resins and wholly aromatic liquid crystal polymers, which are excellent in heat resistance and impact resistance, have been developed.
• condensation polymerization type polymers and addition polymerization type polymers.
• Condensation-polymerized polymers such as polyamides are susceptible to depolymerization at the condensation site by acids or bases.
• addition-polymerized polymers such as polystyrene
• an inert gas atmosphere is required. Therefore, a reaction under high temperature conditions is required, and large energy must be input.
• the decomposition products are dimers, trimers, and tetramers in addition to the monomers. Because of this mixture, only the polymerizable monomer needs to be isolated again, and a large amount of energy is input again. Also, monomer yield is a major issue. Depending on the addition polymerization type polymer such as polypropylene, some resins are difficult to depolymerize by such a method.
• the polymer is After being synthesized and used as a product such as a molded product, it can be cut again at the joint of the component and returned to the original chemical component.
• the parts obtained in this way can be regenerated into polymers by bonding them together again.
• Such an ester bond is cleaved by a hydrolysis reaction, and is again converted into a styrene polymer having a carbonyl group at both ends and butanediol, that is, a reversible reaction is possible.
• a hydrolysis reaction By subjecting the compound thus obtained to the same polycondensation reaction again, it is basically possible to synthesize a high-molecular-weight styrene polymer many times.
• the present invention relates to a polymer (A) represented by the following structural formula (1).
• R represents a linking unit composed of a condensation system
• n represents the number of repeating units, and represents an integer of 2 or more.
• the connecting portion R may be any one selected from the group consisting of -COO-, -CONH-, -NH-CO -0, and -NH-CO-NH-.
• the present invention is characterized in that the bonding site of R represented by the bond between Pi and R in the repeating unit in the structural formula (1) is the same in all repeating units.
• the bonding site of R represented by a bonding mark between P and R in the repeating unit in the structural formula (1) is different between adjacent repeating units.
• the present invention relates to the compound represented by the following formula in the structural formula (1).
• the bonding site of R represented by the bonding label between the bond and R is randomly selected from a plurality of bonding sites of R, and relates to the polymer according to [1].
• the connecting portion R is represented by the following structural formula (2), 6.
• XI and X 2 represent an atomic group linked to Pi in the structural formula (1).
• A represents an atomic group that can bond to XI and X 2.
• the present invention provides a compound according to the present invention, wherein XI and X 2 are each a group consisting of -CO- ⁇ -, -CONH-, -NH-CO-0-, and -NH-CO-NH-.
• the present invention also relates to the polymer according to [6], wherein the XI and X2 are the same atomic group.
• the present invention also relates to the polymer according to [7], wherein the same X 1 and X 2 are —CONH—.
• the present invention also relates to the polymer according to [6], wherein the XI and X2 are different from each other.
• the present invention provides the polymer according to [10], wherein the binding site of X 1 and Z or X 2 to A is randomly selected from a plurality of binding sites of XI and X 2. About.
• the present invention also relates to the polymer according to [10], wherein the bonding site of XI, Z or X2 to A is the same in all repeating units.
• the present invention also relates to the polymer according to [1], wherein the addition polymer Pi is at least one of polystyrene, polybutadiene, polyacrylonitrile, polyethylene, and polypropylene.
• the present invention is characterized in that A is an alkylene group. It relates to the described polymer.
• the present invention also relates to the polymer according to [13], wherein the alkylene group has a phenyl group in a side chain.
• the present invention also relates to the polymer according to [13], wherein the alkylene group has a phenylene group in a main chain.
• the present invention also relates to the polymer according to [5], wherein A is a phenylene group.
• step of depolymerizing by selectively cutting the bond in the connecting portion R and the step of forming the polymer are performed under relatively mild conditions.
• a compound (B) having a condensable functional group and a spin trap group is mixed.
• the polymer (A) is cleaved within the addition polymerization site P i, the polymer (A) and the compound (B) react with each other to form a condensable polymer at the molecular terminal of the polymer (A).
• the term “polymer” in the present invention refers to a polymer in the form of a composition in which another substance is mixed in the polymer represented by the structural formula (1). May also be used).
• the present invention relates to a composition characterized by being mixed with a compound having a condensable functional group and a spin trap group. [18]
• the present invention also relates to the composition according to [17], wherein the polymer is obtained by condensing R with R.
• the present invention also relates to the composition according to [17], wherein the compound having the condensable functional group and the spin trap group is represented by the following structural formula (3). .
• X 3 condensable functional group X 4 is spin trapping groups, 1 ⁇ one (CH 2) n2 -, _C 6 H 4 - and one (CH 2) ml -C 6 H 4 - (CH 2 ) m2 — (ii 2 and m 2 each represent an integer of 1 to 8, where 1 C 6 H 4 — represents a phenylene group).
• the present invention also relates to the composition according to [19], wherein the compound having a condensable functional group and a spin trap group is a nitroso compound.
• a polymer represented by the following structural formula (1) which is obtained by condensation-polymerizing an addition polymer having a functional group at both terminals alone or via a bifunctional compound. Production method.
• Pi is formed by the addition polymerization of one or more types of monomer molecules having a continuous hydrocarbon chain having no internal condensation system as a skeleton, and having a double bond.
• R is a condensed part connecting a plurality of Pis, and n is the number of repeating units and is an integer of 2 or more.
• the present invention is further characterized by further comprising a step of adding a compound having a condensable functional group and a spin trap group to the polymer represented by the structural formula (1). [22] And a process for producing the polymer described. [24] Further, the present invention is characterized in that the polymer represented by the structural formula (1) is any one of [2 to 16 and 35 and 36] [23. And a method for producing the polymer.
• the present invention also relates to the method for producing a polymer according to [23], wherein the compound having the condensable functional group and the spin trap group is represented by the following structural formula (3).
• X 3 is a condensable functional group
• X 4 is a spin trapping group
• Mi is one (CH 2 ) n2 —, _C 6 H 4 — and — (CH 2 ) ml — C 6 H 4 — (CH 2 ) m2 - (n 2, n , m 2 is selected from the group consisting of) each represents an integer of 1 to 8..
• the present invention also relates to the method for producing a polymer according to [22], further comprising a step of molding the polymer represented by the structural formula (1).
• the addition weight is formed by the addition polymerization of one or more types of monomer molecules having a continuous hydrocarbon chain having no internal condensation system as a skeleton and having a double bond.
• R represents a condensed linking unit that connects a plurality of Pis, and n represents the number of repeating units and an integer of 2 or more.
• the present invention also relates to the method for treating a polymer according to [27], further comprising a step of condensing the substance obtained in the depolymerization step to obtain a polymer again.
• the present invention also relates to the method for treating a polymer according to [27], further comprising a step of molding the re-obtained polymer.
• the present invention provides a method for dissolving the polymer in a solvent before the depolymerization step.
• the present invention provides the treatment of a polymer according to [27], wherein the connecting portion R is represented by the following structural formula (2) and cleaves at least one of X1 and X2. About the method.
• the present invention provides a depolymerization step of adding a compound having a condensable functional group and a spin trap group to the polymer represented by the structural formula (1),
• the polymer represented by the structural formula (1) may be one described in any of [2] to [16] and [1] and [11 "]. [32] The method for treating a polymer according to [32].
• the present invention also relates to the method for treating a polymer according to [32], wherein the compound having the condensable functional group and the spin trap group is represented by the following structural formula (3).
• X 3 condensable functional group, X 4 is spin trapping groups, Mi is - (CH 2) n2 -, - C 6 H 4 - ⁇ Pi one (CH 2) ml -C 6 H 4 - ( CH 2) m2 -.. ( n2, mi, m 2 is an integer of 1 to 8) is selected from the group consisting bRIEF dESCRIPTION oF dRAWINGS
• FIG. 1 is a diagram showing a molecular weight distribution (differential curve) of the polymer obtained in Example 10 by GPC.
• FIG. 2 is a view showing the result of FT-IR measurement of the polymer obtained in Example 10.
• FIG. 3 is a diagram showing the results of measuring the thermal decomposition characteristics of the polymer obtained in Example 10.
• FIG. 4 is a diagram showing the molecular weight distribution (differential curve) of the polystyrene polymer decomposed and recovered in Example 35 by GPC.
• the central compound of the present invention is a polymer represented by the structural formula (1).
• Pi is an addition polymer having a continuous hydrocarbon chain as a skeleton, and is a polymer or an oligomer produced by addition polymerization of one or more types of monomer molecules having a double bond.
• R is a concatenated connecting part that connects a plurality of Pis, and n is the number of repeating units and is an integer of 2 or more. In order to selectively depolymerize only at the portion of, Pi must not contain a condensation system such as polyester (described later).
• the connecting portion R is roughly classified into two types, and the polymer type based on this is shown below.
• a first preferred embodiment is one in which the above-mentioned addition polymer Pi is linked by a dissociative bond without directly passing through a spacer. That is, the polymer Pi is formed by bonds such as an ester bond (-CO ⁇ -), an amide bond (-CONH-), a urethane bond (-NH-COO-), and a urine bond (-NH-CO-NH-). It is linked. In this case, the direction of these bonds with respect to the main chain is the same in all the repeating units, and the direction opposite to each other in the adjacent repeating units. I can do it.
• a compound using a low molecular compound represented by the structural formula (2) as the connecting portion R can be mentioned. .
• X 1 and X 2 are a linking group that can be linked to the terminal of the addition polymer P; L, and A is a spacer described later.
• X 1 and X 2 are dissociative bonds, which are an ester bond (-CO ⁇ -), an amide bond (-CONH-), a urethane bond (-NH-COO-), and a urea bond (-NH-CO -NH-) is desirable.
• an amide bond is preferable.
• Examples of the form include those in which X 1 and X 2 are the same, and those in which 1 and 2 are different from each other. These are selected in view of the availability of raw materials and the convenience during depolymerization described below.
• the arrangement of X 1 and X 2 in the repeating unit may be the same in all the repeating units, or may be the opposite in each adjacent repeating unit.
• addition polymer Pi examples include polymers composed of polystyrene, polybutadiene, polyacrylonitrile, polyethylene, polypropylene, and the like. In addition, these copolymers may be used, but a condensation system such as an ester and an amide must not be included.
• the degree of polymerization of the polymer is set based on the overall molecular weight and the content of dissociative bonds, that is, it is set in consideration of the required physical properties such as mechanical strength and the ease of depolymerization. Things. Therefore, the desirable range is not uniquely determined, but as a practical range in view of the synthesis process, it is preferably 2 or more, and particularly preferably 2 to 2000.
• A may be any of an aliphatic compound such as an alkylene group having 1 to 4 carbon atoms and an aromatic compound, that is, a compound containing at least one aromatic compound from the viewpoint of water resistance and polymerization reactivity. More preferred.
• an alkylene group having a phenyl group in the side chain e.g., -CH Ph-CH 2-
• an alkylene group having a phenylene group in the main chain e.g., -CH Ph-CH 2-
• Example: —CH 2 —Plr CH 2 — or a phenylene group (—Ph—) is preferred.
• the linking site having spacer-A for example, as a compound containing at least one aromatic compound, p-phenylenediamine, m-phenylenediamine, p-xylenediamine, m-xylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, Examples include 4,4, -diaminodiphenylsulfone, 2- (4-aminophenyl) ethylamine, and 2,2'-dithiodiamine.
• aliphatic compounds such as 3,3'-diaminodipyrropyramine and 2,2, diaminogetyl ether are also included.
• the polymer of the present invention is synthesized by condensing a compound having a functional group at both terminals alone or using a bifunctional compound. That is, in the case of the linking form 1, a polymer in which both ends of the addition polymer P are functionalized to an amino group, a carboxylic acid group, or the like is prepared, and this is used in a molten state or in a solution, if necessary. Can be obtained by condensation using an active intermediate.
• the compound Pi is similarly obtained by condensing a compound Pi having a functional group at both terminals and a bifunctional compound for linking (a raw material providing a site of the structural formula (2)) by the same method.
• the final overall molecular weight is preferably 10 4 to 10 6 by weight average molecular weight.
• the polymer of the present invention provides the same resin molding capability as when a polymer of the addition polymer itself as a constituent component is used. That is, when the thermoplastic polymer Pi as described above is used, conventionally known compression molding, extrusion molding, and injection molding can be performed, and a resin molding having a novel recyclability described below. Body can be provided.
• the molded article may contain a plasticizer, a coloring material, a filler, a stabilizer, a flame retardant, and the like as long as it does not hinder recycling.
• the polymer of the present invention is obtained by selectively cleaving the dissociative bond in the connecting portion R. Depolymerized to give recondensable parts. Since the depolymerization is for breaking the dissociative bond, it can be performed with a relatively small energy input.
• the reaction used for the depolymerization is not particularly limited, but hydrolysis is an easy one. For example, the molded product itself after use or flaked product is made to work in a suitable solvent under relatively mild conditions using an acid or an alkaline catalyst as a catalyst, and the bond is hydrolyzed to depolymerize. I do. Depolymerization makes it easier to remove deteriorated parts and additives, and allows recovery of recycled materials in a more purified state.
• the cutting method includes a method of cutting both XI and X2 in the connection portion R, and a method of cutting only one of them.
• XI and X2 are different linking groups.
• the method of cutting only one of the two methods is used in purification and recondensation in order to form a single product after depolymerization when the configuration of X1 and X2 is the same in all the repeating units. Has the advantage that it becomes easier.
• the product obtained by the depolymerization can regenerate the initial polymer (2) by recondensing as it is, or after modifying the reactivity if necessary, and further using the polymer
• the molded body can be regenerated. If necessary, the degree of condensation (n in the structural formula (1)) can be changed, and the physical properties can be controlled by changing the connection form, for example, in order to adapt to different applications. .
• Japanese Patent Application Laid-Open No. 9-76372 discloses a method for stabilizing a melt flow and preventing discoloration.
• a method of adding an isoxazolidine compound is described.
• JP-A-7-324028 discloses the addition of a spin trap compound for the purpose of light protection, anti-aging, and / or anti- acne treatment of a cosmetic or dermatological composition. It is stated that These are intended to prevent oxidative degradation of the matrix material, that is, to capture oxygen or peroxide radicals generated by oxidation with a spin trapping compound to prevent the material from deteriorating, and to repair polymer molecules. It has no effect, and there is no such effect.
• the mechanism of the present invention is as follows.
• the polymer is cut by external stress, free radicals are generated at the cutting position.
• the compound (B) having the condensable functional group and the spin trap group coexist, the free radical is trapped by the spin trap group, and as a result, the condensable functional group of the compound (B) is cleaved. It is added to the molecular end of the polymer.
• the compound (B) having such a condensable functional group and a spin trap group can be represented by the structural formula (3).
• X 3 represents a condensable functional group
• X 4 represents a spin trap group
• Mi represents the structure of the structural formula (4).
• n 2 , n and m 2 each represent an integer of 1 to 8.
• the bonding position to the aromatic ring may be an ortho position or a meta position in addition to the para position in the figure.
• the condensable functional group X 3 represents a general functional group capable of a condensation reaction, such as a propyloxyl group, a hydroxyl group, an amino group, and the like.
• the spin trap group X4 is preferably a nitroso compound.
• a compound represented by the structural formula (5) can be used as the nitroso compound.
• a paranitrosodulene derivative or the like can also be used.
• Molecular repair by such a reaction is useful, for example, in the following steps. First, in the system where polymer polymerization and depolymerization are repeated using the above-mentioned addition polymer having condensable functional groups at both ends of the molecule, especially when the molecule is cut by stirring etc. in the depolymerization process. is there. If a compound having a condensable functional group and a spin trap group is mixed in this step, radicals generated by the cleavage are captured by the spin trap group.
• a compound having a condensable functional group and a spin trap group may be mixed in the polymer in advance.
• large stresses such as heat and shear stress are applied to the resin, and the molecular chains are cut.
• the molecular chain cutting radicals are captured by the spin trap group.
• the concentration of the compound having a condensable functional group and a spin trap group is 0.01% to 5%, preferably 0.1% to 3%, based on the raw resin. .
• the movement of molecules is more restricted than the reaction in a solution, so that about 0.1% to 5% is preferable.
• this technology is a conventional technology for reuse of molded products, a material recycling technology such as sandwich molding, a chemical recycling technology for decomposing resin into monomers of raw materials, and a thermal recycling technology that uses heat during combustion. It can be implemented in combination with various technologies such as recycling technology, and does not limit the model of material circulation.
• the weight average molecular weight of the obtained polymer was 400,000, and the number n of repeating units was estimated to be about 16.
• Examples 2 to 5 Synthesis of ester-bonded polymer having a spacer 2 to 5
• the polymer portion (P) of polystyrene (PS) at both ends was replaced with polystyrene having different molecular weights.
• the synthesis was also performed in the same manner as above, except that polypropylene and polypropylene (PP) and polyethylene (PE) were replaced with 1,4-butanediol and other diol compounds.
• Examples 1 to 5 are specifically shown in Table 1 below.
• the number of repeating units II was calculated from 1,4-butanediol of Example 1 and polystyrene of both terminal dicarboxylic acids (Mw. 25,000; Mw. Represents weight average molecular weight).
• Mw. 25,000; Mw. Represents weight average molecular weight The case where the ester-bonded polymer was synthesized was shown as A-1 in Table 1, and the same applies to Examples 2 to 5 below.
• the weight average molecular weight of the obtained polymer was estimated to be 465,000, and the number n of repeating units was estimated to be approximately 31. .
• Examples 7 to 9 Synthesis of a amide-bonded polymer having a spacer 2 to 4
• PS dicarboxylic acid polystyrene
• P polymer part
• Examples 6 to 9 are specifically shown in Table 2 below.
• the obtained polymer was refluxed for 1 hour in 100 ml of methanol, filtered off and dried under reduced pressure to obtain a white fibrous polymer (compound No.B-5).
• the molecular weight was measured by GPC under the following conditions.
• Fig. 1 shows the molecular weight distribution (differential curve) by GPC. 1 is a curve for the raw material PS, 2 is a curve in the course of polymerization, and 3 is a curve for the obtained polymer.
• FIG. 2 shows the results of measuring the FT-IR of the obtained polymer. It was measured by the KBr disintegrant method using a 1720X device manufactured by PerkinElmer.
• the absorption peak a derived from amide I is at 1687 and 1653 cm-i
• the peak a derived from amide ⁇ is at 1560 cm-i
• the peak b derived from aromatic ether is at 1262 and 1217 cm-i. It was confirmed that polymerization was performed.
• the thermal decomposition characteristics were measured using TG-DTA 2000 S manufactured by MAC SCIENCE (temperature range-500 ° C, heating rate 10 / min in N 2 gas).
• Figure 3 shows the results.
• A is the curve of the polymer obtained in this example
• B is the curve of the PS commercial product.
• the thermal decomposition characteristics were the same as those of PS without amide bond (PS manufactured by Wako Pure Chemical Industries, Ltd., PS), and showed the same heat resistance with the same thermal decomposition onset temperature.
• the obtained polymer was refluxed in 150 ml of methanol for 1 hour, filtered off, and dried under reduced pressure to obtain a white fibrous polymer (Compound No. B-7). According to GPC measurement, the weight average molecular weight of the obtained polymer was 120,000.
• the weight average molecular weight of the obtained polymer was estimated to be 700,000, and the number n of repeating units was estimated to be about 14.
• ester-bonded polymers of Examples 16 and 17 were synthesized under the same conditions as in Example 15 except that polystyrene and polyethylene having different molecular weights were substituted for the ⁇ -hydroxy- ⁇ -carboxy-terminated polystyrene.
• amide-bonded polymers of Examples 18 and 19 were synthesized by replacing the ⁇ -hydroxy- ⁇ -carboxy-terminated polystyrene with the amino- ⁇ -carboxyl-terminated polystyrene / polypropylene.
• 3 g of 1,4-butanediol and 120 ml of a solvent were placed in a four-necked flask equipped with a reflux condenser equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a drying tube. After sufficiently replacing with nitrogen, the nitrogen introduction tube was removed and replaced with a dropping funnel equipped with a drying tube, and 5 g of isocyanate polystyrene at both ends and 60 ml of a solvent were added thereto. Heat while stirring, and when stirring starts, add half of the contents of the dropping funnel at once and stir vigorously.
• the weight average molecular weight of the obtained polymer was 300,000, and the degree of polymerization was estimated to be about 30.
• Example 22 to 25 Synthesis of urethane-bound polymer having spacers 2 to 5
• PS isocyanate polystyrene
• the synthesis was performed in the same manner, except that polystyrene, polypropylene (PP), and polyethylene (PE) were replaced with 1,4-butanediol, and other polyol compounds.
• Examples 21 to 25 are specifically shown in Table 4 below.
• EXAMPLE 21 E-1 PS (1 million in) OCONH 1,4-C 4 H 8 NHOCO 30
• Example 22 E-2 PS (5000) OCONH 1, iZ-C 12 H 24 NHOCO 22
• Example 23 E-3 PS (50,000) OCONH G 2 H 4 NHOCO
• Example 24 E-4 PE (10,000) OCONH NHOCO 6
• Example 25 E-5 PS (25,000) OCONH 1,8-G 9 H 18 NHOCO 12
• Example 26 Synthesis of Urea-Binding Polymer Having a Spacer 1) A mixture of distilled benzene and 0-dichlorobenzene at 80 I 20 (volume ratio) was used as a reaction solvent.
• Hexane-1,6-diamine (3 g) and a solvent (120 ml) were placed in a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser equipped with a drying tube. After sufficiently replacing with nitrogen, the nitrogen introduction tube was removed, and the flask was replaced with a dropping funnel equipped with a drying tube, into which was added isocyanate polystyrene (M w. 5000) 5 at both ends and 60 ml of a solvent. While stirring, add half the contents of the dropping funnel at once and stir vigorously. The other half was added dropwise over 3 hours, and further stirred for 1 hour.
• M w. 5000 isocyanate polystyrene
• the weight average molecular weight of the obtained polymer was estimated to be 100,000 by GPC measurement, and the number n of repeating units was estimated to be about 20.
• Example 26 is specifically shown in Table 5 below.
• n 20 from the hexane-1,6-diamine of Example 26 and polystyrene of both ends cisocyanate (Mw.5000; Mw. Represents a weight average molecular weight).
• Mw.5000 Mw. Represents a weight average molecular weight
• F-1 F-1 in Table 5.
• Example 30 The molded body produced in Example 30 was crushed, and 10 g thereof was dissolved in 400 ml of toluene. 400 ml of a 1 mol / L (1N) sodium hydroxide aqueous solution was added, and the mixture was stirred with ICTC for 24 hours. GPC confirmed that the molecular weight had decreased to that of the raw polystyrene polymer. After the solvent was distilled off, the residue was washed with a 10% aqueous acetic acid solution, further washed with ethanol, and dried. The recovered product was confirmed to be a polystyrene derivative by an infrared absorption spectrum. Using this powder, synthesis was performed in the same manner as in Example 1, and similar results were obtained.
• FIG. 4 shows the molecular weight distribution derivative curve.
• 4 is the curve of the molded polymer
• 5 is the curve of the material 7 hours after the start of the treatment
• 6 is the curve of the recycled product.
• the molecular weight was reduced by GPC to the value of the raw polystyrene polymer. confirmed.
• a styrene polymer having a molecular weight of 25,000 and having a hydroxyl group at both ends of the molecule is prepared. Further, butanediol is prepared as a molecule that serves as a joint of the polymer having two functional groups capable of binding to these two hydroxyl groups.
• the temperature of these compounds is raised to 180 ° C in a flask, and titanium isopropoxide (0.5% by mass) is added as a catalyst with stirring.
• the atmosphere in the reaction flask is replaced with nitrogen gas, and the pressure is gradually reduced to 6.67 kPa to remove water generated in the dehydration condensation reaction. The reaction is performed for 3 hours and the polymer is recovered.
• the synthesized polymer is dissolved in ⁇ , ⁇ '-dimethylformamide (DMF) at a concentration of 10% by mass, and lmol / L (l ⁇ ) hydrochloric acid is added. Water is stirred at 40 ° C for 5 hours while stirring. Perform disassembly. At this time, the following compound represented by the structural formula (6) as a compound having a condensable functional group and a spin trap group is added at 0.1% to the polymer.
• DMF ⁇ , ⁇ '-dimethylformamide
• the resulting styrene polymer having a molecular weight of 25,000 and having carboxylic acid groups at both ends of the molecule is repeatedly recovered by dissolving in toluene and precipitating in methanol.
• the butanediol formed by the decomposition is recovered by distillation.
• a polymer is synthesized from the obtained styrene polymer having carboxyl groups at both ends of the molecule and having a molecular weight of 25,000 and butanediol in the same manner as in (Synthesis of polymer 1).
• extrusion molding is performed at 180 ° C to form the housing of the printer. .
• the molded polymer is hydrolyzed in the same manner as in Example 1 (decomposition of polymer 1). At this time, in this example, since the compound of the structural formula (7) is already added as a compound having a condensable functional group and a spin trap group, it is not always necessary to newly add it.
• a polymer is polymerized in the same manner as in (Resynthesis 1 of polymer) in Example 36.
• the polymer thus obtained and the molding process of this example Compare the GPC of the previous polymer and confirm that it has the same molecular weight distribution.
• a styrene polymer having a carboxyl group at both molecular terminals and having a hydroxyl group at the molecular weight terminal as well as a styrene polymer having a molecular weight of 25,000 is prepared.
• the temperature of these compounds is raised to 180 ° C in a flask, and titanium isopropoxide, 0.5% by mass as a catalyst is added with stirring.
• the atmosphere in the reaction flask is replaced with nitrogen gas, and the pressure is gradually reduced to 6.67 kPa to remove water generated in the dehydration condensation reaction.
• the reaction is carried out for 5 hours and the polymer is recovered.
• the polymer synthesized in (Synthesis of polymer 2) was dissolved in ⁇ , ⁇ '-dimethylformamide (DMF) at a concentration of 10% by mass, and lmol / L (IN) hydrochloric acid was added. 4 (Hydrolysis with TC for 5 hours. At this time, as a compound having a condensable functional group and a spin trap group, the compound represented by the structural formula (6) described in Example 36 was added in an amount of 0.1% based on the polymer. Added.
• the resulting styrene polymer having a molecular weight of 25,000 and having a hydroxyl group at both ends of the molecule and a styrene polymer having a hydroxy group at both ends of the molecule are repeatedly recovered by dissolving in toluene and precipitating in methanol. .
• Example 36 The polymer obtained in Example 36 is molded by the method (Example 1 of polymer molding 1) of Example 36 to produce a printer housing.
• the product is recovered after the end of use by the consumer, and a part thereof is decomposed by the method of Example 36 (decomposition of polymer 1) to obtain a new raw material for polymer synthesis.
• a new polymer is synthesized by the method of (Resynthesis 1 of polymer) in Example 36.
• the remaining portion similarly collected is chipped as it is, and a sandwich is formed by the method described in Japanese Patent Publication No. Hei 6-24739 (Patent Document 1) to newly form a housing for the pudding.
• Example 36 The polymer obtained in Example 36 is hydrolyzed in the same manner as in (Decomposition of polymer 1) in Example 36, except that the compound of the structural formula (6) is not added. Then, the styrene polymer having both terminal propyloxyl groups and butanediol are recovered.

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