WO2017078478A1 - Crosslinked polyglutarimide including isosorbide, and method of producing same - Google Patents

Crosslinked polyglutarimide including isosorbide, and method of producing same Download PDF

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WO2017078478A1
WO2017078478A1 PCT/KR2016/012690 KR2016012690W WO2017078478A1 WO 2017078478 A1 WO2017078478 A1 WO 2017078478A1 KR 2016012690 W KR2016012690 W KR 2016012690W WO 2017078478 A1 WO2017078478 A1 WO 2017078478A1
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group
substituted
unsubstituted
branched
polyglutarimide
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French (fr)
Korean (ko)
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정민경
임병탁
김인범
조대희
김승환
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에스케이이노베이션 주식회사
에스케이종합화학 주식회사
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Publication of WO2017078478A1 publication Critical patent/WO2017078478A1/en

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    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a crosslinked polyglutarimide comprising isosorbide and a process for preparing the same.
  • Polymethyl methacrylate is one of the polymers of methyl methacrylate. It is not only excellent in transparency and weather resistance, but also excellent in hardness, chemical resistance, surface gloss and adhesion, and is widely used as a substitute for glass. It is used to replace tempered glass, which is used as a window material applied to the housing of a home appliance and a touch surface of a mobile phone.
  • methacrylate-based resins have a problem that heat distortion temperature (HDT) is 80 to 97 ° C. and continuous use temperature is low to 60 to 80 ° C., compared with other plastic materials, and thus has low heat resistance. .
  • HDT heat distortion temperature
  • continuous use temperature is low to 60 to 80 ° C.
  • Polyglutalimide which is applied as a substitute for polymethyl methacrylate, contains imide bonds, has excellent mechanical properties and optical properties with high modulus, viscosity, and refractive index, and has a glass transition temperature of 130 ° C. or higher. It has a better heat resistance than polymethyl methacrylate.
  • polyglutarimide has a glass transition temperature of up to 180 ° C., and when a high temperature is applied thereto, mechanical properties and optical properties change. Accordingly, there is a demand for a method for imparting heat resistance and mechanical properties to the polyglutarimide chemical structure to solve the above problem.
  • the present invention has been made to solve the problems described above, as a cross-linking agent to polyglutarimide, two tetrahydrofuran ring has a structure bonded at an angle of 120 °, giving heat resistance, transparency and surface hardness improvement effect
  • isosorbide which is capable of crosslinking polyglutarimide
  • the present invention provides a crosslinked polyglutarimide and a method for preparing the same, which have better mechanical, optical and thermal properties than general polyglutarimide. .
  • the present invention provides a polyglutarimide comprising a glutarimide repeating unit represented by the following formula (1),
  • 0.001 to 1.2 mole% of the glutarimide repeating unit relates to a polyglutarimide which forms a crosslinked structure represented by Chemical Formula 2.
  • R 1 And R 3 are independently of each other hydrogen or CH 3 ;
  • R 2 Is a substituted or unsubstituted linear or branched C1-C20 alkyl group, a substituted or unsubstituted straight or branched C3-C20 alkenyl group, a substituted or unsubstituted C3-C20 alkynyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, substituted or unsubstituted C6-C18 aryl group, straight or branched C1-C20 hydroxyalkyl group, straight or branched C1-C18 epoxyalkyl group, acryloyl group, methacryloyl group And acrylooxy group is any one selected from the group consisting of;
  • R z Is a substituted or unsubstituted linear or branched C1-C20 alkyl group, a substituted or unsubstituted straight or branched C3-C20 alkenyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted Any one selected from the group consisting of a C6-C18 aryl group, a straight or branched C1-C18 epoxyalkyl group, an acryloyl group, a methacryloyl group, and an acrylooxy group;
  • a and b are each independently an integer of 1 to 1,000, and may be 0.001a ⁇ b ⁇ 0.33a.
  • the crosslinked polyglutarimide including isosorbide according to the present invention includes isosorbide, which exhibits transparency and surface hardness enhancement effect, as a crosslinking agent in the polyglutarimide, thereby significantly improving heat resistance and mechanical properties. It is possible to enable the production of molded articles such as improved display optical members and electrical and electronic circuit members.
  • Example 1 is prepared according to the method of Example 1 (top right), Example 2 (center top), Example 3 (top left), Example 6 (bottom left) and Example 8 (bottom right) of the present invention. It is the result of visual observation whether the film of the formed XLPGI was formed.
  • Comparative Example 2 is prepared according to the method of Comparative Example 1 (top right), Comparative Example 2 (top left), Comparative Example 3 (bottom left), Comparative Example 4 (center bottom) and Comparative Example 5 (bottom right) of the present invention. It is the result of visual observation whether the film of the formed XLPGI was formed.
  • substituted silver 'in the compound or structure constituting the compound, a hydrogen element bonded to a carbon element is halogen, nitro, hydroxy, C1-C7 alkyl, C1-C7 alkoxy, C1-C7 alkylcarbonyl, Substituted with one or more substituents selected from C1-C7 alkoxycarbonyl, formyl (-CHO) and the like.
  • polyglutarimide means 'crosslinked polyglutarimide comprising isosorbide structure'.
  • the present invention relates to a polyglutarimide having excellent optical properties and remarkably improved heat resistance and mechanical properties, and in the polyglutarimide comprising a glutarimide repeating unit represented by Formula 1 below,
  • 0.001 to 1.2 mole% of the glutarimide repeating unit relates to a polyglutarimide which forms a crosslinked structure represented by Chemical Formula 2.
  • R 1 in Formula 1 And R 3 can independently be hydrogen or CH 3 ;
  • R 2 Is a substituted or unsubstituted linear or branched C1-C20 alkyl group, a substituted or unsubstituted straight or branched C3-C20 alkenyl group, a substituted or unsubstituted C3-C20 alkynyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, substituted or unsubstituted C6-C18 aryl group, straight or branched C1-C20 hydroxyalkyl group, straight or branched C1-C18 epoxyalkyl group, acryloyl group, methacryloyl group And it may be any one selected from the group consisting of acrylooxy group and the like, preferably any one selected from C1-C20 alkyl group, C3-C20 alkenyl group, C3-C20 alkynyl group and C6
  • the alkyl group and alkenyl group which may be included in the R 2 may be a linear or branched C1 to C20 alkyl group and a linear or branched C3 to C20 alkenyl group, preferably C1 to C10 alkyl group , C3 to C10 alkenyl group and C3 to C10 alkynyl group
  • the cycloalkyl group may be a C3 to C10 cycloalkyl group, preferably C3 to C6 cycloalkyl group, but is not limited thereto.
  • R z Is a substituted or unsubstituted linear or branched C1-C20 alkyl group, a substituted or unsubstituted straight or branched C3-C20 alkenyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C6-C18 aryl group, linear or branched C1-C18 epoxyalkyl group, acryloyl group, methacryloyl group and acrylooxy group and the like can be any one selected from the group consisting of, preferably C1-C20 It may be any one selected from an alkyl group, a C3-C20 alkenyl group, a C3-C20 alkynyl group, and a C6-C18 aryl group, but is not particularly limited thereto.
  • a and B may be any one selected from a single bond and 'R'-X-' form independently of each other, and when A and B are in the 'R'-X-' form, R ′ is bonded to an imide group, and substituted or unsubstituted linear or branched C1-C20 alkylene, substituted or unsubstituted linear or branched C3-C20 alkenylene, substituted or unsubstituted C3-C20 alkynylene, substituted or unsubstituted C3-C10 cycloalkylene and substituted or unsubstituted C6-C18 arylene and the like, and the like, wherein X- is combined with isosorbide May be a single bond, O—, —S—, C ( ⁇ O) —, —C ( ⁇ O) O— or SO 2 —, wherein a and b are integers of 1 to 1,000 independently of each other, 0.001a ⁇ b
  • the polyglutarimide polymer chain bonded with the crosslinked structure represented by Chemical Formula 2 may be a crosslink between different glutarimide repeat units in the same polymer molecule or a bond between glutarimide repeat units between different polymer molecules. Can be.
  • a and B are preferably a single bond
  • It may be any one selected from the group consisting of, but is not particularly limited thereto.
  • Polyglutalimide including the repeating unit of Formula 1 according to the present invention may have a weight average molecular weight of 50,000 to 500,000 g / mol.
  • the weight average molecular weight was measured by using Agilent Technologies' 1260 Infinity (standard sample: Polystyrene), column was used PL gel Olexis, sample was 100ml LiCl (concentration) using DMAc as a solvent : 0.5wt%) contained 4mg.
  • the present invention relates to a method for producing a polyglutarimide crosslinked with an isosorbide structure
  • the method for producing a polyglutarimide is a diamine represented by the formula (3) comprising an acrylate-based polymer, isosorbide It may include the step of reacting the compound and the amine compound represented by the formula (4), wherein the poly glutarimide comprising a repeating unit of the formula (1) prepared through the above step is from 0.001 to the total glutarimide repeating unit 1.2 mol% may include a crosslinked structure represented by Formula 2 below.
  • R 1 of Chemical Formula 1 and Chemical Formula 2 And R 3 Can independently be hydrogen or CH 3 ;
  • R 2 Is a substituted or unsubstituted linear or branched C1-C20 alkyl group, a substituted or unsubstituted straight or branched C3-C20 alkenyl group, a substituted or unsubstituted C3-C20 alkynyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, substituted or unsubstituted C6-C18 aryl group, straight or branched C1-C20 hydroxyalkyl group, straight or branched C1-C18 epoxyalkyl group, acryloyl group, methacryloyl group And it may be any one selected from the group consisting of acrylooxy group and the like;
  • R z Is a substituted or unsubstituted linear or branched C1-C
  • a and B of Formula 2 may be any one selected from a single bond and 'R'-X-' form independently of each other, when A and B is a 'R'-X-' form, the R ' Is bonded to an imide group and is substituted or unsubstituted straight or branched C1-C20 alkylene, substituted or unsubstituted straight or branched C3-C20 alkenylene, substituted or unsubstituted C3-C20 It may be one or more selected from the group consisting of alkynylene, substituted or unsubstituted C3-C10 cycloalkylene, substituted or unsubstituted C6-C18 arylene, and the like, wherein X- is combined with isosorbide, May be a bond, O—, —S—, C ( ⁇ O) —, —C ( ⁇ O) O—, or SO 2 —, wherein a and b in Formula 1 are each independently an integer of 1
  • a and B are the same as A and B defined in Chemical Formula 2, and may be any one selected from a single bond and a 'R'-X-' form independently of each other, and A and B Is a 'R'-X-' form, R 'is bonded to an amine group, and substituted or unsubstituted linear or branched C1-C20 alkylene, substituted or unsubstituted linear or branched One or more selected from the group consisting of C3-C20 alkenylene, substituted or unsubstituted C3-C20 alkynylene, substituted or unsubstituted C3-C10 cycloalkylene, substituted or unsubstituted C6-C18 arylene, and the like.
  • a and B are preferably a single bond,
  • It may be any one selected from the group consisting of, but is not particularly limited thereto.
  • R 4 z R z is as defined in formula (I)
  • a substituted or unsubstituted linear or branched C1-C20 alkyl group a substituted or unsubstituted straight or branched C3-C20 alkenyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or It may be any one selected from the group consisting of an unsubstituted C6-C18 aryl group, linear or branched C1-C18 epoxyalkyl group, acryloyl group, methacryloyl group and acrylooxy group, and the like.
  • It may be any one selected from the group consisting of linear or branched C1-C20 alkyl group, linear or branched C3-C20 alkenyl group, C3-C10 cycloalkyl and C6-C18 aryl group, but is not particularly limited thereto. .
  • the said acrylate-type monomer used by the manufacturing method of the polyglutarimide of this invention is a monofunctional or polyfunctional alkyl (meth) acrylate and alkenyl (meth) acrylate containing one or more acrylate functional groups.
  • the acrylate polymer may be prepared through polymerization of an acrylate monomer, wherein the polymerization further includes one or more other additives such as radical initiators, suspending agents, buffer salts and chain transfer transfer agents. It can be carried out by conventional polymerization reactions such as suspension polymerization, emulsion polymerization, dispersion polymerization and precipitation polymerization. In this case, any radical initiator, suspending agent, buffer salt, and chain transfer transfer agent used in the polymerization may be used without particular limitation as long as they are commonly used in the polymerization of the acrylate polymer.
  • the acrylate polymer used in the present invention may have a weight average molecular weight of 5,000 to 300,000 g / mol, preferably 10,000 to 200,000 g / mol, more preferably 15,000 to 120,000 g / mol.
  • the weight average molecular weight of the acrylate-based polymer is not particularly limited thereto, but when satisfying the above range, it is possible to dissolve the acrylate-based polymer in a polar organic solvent, so that the acrylate-based polymer and The condensation crosslinking reaction of the diamine of the present invention can be evenly generated, and the XLPGI can be produced as a film having high heat resistance and high elasticity through a solution process.
  • the diamine compound used in the present invention includes an isosorbide structure in the mother nucleus, any diamine compound having an amine group at both ends can be used without limitation, the amine compound also has a compound having one amine group at the end of the chemical structure If it is not limited, all can be used.
  • the addition content of the diamine compound used in the present invention is not particularly limited thereto, but when the content range is satisfied, the cross-linked polyglutarimide (XLPGI) prepared by the reaction with the acrylate polymer of the present invention ) Does not exhibit a gel form, and the efficiency of improving the heat resistance and surface strength of the acrylate-based polymer may be maximized, and thus, polyglutarimide having excellent mechanical strength and heat resistance may be effectively produced.
  • the excessive crosslinking reaction does not occur in the molecular structure of the crosslinked polyglutalimide (XLPGI) to be produced, so that the XLPGI has a thermal crosslinking property, and thus secondary processing is performed. As it becomes possible, it is desirable to be widely used in various forms in various fields.
  • the acrylate-based polymer, the diamine compound and the amine compound may be dissolved in a solvent, and may be prepared as polyglutarimide through a polymerization reaction in a solution.
  • a solvent used for the reaction a polar organic solvent capable of dissolving the acrylate-based polymer and the diamine compound may be used.
  • NMP N-methyl-2-pyrrolidone
  • DMF Dimethylformamide
  • DMAc dimethylacetamide
  • DMSO dimethyl sulfoxide
  • acetone and diethyl acetate and the like, but may include one or more selected from the above.
  • one or more selected from a low boiling point solvent such as tetrahydrofuran (THF) and chloroform and a low absorbing solvent such as ⁇ -butyrolactone may be used as the reaction solvent.
  • the content of the solvent used in the reaction is not particularly limited, but the content of the solvent is 20 to 100 wt%, preferably 30 to 75 wt% based on the total weight of the acrylate-based polymer, diamine compound and amine compound.
  • the condensation polymerization reaction of the acrylate-based polymer and the diamine compound can proceed smoothly and at the same time can prevent excessive use of the solvent, it is preferable in terms of environmental and economic.
  • the reaction may be carried out through a conventional method of stirring or heat treating a solution, and stirring or heat treatment for 6 to 10 hours at a temperature condition of 200 to 250 ° C. and a pressure condition of 10 to 30 kPa. It may be carried out by, but is not particularly limited thereto.
  • the weight average molecular weight of the crosslinked polyglutarimide including the isosorbide structure synthesized from the method for preparing polyglutarimide of the present invention may be 50,000 to 500,000 g / mol.
  • the weight average molecular weight of the polyglutarimide produced through the present invention is not particularly limited thereto, but if the above range is satisfied, not only excellent optical properties but also mechanical properties suitable for use as members in the field of optical members and electrical and electronic materials And it has a high heat resistance, does not cause deformation at a high temperature of 200 to 500 °C, and at the same time can exhibit mechanical properties such as strength, elasticity and surface hardness is preferred.
  • the polyglutarimide prepared from the method for producing polyglutarimide of the present invention is excellent in optical, mechanical and thermal properties through secondary processing such as solution process, extrusion or injection process in a dissolved state in a solution. It can be produced in various forms such as injection molded articles, such as electronic components, automotive parts, and extrusion molded articles such as films, monofilaments, and fibers.
  • the present invention comprises the steps of (1) preparing a mixture by adding a diamine compound comprising a poly glutimide and isosorbide structure to the solvent; And (2) preparing the molded article by secondary processing the mixture.
  • the polyglutarimide used in step (1) of the present invention comprises a polyglutarimide comprising a glutarimide repeat unit represented by the following formula (1); And a polyglutarimide comprising a glutarimide repeating unit represented by Formula 1 below, wherein 0.001 to 1.2 mol% of the glutarimide repeating unit forms a crosslinked structure represented by the following Formula 2; It may be one or more polyglutarimides.
  • R 1 And R 3 are independently of each other hydrogen or CH 3 ;
  • R 2 Is a substituted or unsubstituted linear or branched C1-C20 alkyl group, a substituted or unsubstituted straight or branched C3-C20 alkenyl group, a substituted or unsubstituted C3-C20 alkynyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, substituted or unsubstituted C6-C18 aryl group, straight or branched C1-C20 hydroxyalkyl group, straight or branched C1-C18 epoxyalkyl group, acryloyl group, methacryloyl group And it is any one selected from the group consisting of acrylooxy group, etc .;
  • R z Is a substituted or unsubstituted linear or branched C1-C20 alkyl group, a substituted or unsubstituted
  • a polar organic solvent capable of dissolving the polyglutarimide and the diamine compound may be used, and the diamine compound including the isosorbide structure may be used as the polyglue. 2 to 100 mol% may be used based on the content of the acrylate repeating unit in the acrylate polymer used to synthesize the tarimide, but is not limited thereto.
  • the mixture prepared through step (1) of the present invention may be manufactured into a molded article through the processing step of step (2), and the processing of step (2) is a molding method generally used for thermoplastic resins, specifically As an injection molding, it may be carried out by a method such as extrusion molding and press molding, but is not particularly limited thereto.
  • the molded article prepared through step (2) of the present invention is crosslinked by a diamine compound containing the isosorbide structure in which the acrylate repeating unit present in the polyglutarimide of the present invention is added during the secondary process.
  • a fully-crosslinked polyglutarimide hereinafter referred to as cross-linked polyglutarimide
  • cross-linked polyglutarimide molded article including the cross-linked glutarimide repeat unit of Formula 2, wherein the optical, mechanical and thermal properties Injection molded articles such as excellent electrical, electronic components, automotive parts, and extrusion molded articles such as films, monofilaments, fibers, and the like, and preferably, may include display optical members, electronic circuit members, and the like.
  • the polyglutarimide molded article produced through the present invention includes the cross-linked polyglutarimide, in addition to the light stabilizer, impact modifier, catalyst, plasticizer, dye, colorant, organic pigment, inorganic pigment, flame retardant, antistatic agent, It may further comprise one or more other components such as bio-stabilizers, compatibilizers, curing agents, lubricants, heat stabilizers, antioxidants, UV stabilizers.
  • the display optical member and the electronic circuit member can be adjusted by controlling the degree of crosslinking of the cross-linked polyglutarimide, optical properties, mechanical properties and thermal properties can be adjusted It can be characterized.
  • the display optical member typically includes a window applied to a touch surface of a refrigerator, an air conditioner, a mobile phone, and the like, a resin for a large backlight unit light guide plate, and the electronic circuit member includes electrical wiring for a radio, a television, and a computer. Electrical wiring coatings, printed wiring boards, dielectrics of semiconductors and electrical networks, and the like, but is not limited thereto.
  • the gel synthesis phenomenon was observed by visually observing a solution synthesized with each of the polyglutarimides (XLPGI) prepared in Example 2 and Comparative Example, step 2). At this time, when gelation occurs, it is indicated by ⁇ , when partially generated by ⁇ , and when not generated, by x.
  • the XLPGI film samples prepared through Examples and Comparative Examples were visually observed to observe the formation of the XLPGI film and the yellowness of the formed XLPGI film.
  • the glass transition temperature of the XLPGI film samples prepared in Examples and Comparative Examples was measured.
  • the sample was vacuum dried at 60 ° C. for 24 hours at a heating rate of 10 ° C./min, and the glass transition temperature was measured under nitrogen atmosphere.
  • the coating was cast on a glass substrate at a coating gap of 200 ⁇ m and a coating rate of 4 mm / min, followed by drying at 50 ° C. for 24 hours.
  • a partially crosslinked XLPGI film sample having an isosorbide structure having a thickness of 30 ⁇ m was prepared.
  • the physical properties of the prepared samples were measured and listed in Table 1.
  • step 1) of Example 1 polymethyl methacrylate having a weight average molecular weight of 120,000 g / mol (PMMA; Sigma Aldrich, USA) is used in place of polymethyl methacrylate having a weight average molecular weight of 15,000 g / mol. Except for the rest, XLPGI film samples partially crosslinked with an isosorbide structure having a thickness of 30 ⁇ m were prepared in the same process.
  • Example 1 of Example 1 Except for using butylamine (hereinafter, BA; Sigma Aldrich, USA) in place of isopropylamine (IPA) in Example 1 of Example 1, a polyglutalimide film sample was prepared in the same process. .
  • BA butylamine
  • IPA isopropylamine
  • the second mixed solution was prepared by further adding 0.115 g (0.0008 mol) of isosorbide diamine to the mixed solution including partially crosslinked XLPGI prepared in Step 1) of Example 1 to Example 8, respectively.
  • a polyglutalimide (XLPGI) film sample was prepared by crosslinking the second mixed solution with an isosorbide structure having a thickness of 30 ⁇ m through an injection machine at 330 ° C.
  • Example 1 Except for using the polymethyl methacrylate having a weight average molecular weight of 10,000g / mol in place of the polymethyl methacrylate having a weight average molecular weight of 15,000g / mol in step 1) of Example 1 the rest are the same Polyglutalimide film samples were prepared by the procedure.
  • Example 1 Except for using a polymethyl methacrylate having a weight average molecular weight of 400,000 g / mol in place of the polymethyl methacrylate having a weight average molecular weight of 15,000 g / mol in step 1) of Example 1 A polyglutarimide film was prepared by the procedure.
  • Example 1 PMMA Diamine Compound (Content) Amine compound (content) Solvent (usage) Mw content
  • Example 1 15,000 4 g ISBDA 0.028 g IPA 9.45 g 10 g of toluene
  • Example 2 120,000
  • Example 3 15,000 BA 9.45 g
  • Example 4 120,000
  • Example 5 15,000 ISBDA 0.0575 g IPA 9.45 g
  • Example 6 120,000
  • Example 7 15,000 BA 9.45 g
  • Example 8 120,000
  • Example 9 15,000 4 g ISBDA 0.143 g (0.028 + 0.115) IPA 9.45 g
  • Example 10 120,000
  • Example 11 15,000 BA 9.45 g
  • Example 12 120,000
  • Example 13 15,000 ISBDA 0.1725 g (0.0575 + 0.115) IPA 9.45 g
  • Example 14 120,000
  • Example 15 15,000 BA 9.45 g
  • Example 16 120,000 Comparative Example 1 1,000 4 g ISBDA 0.028 g IPA 9.45 g Comparative Example 2 400,000
  • Examples 1 to 16 of the present invention shows that the gelled polyglutarimide (XLPGI) is not produced on the crosslinked solution, and according to the embodiment of the present invention through the above results.
  • the crosslinked polyglutarimide (XLPGI) produced is partially crosslinked without excessive crosslinking reaction and uniformly crosslinked, so that crosslinked polyglutalimide (XLPGI) is prepared by dissolving in a solvent to enable secondary processing. It can be confirmed.
  • the comparative example of the present invention the result of the formation of the partially or fully gelled XLPGI in the solution, it can be seen that the cross-linking reaction in the resulting XLPGI occurs unevenly.
  • the polyglutalimide film samples of Examples 1 to 16 of the present invention have a glass transition temperature of 138.32 to 153.72 °C, it can be seen that the glass transition temperature is up to 47 °C compared to the film sample of the comparative example, through this general Compared with the case of using a diamine compound, it turns out that the heat resistance of the polyglutarimide manufactured by using the diamine compound which has the isosorbide mother nucleus of this invention can be improved effectively.
  • the existing polymethyl methacrylate through the polyglutarimide prepared according to Examples 1 to 16 of the present invention It can be seen that the low heat resistance of the acrylate can be effectively improved, and thus it can maintain a stable state even at high temperatures.
  • the polyglutarimide of the comparative example is dried after casting. Due to the cracking phenomenon in the process, it is impossible to produce a film, and also the polyglutarimide of the comparative example may be colored and thus, it may be confirmed that the production of a transparent film is impossible.
  • the low-molecular-weight PMMA is included through a contrast between the polyglutalimide film sample of Example 1 present in the upper right side of FIG. 1 and the polyglutarimide film sample of Comparative Example 1 present in the upper right side of FIG. 2.

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Abstract

The present invention relates to a crosslinked polyglutarimide including isosorbide, and a method of producing same. The crosslinked polyglutarimide including isosorbide according to the present invention includes isosorbide as a cross linking agent that displays improved effects of transparency and surface hardness with respect to polyglutarimide, and has not only excellent optical properties, but also significantly improved heat resistance and mechanical physical properties, such that the crosslinked polyglutarimide including isosorbide can be produced as a forming material such as for a display optical member and an electrical/electronic circuit member.

Description

이소소르비드를 포함하는 가교된 폴리글루타르이미드 및 이의 제조방법Cross-linked polyglutarimide containing isosorbide and preparation method thereof
본 발명은 이소소르비드를 포함하는 가교된 폴리글루타르이미드 및 이의 제조방법에 관한 것이다.The present invention relates to a crosslinked polyglutarimide comprising isosorbide and a process for preparing the same.
최근 디스플레이 기술이 발전함에 따라 LCD, LED 등 화면을 출력하기 위해 다양한 디스플레이장치가 적용되고 있으며, 이러한 디스플레이장치는 휴대폰이나 컴퓨터 모니터, TV 등 다양한 분야에 적용되고 있는 실정이다. 이러한 디스플레이장치는 극대화 된 화상의 출력 효과, 외부 충격으로부터 견디는 효과 및 휴대성을 갖추기 위하여 꾸준히 연구되고 있으며, 이에 따라 최근에는 디스플레이 장치에 가벼우며 고강도, 내구성 및 투명성이 뛰어난, 우수한 기계적 물성 및 광학특성을 가지는 폴리메틸메타크릴레이트(Polymethyl methacrylate, PMMA)가 보편적으로 포함되고 있다.Recently, with the development of display technology, various display devices are being applied to output a screen such as LCD and LED. Such display devices are applied to various fields such as mobile phones, computer monitors, and TVs. Such display devices have been steadily researched in order to maximize the image output effect, endurance from external impact, and portability. Accordingly, in recent years, the display devices are light in display devices and have excellent mechanical properties and optical properties with high strength, durability, and transparency. Polymethyl methacrylate (PMMA) having a universally contained.
폴리메틸메타크릴레이트는 메틸메타크릴레이트의 중합물의 하나로서, 투명성, 내후성이 탁월할 뿐만 아니라 경도, 내약품성, 표면광택, 접착성 등이 우수하여 유리의 대용품으로 널리 사용되고 있으며, 현재 냉장고, 에어컨 등 가전제품의 하우징(housing)과 휴대폰 터치 면에 적용되는 창(window)소재로 사용되고 있는 강화 유리를 대체하여 사용되고 있다. 그러나, 메타크릴레이트계 수지는 다른 플라스틱 소재와 비교하여 열 변형 온도(Heat Distortion Temperature, HDT)가 80 내지 97℃ 수준이고 연속 사용온도가 60 내지 80℃ 수준으로 낮아, 내열성이 낮은 문제점을 가지고 있다. 상기 문제점을 해결하기 위하여, 기계적 물성, 광학특성 및 내열성이 모두 우수한 특성을 가지는 폴리글루타르이미드 중합체를 도입하기에 이르렀다.Polymethyl methacrylate is one of the polymers of methyl methacrylate. It is not only excellent in transparency and weather resistance, but also excellent in hardness, chemical resistance, surface gloss and adhesion, and is widely used as a substitute for glass. It is used to replace tempered glass, which is used as a window material applied to the housing of a home appliance and a touch surface of a mobile phone. However, methacrylate-based resins have a problem that heat distortion temperature (HDT) is 80 to 97 ° C. and continuous use temperature is low to 60 to 80 ° C., compared with other plastic materials, and thus has low heat resistance. . In order to solve the above problems, it has been introduced to a polyglutarimide polymer having excellent mechanical properties, optical properties and heat resistance.
폴리메틸메타크릴레이트를 대체하는 물질로 적용되는 폴리글루타르이미드는 이미드 결합을 포함하고 있어, 탄성계수, 점성 및 굴절률이 높은 우수한 기계적 물성 및 광학특성을 가지며, 130℃ 이상의 유리전이온도를 가져, 폴리메틸메타크릴레이트보다 내열성이 우수한 특성을 가지고 있다.Polyglutalimide, which is applied as a substitute for polymethyl methacrylate, contains imide bonds, has excellent mechanical properties and optical properties with high modulus, viscosity, and refractive index, and has a glass transition temperature of 130 ° C. or higher. It has a better heat resistance than polymethyl methacrylate.
일반적인 폴리글루타르이미드는 최대 180℃의 유리전이온도를 가져 그 이상의 고온이 가해질 경우, 기계적 물성 및 광학특성이 변하는 문제점이 있다. 이에, 폴리글루타르이미드 화학 구조에 상기 문제를 해결할 수 있는 정도의 내열성 및 기계적 물성을 부여하기 위한 방법이 요구되고 있다.In general, polyglutarimide has a glass transition temperature of up to 180 ° C., and when a high temperature is applied thereto, mechanical properties and optical properties change. Accordingly, there is a demand for a method for imparting heat resistance and mechanical properties to the polyglutarimide chemical structure to solve the above problem.
본 발명은 상기한 바와 같은 문제점을 해결하고자 한 것으로, 폴리글루타르이미드에 가교제로서, 2개의 테트라하이드로 퓨란링이 120°의 각도로 결합된 구조를 가지며, 내열성, 투명도 및 표면경도 향상 효과를 부여할 수 있는 이소소르비드를 도입함으로써 폴리글루타르이미드를 가교시켜, 기계적 물성, 광학특성 및 열적 특성이 일반적인 폴리글루타르이미드에 대비하여 더 우수한, 가교된 폴리글루타르이미드 및 이의 제조방법을 제공한다.The present invention has been made to solve the problems described above, as a cross-linking agent to polyglutarimide, two tetrahydrofuran ring has a structure bonded at an angle of 120 °, giving heat resistance, transparency and surface hardness improvement effect By introducing isosorbide, which is capable of crosslinking polyglutarimide, the present invention provides a crosslinked polyglutarimide and a method for preparing the same, which have better mechanical, optical and thermal properties than general polyglutarimide. .
본 발명은 하기 화학식 1로 표시되는 글루타르이미드 반복단위를 포함하는 폴리글루타르이미드에 있어서,The present invention provides a polyglutarimide comprising a glutarimide repeating unit represented by the following formula (1),
[화학식 1][Formula 1]
Figure PCTKR2016012690-appb-I000001
Figure PCTKR2016012690-appb-I000001
[화학식 2][Formula 2]
Figure PCTKR2016012690-appb-I000002
Figure PCTKR2016012690-appb-I000002
상기 글루타르이미드 반복단위의 0.001 내지 1.2 몰%는 상기 화학식 2로 표시되는 가교구조를 형성하는 것인 폴리글루타르이미드에 관한 것이다.0.001 to 1.2 mole% of the glutarimide repeating unit relates to a polyglutarimide which forms a crosslinked structure represented by Chemical Formula 2.
상기 화학식 1 및 화학식 2에서, In Chemical Formula 1 and Chemical Formula 2,
R1 및 R3 는 서로 독립적으로 수소 또는 CH3이고; R 1 And R 3 Are independently of each other hydrogen or CH 3 ;
R2 는 치환 또는 비치환된 직쇄상 또는 분지상의 C1-C20 알킬기, 치환 또는 비치환된 직쇄상 또는 분지상의 C3-C20 알케닐기, 치환 또는 비치환된 C3-C20 알키닐기, 치환 또는 비치환된 C3-C10 사이클로알킬기, 치환 또는 비치환된 C6-C18 아릴기, 직쇄상 또는 분지상의 C1-C20 하이드록시알킬기, 직쇄상 또는 분지상의 C1-C18 에폭시알킬기, 아크릴로일기, 메타크릴로일기 및 아크릴로옥시기로 이루어진 군에서 선택되는 어느 하나이며; R 2 Is a substituted or unsubstituted linear or branched C1-C20 alkyl group, a substituted or unsubstituted straight or branched C3-C20 alkenyl group, a substituted or unsubstituted C3-C20 alkynyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, substituted or unsubstituted C6-C18 aryl group, straight or branched C1-C20 hydroxyalkyl group, straight or branched C1-C18 epoxyalkyl group, acryloyl group, methacryloyl group And acrylooxy group is any one selected from the group consisting of;
Rz 는 치환 또는 비치환된 직쇄상 또는 분지상의 C1-C20 알킬기, 치환 또는 비치환된 직쇄상 또는 분지상의 C3-C20 알케닐기, 치환 또는 비치환된 C3-C10 사이클로알킬기, 치환 또는 비치환된 C6-C18 아릴기, 직쇄상 또는 분지상의 C1-C18 에폭시알킬기, 아크릴로일기, 메타크릴로일기 및 아크릴로옥시기로 이루어진 군에서 선택되는 어느 하나이고;R z Is a substituted or unsubstituted linear or branched C1-C20 alkyl group, a substituted or unsubstituted straight or branched C3-C20 alkenyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted Any one selected from the group consisting of a C6-C18 aryl group, a straight or branched C1-C18 epoxyalkyl group, an acryloyl group, a methacryloyl group, and an acrylooxy group;
A 및 B는 서로 독립적으로 단일결합 및 R′-X- 형태에서 선택되는 어느 하나이며, 상기 R′은 이미드기와 결합되는 것으로, 치환 또는 비치환된 직쇄상 또는 분지상의 C1-C20 알킬렌, 치환 또는 비치환된 직쇄상 또는 분지상의 C3-C20 알케닐렌, 치환 또는 비치환된 C3-C20 알키닐렌, 치환 또는 비치환된 C3-C10 사이클로알킬렌 및 치환 또는 비치환된 C6-C18 아릴렌으로 이루어진 군에서 선택되는 하나 이상이고, 상기 X-는 이소소르비드와 결합되는 것으로, 단일결합, O-, -S-, C(=O)-, -C(=O)O- 또는 SO2- 이며;A and B are each independently selected from a single bond and R'-X- form, wherein R 'is bonded to an imide group, and substituted or unsubstituted linear or branched C1-C20 alkylene , Substituted or unsubstituted straight or branched C3-C20 alkenylene, substituted or unsubstituted C3-C20 alkynylene, substituted or unsubstituted C3-C10 cycloalkylene and substituted or unsubstituted C6-C18 aryl At least one selected from the group consisting of lens, wherein X- is combined with isosorbide, a single bond, O-, -S-, C (= 0)-, -C (= 0) O- or SO 2- ;
a 및 b는 서로 독립적으로 1 내지 1,000의 정수이고, 0.001a≤b≤0.33a 일 수 있다.a and b are each independently an integer of 1 to 1,000, and may be 0.001a ≦ b ≦ 0.33a.
본 발명에 따른 이소소르비드를 포함하는 가교된 폴리글루타르이미드는 폴리글루타르이미드에 투명도 및 표면경도 향상 효과를 나타내는 이소소르비드를 가교제로 포함함으로써 우수한 광학특성뿐만 아니라 내열성 및 기계적 물성 특성이 현저히 향상된 디스플레이 광학부재 및 전기 전자 회로 부재 등의 성형품의 제조를 가능하게 할 수 있다.The crosslinked polyglutarimide including isosorbide according to the present invention includes isosorbide, which exhibits transparency and surface hardness enhancement effect, as a crosslinking agent in the polyglutarimide, thereby significantly improving heat resistance and mechanical properties. It is possible to enable the production of molded articles such as improved display optical members and electrical and electronic circuit members.
도 1은 본 발명의 실시예 1(우측 상단), 실시예 2(중앙 상단), 실시예 3(좌측 상단), 실시예 6(좌측 하단) 및 실시예 8(우측 하단)의 방법에 따라 제조된 XLPGI의 필름 형성 여부를 육안으로 관찰한 결과이다.1 is prepared according to the method of Example 1 (top right), Example 2 (center top), Example 3 (top left), Example 6 (bottom left) and Example 8 (bottom right) of the present invention. It is the result of visual observation whether the film of the formed XLPGI was formed.
도 2는 본 발명의 비교예 1(우측 상단), 비교예 2(좌측 상단), 비교예 3(좌측 하단), 비교예 4(중앙 하단) 및 비교예 5(우측 하단)의 방법에 따라 제조된 XLPGI의 필름 형성 여부를 육안으로 관찰한 결과이다.2 is prepared according to the method of Comparative Example 1 (top right), Comparative Example 2 (top left), Comparative Example 3 (bottom left), Comparative Example 4 (center bottom) and Comparative Example 5 (bottom right) of the present invention. It is the result of visual observation whether the film of the formed XLPGI was formed.
이하 본 발명의 이소소르비드를 포함하는 가교된 폴리글루타르이미드 및 이의 제조방법에 대하여 상세히 설명한다. 다음에 소개되는 실시예는 당업자에게 본 발명의 사상이 충분히 전달될 수 있도록 하기 위해 예로서 제공되는 것이다. 또한, 사용되는 기술 용어 및 과학 용어에 있어서 다른 정의가 없다면, 이 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가지며, 하기의 설명에서 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 설명은 생략한다.Hereinafter, a cross-linked polyglutarimide including the isosorbide of the present invention and a method for preparing the same will be described in detail. The following embodiments are provided as examples to ensure that the spirit of the present invention to those skilled in the art will fully convey. In addition, unless there is another definition in the technical terms and scientific terms used, it has the meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and unnecessarily obscure the subject matter of the present invention in the following description. Description of known functions and configurations that may be omitted.
명세서 전체에서, 치환된은 '화합물 또는 화합물을 구성하는 구조에서, 탄소 원소에 결합된 수소 원소가 할로겐원소, 니트로기, 히드록시기, C1-C7 알킬, C1-C7 알콕시, C1-C7 알킬카보닐, C1-C7 알콕시카보닐 및 포밀기(-CHO) 등으로부터 선택되는 하나 이상의 치환기로 치환된'것을 의미한다.Throughout the specification, substituted silver 'in the compound or structure constituting the compound, a hydrogen element bonded to a carbon element is halogen, nitro, hydroxy, C1-C7 alkyl, C1-C7 alkoxy, C1-C7 alkylcarbonyl, Substituted with one or more substituents selected from C1-C7 alkoxycarbonyl, formyl (-CHO) and the like.
또한, 명세서 전체에서, 폴리글루타르이미드는 '이소소르비드 구조를 포함하는 가교된 폴리글루타르이미드'를 의미한다.In addition, throughout the specification, polyglutarimide means 'crosslinked polyglutarimide comprising isosorbide structure'.
본 발명은 우수한 광학특성을 가지며 내열성 및 기계적 물성 특성이 현저히 향상된 폴리글루타르이미드에 관한 것으로, 하기 화학식 1로 표시되는 글루타르이미드 반복단위를 포함하는 폴리글루타르이미드에 있어서,The present invention relates to a polyglutarimide having excellent optical properties and remarkably improved heat resistance and mechanical properties, and in the polyglutarimide comprising a glutarimide repeating unit represented by Formula 1 below,
[화학식 1][Formula 1]
Figure PCTKR2016012690-appb-I000003
Figure PCTKR2016012690-appb-I000003
[화학식 2][Formula 2]
Figure PCTKR2016012690-appb-I000004
Figure PCTKR2016012690-appb-I000004
상기 글루타르이미드 반복단위의 0.001 내지 1.2 몰%는 상기 화학식 2로 표시되는 가교구조를 형성하는 것인 폴리글루타르이미드에 관한 것이다.0.001 to 1.2 mole% of the glutarimide repeating unit relates to a polyglutarimide which forms a crosslinked structure represented by Chemical Formula 2.
이때, 상기 화학식 1에서 상기 R1 및 R3 는 서로 독립적으로 수소 또는 CH3일 수 있으며; 상기 R2 는 치환 또는 비치환된 직쇄상 또는 분지상의 C1-C20 알킬기, 치환 또는 비치환된 직쇄상 또는 분지상의 C3-C20 알케닐기, 치환 또는 비치환된 C3-C20 알키닐기, 치환 또는 비치환된 C3-C10 사이클로알킬기, 치환 또는 비치환된 C6-C18 아릴기, 직쇄상 또는 분지상의 C1-C20 하이드록시알킬기, 직쇄상 또는 분지상의 C1-C18 에폭시알킬기, 아크릴로일기, 메타크릴로일기 및 아크릴로옥시기 등으로 이루어진 군에서 선택되는 어느 하나일 수 있으며, 바람직하게는 C1-C20 알킬기, C3-C20 알케닐기, C3-C20 알키닐기 및 C6-C18 아릴기에서 선택되는 어느 하나일 수 있으나, 이에 특별히 제한되는 것은 아니다. 이 때, 상기 R2 에 포함될 수 있는 상기 알킬기 및 알케닐기로는 직쇄상 또는 분지상의 C1 내지 C20 알킬기 및 직쇄상 또는 분지상의 C3 내지 C20 알케닐기일 수 있고, 바람직하게는 C1 내지 C10 알킬기, C3 내지 C10 알케닐기 및 C3 내지 C10 알키닐기일 수 있으며, 상기 사이클로알킬기로는 C3 내지 C10의 사이클로알킬기, 바람직하게는 C3 내지 C6 사이클로알킬기일 수 있으나, 이에 제한되는 것은 아니다. At this time, the R 1 in Formula 1 And R 3 Can independently be hydrogen or CH 3 ; R 2 Is a substituted or unsubstituted linear or branched C1-C20 alkyl group, a substituted or unsubstituted straight or branched C3-C20 alkenyl group, a substituted or unsubstituted C3-C20 alkynyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, substituted or unsubstituted C6-C18 aryl group, straight or branched C1-C20 hydroxyalkyl group, straight or branched C1-C18 epoxyalkyl group, acryloyl group, methacryloyl group And it may be any one selected from the group consisting of acrylooxy group and the like, preferably any one selected from C1-C20 alkyl group, C3-C20 alkenyl group, C3-C20 alkynyl group and C6-C18 aryl group. However, the present invention is not particularly limited thereto. At this time, the alkyl group and alkenyl group which may be included in the R 2 may be a linear or branched C1 to C20 alkyl group and a linear or branched C3 to C20 alkenyl group, preferably C1 to C10 alkyl group , C3 to C10 alkenyl group and C3 to C10 alkynyl group, the cycloalkyl group may be a C3 to C10 cycloalkyl group, preferably C3 to C6 cycloalkyl group, but is not limited thereto.
또한, 상기 Rz 는 치환 또는 비치환된 직쇄상 또는 분지상의 C1-C20 알킬기, 치환 또는 비치환된 직쇄상 또는 분지상의 C3-C20 알케닐기, 치환 또는 비치환된 C3-C10 사이클로알킬기, 치환 또는 비치환된 C6-C18 아릴기, 직쇄상 또는 분지상의 C1-C18 에폭시알킬기, 아크릴로일기, 메타크릴로일기 및 아크릴로옥시기 등으로 이루어진 군에서 선택되는 어느 하나일 수 있으며, 바람직하게는 C1-C20 알킬기, C3-C20 알케닐기, C3-C20 알키닐기 및 C6-C18 아릴기에서 선택되는 어느 하나일 수 있으나, 이에 특별히 제한되는 것은 아니다. In addition, the R z Is a substituted or unsubstituted linear or branched C1-C20 alkyl group, a substituted or unsubstituted straight or branched C3-C20 alkenyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C6-C18 aryl group, linear or branched C1-C18 epoxyalkyl group, acryloyl group, methacryloyl group and acrylooxy group and the like can be any one selected from the group consisting of, preferably C1-C20 It may be any one selected from an alkyl group, a C3-C20 alkenyl group, a C3-C20 alkynyl group, and a C6-C18 aryl group, but is not particularly limited thereto.
더불어, 상기 화학식 1에서 상기 A 및 B는 서로 독립적으로 단일결합 및 'R′-X-' 형태에서 선택되는 어느 하나일 수 있으며, 상기 A 및 B가 'R′-X-' 형태일 경우, 상기 R′은 이미드기와 결합되는 것으로, 치환 또는 비치환된 직쇄상 또는 분지상의 C1-C20 알킬렌, 치환 또는 비치환된 직쇄상 또는 분지상의 C3-C20 알케닐렌, 치환 또는 비치환된 C3-C20 알키닐렌, 치환 또는 비치환된 C3-C10 사이클로알킬렌 및 치환 또는 비치환된 C6-C18 아릴렌 등으로 이루어진 군에서 선택되는 하나 이상일 수 있고, 상기 X-는 이소소르비드와 결합되는 것으로, 단일결합, O-, -S-, C(=O)-, -C(=O)O- 또는 SO2- 일 수 있으며, 상기 a 및 b는 서로 독립적으로 1 내지 1,000의 정수이고, 0.001a≤b≤0.33a 일 수 있다. In addition, in Formula 1, A and B may be any one selected from a single bond and 'R'-X-' form independently of each other, and when A and B are in the 'R'-X-' form, R ′ is bonded to an imide group, and substituted or unsubstituted linear or branched C1-C20 alkylene, substituted or unsubstituted linear or branched C3-C20 alkenylene, substituted or unsubstituted C3-C20 alkynylene, substituted or unsubstituted C3-C10 cycloalkylene and substituted or unsubstituted C6-C18 arylene and the like, and the like, wherein X- is combined with isosorbide May be a single bond, O—, —S—, C (═O) —, —C (═O) O— or SO 2 —, wherein a and b are integers of 1 to 1,000 independently of each other, 0.001a ≦ b ≦ 0.33a.
본 발명에서 상기 화학식 2로 표시되는 가교구조로 결합되는 폴리글루타르이미드 중합체 사슬은 동일한 중합체 분자 내의 서로 다른 글루타르이미드 반복단위 사이의 가교결합 또는 서로 다른 중합체 분자간의 글루타르이미드 반복단위 사이의 결합일 수 있다.In the present invention, the polyglutarimide polymer chain bonded with the crosslinked structure represented by Chemical Formula 2 may be a crosslink between different glutarimide repeat units in the same polymer molecule or a bond between glutarimide repeat units between different polymer molecules. Can be.
본 발명에서 상기 A 및 B는, 바람직하게는 단일결합,In the present invention, A and B are preferably a single bond,
Figure PCTKR2016012690-appb-I000005
Figure PCTKR2016012690-appb-I000005
등으로 이루어진 군에서 선택되는 어느 하나일 수 있으나, 이에 특별히 제한되는 것은 아니다.It may be any one selected from the group consisting of, but is not particularly limited thereto.
본 발명에 따른 상기 화학식 1의 반복단위를 포함하는 폴리글루타르이미드는 중량평균분자량이 50,000 내지 500,000g/mol일 수 있다. 이때, 중량평균분자량은 Agilent Technologies사의 1260 Infinity를 이용(표준시료: 폴리스티렌(Polystyrene))하여 측정된 것으로, 칼럼(Column)은 PL gel Olexis를 사용하였고, 샘플은 DMAc 를 용매로 하여 100ml LiCl(농도: 0.5wt%)에 4mg 함유된 것을 사용한 것이다.Polyglutalimide including the repeating unit of Formula 1 according to the present invention may have a weight average molecular weight of 50,000 to 500,000 g / mol. At this time, the weight average molecular weight was measured by using Agilent Technologies' 1260 Infinity (standard sample: Polystyrene), column was used PL gel Olexis, sample was 100ml LiCl (concentration) using DMAc as a solvent : 0.5wt%) contained 4mg.
또한, 본 발명은 이소소르비드 구조로 가교된 폴리글루타르이미드의 제조방법에 관한 것으로, 상기 폴리글루타르이미드의 제조방법은 아크릴레이트계 중합체, 이소소르비드를 포함하는 하기 화학식 3으로 표시되는 디아민 화합물 및 하기 화학식 4로 표시되는 아민 화합물을 반응하는 단계를 포함할 수 있으며, 상기 단계를 통하여 제조되는 하기 화학식 1의 반복단위를 포함하는 폴리글루타르이미드는 총 글루타르이미드 반복단위에 대하여 0.001 내지 1.2 몰%가 하기 화학식 2로 표시되는 가교구조를 포함할 수 있다.In addition, the present invention relates to a method for producing a polyglutarimide crosslinked with an isosorbide structure, the method for producing a polyglutarimide is a diamine represented by the formula (3) comprising an acrylate-based polymer, isosorbide It may include the step of reacting the compound and the amine compound represented by the formula (4), wherein the poly glutarimide comprising a repeating unit of the formula (1) prepared through the above step is from 0.001 to the total glutarimide repeating unit 1.2 mol% may include a crosslinked structure represented by Formula 2 below.
[화학식 1][Formula 1]
Figure PCTKR2016012690-appb-I000006
Figure PCTKR2016012690-appb-I000006
[화학식 2][Formula 2]
Figure PCTKR2016012690-appb-I000007
Figure PCTKR2016012690-appb-I000007
[화학식 3][Formula 3]
Figure PCTKR2016012690-appb-I000008
Figure PCTKR2016012690-appb-I000008
[화학식 4][Formula 4]
Figure PCTKR2016012690-appb-I000009
Figure PCTKR2016012690-appb-I000009
본 발명의 폴리글루타르이미드의 제조방법에서, 상기 화학식 1 및 화학식 2의 R1 및 R3 는 서로 독립적으로 수소 또는 CH3일 수 있고; R2 는 치환 또는 비치환된 직쇄상 또는 분지상의 C1-C20 알킬기, 치환 또는 비치환된 직쇄상 또는 분지상의 C3-C20 알케닐기, 치환 또는 비치환된 C3-C20 알키닐기, 치환 또는 비치환된 C3-C10 사이클로알킬기, 치환 또는 비치환된 C6-C18 아릴기, 직쇄상 또는 분지상의 C1-C20 하이드록시알킬기, 직쇄상 또는 분지상의 C1-C18 에폭시알킬기, 아크릴로일기, 메타크릴로일기 및 아크릴로옥시기 등으로 이루어진 군에서 선택되는 어느 하나일 수 있으며; Rz 는 치환 또는 비치환된 직쇄상 또는 분지상의 C1-C20 알킬기, 치환 또는 비치환된 직쇄상 또는 분지상의 C3-C20 알케닐기, 치환 또는 비치환된 C3-C10 사이클로알킬기, 치환 또는 비치환된 C6-C18 아릴기, 직쇄상 또는 분지상의 C1-C18 에폭시알킬기, 아크릴로일기, 메타크릴로일기 및 아크릴로옥시기 등으로 이루어진 군에서 선택되는 어느 하나일 수 있다. In the method for preparing polyglutarimide of the present invention, R 1 of Chemical Formula 1 and Chemical Formula 2 And R 3 Can independently be hydrogen or CH 3 ; R 2 Is a substituted or unsubstituted linear or branched C1-C20 alkyl group, a substituted or unsubstituted straight or branched C3-C20 alkenyl group, a substituted or unsubstituted C3-C20 alkynyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, substituted or unsubstituted C6-C18 aryl group, straight or branched C1-C20 hydroxyalkyl group, straight or branched C1-C18 epoxyalkyl group, acryloyl group, methacryloyl group And it may be any one selected from the group consisting of acrylooxy group and the like; R z Is a substituted or unsubstituted linear or branched C1-C20 alkyl group, a substituted or unsubstituted straight or branched C3-C20 alkenyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted It may be any one selected from the group consisting of C6-C18 aryl group, linear or branched C1-C18 epoxyalkyl group, acryloyl group, methacryloyl group and acrylooxy group.
상기 화학식 2의 A 및 B는 서로 독립적으로 단일결합 및 'R′-X-' 형태에서 선택되는 어느 하나일 수 있으며, 상기 A 및 B가 'R′-X-' 형태일 경우, 상기 R′은 이미드기와 결합되는 것으로, 치환 또는 비치환된 직쇄상 또는 분지상의 C1-C20 알킬렌, 치환 또는 비치환된 직쇄상 또는 분지상의 C3-C20 알케닐렌, 치환 또는 비치환된 C3-C20 알키닐렌, 치환 또는 비치환된 C3-C10 사이클로알킬렌 및 치환 또는 비치환된 C6-C18 아릴렌 등으로 이루어진 군에서 선택되는 하나 이상일 수 있고, 상기 X-는 이소소르비드와 결합되는 것으로, 단일결합, O-, -S-, C(=O)-, -C(=O)O- 또는 SO2- 일 수 있으며, 상기 화학식 1의 a 및 b는 서로 독립적으로 1 내지 1,000의 정수이고, 0.001a≤b≤0.33a 일 수 있으나, 이에 특별히 제한되는 것은 아니다.A and B of Formula 2 may be any one selected from a single bond and 'R'-X-' form independently of each other, when A and B is a 'R'-X-' form, the R ' Is bonded to an imide group and is substituted or unsubstituted straight or branched C1-C20 alkylene, substituted or unsubstituted straight or branched C3-C20 alkenylene, substituted or unsubstituted C3-C20 It may be one or more selected from the group consisting of alkynylene, substituted or unsubstituted C3-C10 cycloalkylene, substituted or unsubstituted C6-C18 arylene, and the like, wherein X- is combined with isosorbide, May be a bond, O—, —S—, C (═O) —, —C (═O) O—, or SO 2 —, wherein a and b in Formula 1 are each independently an integer of 1 to 1,000, 0.001a ≦ b ≦ 0.33a, but is not particularly limited thereto.
또한, 상기 화학식 3에서, A 및 B는 상기 화학식 2에서 정의한 A 및 B와 동일한 것으로, 서로 독립적으로 단일결합 및 'R′-X-' 형태에서 선택되는 어느 하나일 수 있으며, 상기 A 및 B가 'R′-X-' 형태일 경우, 상기 R′은 아민기와 결합되는 것으로, 치환 또는 비치환된 직쇄상 또는 분지상의 C1-C20 알킬렌, 치환 또는 비치환된 직쇄상 또는 분지상의 C3-C20 알케닐렌, 치환 또는 비치환된 C3-C20 알키닐렌, 치환 또는 비치환된 C3-C10 사이클로알킬렌 및 치환 또는 비치환된 C6-C18 아릴렌 등으로 이루어진 군에서 선택되는 하나 이상일 수 있고, 상기 X-는 이소소르비드와 결합되는 것으로, 단일결합, O-, -S-, C(=O)-, -C(=O)O- 또는 SO2- 일 수 있다. 본 발명에서 상기 A 및 B는, 바람직하게는 단일결합,In addition, in Chemical Formula 3, A and B are the same as A and B defined in Chemical Formula 2, and may be any one selected from a single bond and a 'R'-X-' form independently of each other, and A and B Is a 'R'-X-' form, R 'is bonded to an amine group, and substituted or unsubstituted linear or branched C1-C20 alkylene, substituted or unsubstituted linear or branched One or more selected from the group consisting of C3-C20 alkenylene, substituted or unsubstituted C3-C20 alkynylene, substituted or unsubstituted C3-C10 cycloalkylene, substituted or unsubstituted C6-C18 arylene, and the like. , X- is combined with isosorbide, and may be a single bond, O-, -S-, C (= 0)-, -C (= 0) O-, or SO 2- . In the present invention, A and B are preferably a single bond,
Figure PCTKR2016012690-appb-I000010
Figure PCTKR2016012690-appb-I000010
등으로 이루어진 군에서 선택되는 어느 하나일 수 있으나, 이에 특별히 제한되는 것은 아니다.It may be any one selected from the group consisting of, but is not particularly limited thereto.
더불어, 상기 화학식 4의 Rz는 상기 화학식 1에서 정의한 Rz 와 동일한 것으로, 치환 또는 비치환된 직쇄상 또는 분지상의 C1-C20 알킬기, 치환 또는 비치환된 직쇄상 또는 분지상의 C3-C20 알케닐기, 치환 또는 비치환된 C3-C10 사이클로알킬기, 치환 또는 비치환된 C6-C18 아릴기, 직쇄상 또는 분지상의 C1-C18 에폭시알킬기, 아크릴로일기, 메타크릴로일기 및 아크릴로옥시기 등으로 이루어진 군에서 선택되는 어느 하나일 수 있으며, 바람직하게는 직쇄상 또는 분지상의 C1-C20 알킬기, 직쇄상 또는 분지상의 C3-C20 알케닐기, C3-C10 사이클로알킬 및 C6-C18 아릴기로 이루어진 군에서 선택되는 어느 하나일 수 있으나 이에 특별히 제한되는 것은 아니다.In addition, of the formula R 4 z R z is as defined in formula (I) The same as, a substituted or unsubstituted linear or branched C1-C20 alkyl group, a substituted or unsubstituted straight or branched C3-C20 alkenyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or It may be any one selected from the group consisting of an unsubstituted C6-C18 aryl group, linear or branched C1-C18 epoxyalkyl group, acryloyl group, methacryloyl group and acrylooxy group, and the like. It may be any one selected from the group consisting of linear or branched C1-C20 alkyl group, linear or branched C3-C20 alkenyl group, C3-C10 cycloalkyl and C6-C18 aryl group, but is not particularly limited thereto. .
본 발명의 폴리글루타르이미드의 제조방법에서 사용되는 상기 아크릴레이트계 단량체는, 아크릴레이트 관능기를 1개 이상 포함하는, 단관능성 또는 다관능성의 알킬 (메타)아크릴레이트, 알케닐 (메타)아크릴레이트, 알키닐 (메타)아크릴레이트, 사이클로알킬 (메타)아크릴레이트, 아릴 (메타)아크릴레이트, 하이드록시알킬 (메타)아크릴레이트, 에폭시알킬(메타)아크릴레이트, 아크릴로일(메타)아크릴레이트, 메타크릴로일(메타)아크릴레이트 및 아크릴로옥시알킬(메타)아크릴레이트 등으로 이루어진 군에서 선택되는 어느 하나일 수 있으며, 상세하게는, 메틸 (메타)아크릴레이트, 에틸 (메타)아크릴레이트, n-부틸 (메타)아크릴레이트, 옥틸 (메타)아크릴레이트, 이소부틸 (메타)아크릴레이트, 이소옥실 (메타)아크릴레이트, 이소데실 (메타)아크릴레이트, 2-에틸헥실 (메타)아크릴레이트, 이소보닐 (메타)아크릴레이트, 2-하이드록시에틸 (메타)아크릴레이트, 2-하이드록시프로필 (메타)아크릴레이트, 2-하이드록시부틸 (메타)아크릴레이트, 글리시딜 (메타)아크릴레이트, 라우릴 (메타)아크릴레이트, 스테아릴 (메타)아크릴레이트, 알릴 (메타)아크릴레이트, 2-에톡시에틸(메타)아크릴레이트, 2-도데실티오에틸(메타)아크릴레이트, 2-메톡시에틸(메타)아크릴레이트, 테트라퍼푸릴(메타)아크릴레이트, 페녹시에틸(메타)아크릴레이트, 우레탄아크릴레이트, 아미노에틸(메타)아크릴레이트, 디메틸아미노에틸(메타)아크릴레이트, 1,3-부탄디올디(메타)아크릴레이트, 1,4-부탄디올디(메타)아크릴레이트, 1,6-헥산디올디(메타)아크릴레이트, 에틸렌글리콜디(메타)아크릴레이트, 비스페놀A-에틸렌글리콜디아크릴레이트, 디에틸렌글리콜디(메타)아크릴레이트, 트리에틸렌글리콜디(메타)아크릴레이트, 폴리에틸렌글리콜디(메타)아크릴레이트, 프로필렌글리콜디(메타)아크릴레이트, 디프로필렌글리콜디(메타)아크릴레이트, 네오펜틸글리콜디(메타)아크릴레이트, 디시클로펜타닐디(메타)아크릴레이트, 카프로락톤 변성 디시클로펜테닐디(메타)아크릴레이트, 에틸렌옥사이드 변성 인산디(메타)아크릴레이트, 비스(2-히드록시에틸)이소시아누레이트디(메타)아크릴레이트, 알릴화 시클로헥실디(메타)아크릴레이트, 디메틸올디시클로펜탄디아크릴레이트, 에틸렌옥사이드 변성 헥사히드로프탈산디아크릴레이트, 트리시클로데칸디메탄올아크릴레이트, 네오펜틸글리콜 변성 트리메틸올프로판디아크릴레이트, 아다만탄디아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, 디펜타에리트리톨트리(메타)아크릴레이트, 프로피온산 변성 디펜타에리트리톨트리(메타)아크릴레이트, 펜타에리트리톨트리(메타)아크릴레이트, 프로필렌옥사이드 변성 트리메틸올프로판트리(메타)아크릴레이트, 트리스(2-히드록시에틸)이소시아누레이트트리(메타)아크릴레이트, 트리스(아크릴옥시에틸)이소시아누레이트, 글리세롤트리(메타) 아크릴레이트, 디글리세린테트라(메타)아크릴레이트, 펜타에리트리톨테트라(메타)아크릴레이트, 디트리메틸올프로판테트라(메타)아크릴레이트, 프로피온산 디펜타에리트리톨펜타(메타)아크릴레이트 및 카프로락톤 디펜타에리트리톨헥사(메타)아크릴레이트 등으로 이루어진 군에서 선택되는 하나 이상을 포함할 수 있으나, 이에 특별히 제한되는 것은 아니다.The said acrylate-type monomer used by the manufacturing method of the polyglutarimide of this invention is a monofunctional or polyfunctional alkyl (meth) acrylate and alkenyl (meth) acrylate containing one or more acrylate functional groups. , Alkynyl (meth) acrylate, cycloalkyl (meth) acrylate, aryl (meth) acrylate, hydroxyalkyl (meth) acrylate, epoxyalkyl (meth) acrylate, acryloyl (meth) acrylate, It may be any one selected from the group consisting of methacryloyl (meth) acrylate and acrylooxyalkyl (meth) acrylate, in detail, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, octyl (meth) acrylate, isobutyl (meth) acrylate, isooxyl (meth) acrylate, isodecyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, isobonyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylic Glycidyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-dodecylthio Ethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, tetraperfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, urethane acrylate, aminoethyl (meth) acrylate, dimethylamino Ethyl (meth) acrylate, 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, ethylene glycol di (meth) Acrylate, bisphenol A-ethylene glycol diacrylate, Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, neopentyl Glycoldi (meth) acrylate, dicyclopentanyldi (meth) acrylate, caprolactone modified dicyclopentenyldi (meth) acrylate, ethylene oxide modified phosphoric acid di (meth) acrylate, bis (2-hydroxyethyl) Isocyanurate di (meth) acrylate, allylated cyclohexyldi (meth) acrylate, dimethyloldicyclopentanediacrylate, ethylene oxide modified hexahydrophthalic acid diacrylate, tricyclodecane dimethanol acrylate, neopentyl Glycol-Modified Trimethylolpropanediacrylate, Adamantanediacrylate, Trimethylolpropanetri (meth) acrylate , Dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris ( 2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, glycerol tri (meth) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol tetra ( At least one selected from the group consisting of meta) acrylate, ditrimethylolpropane tetra (meth) acrylate, propionic acid dipentaerythritol penta (meth) acrylate, and caprolactone dipentaerythritol hexa (meth) acrylate; It may include, but is not particularly limited thereto.
본 발명에서, 상기 아크릴레이트계 중합체는 아크릴레이트계 단량체의 중합반응을 통하여 제조될 수 있으며, 이때, 상기 중합은 라디칼 개시제, 현탁제, 완충염 및 사슬 전이 이동제 등의 기타 첨가제를 하나 이상 더 포함하여 현탁중합, 유화중합, 분산중합 및 침전중합 등의 통상적인 중합반응에 의해 수행될 수 있다. 이때, 상기 중합 시 사용되는 라디칼 개시제, 현탁제, 완충염 및 사슬 전이 이동제는 아크릴레이트계 중합체의 중합반응에 통상적으로 사용되는 것이라면 특별한 제한 없이 모두 사용될 수 있다. In the present invention, the acrylate polymer may be prepared through polymerization of an acrylate monomer, wherein the polymerization further includes one or more other additives such as radical initiators, suspending agents, buffer salts and chain transfer transfer agents. It can be carried out by conventional polymerization reactions such as suspension polymerization, emulsion polymerization, dispersion polymerization and precipitation polymerization. In this case, any radical initiator, suspending agent, buffer salt, and chain transfer transfer agent used in the polymerization may be used without particular limitation as long as they are commonly used in the polymerization of the acrylate polymer.
본 발명에서 사용되는 상기 아크릴레이트계 중합체는 중량평균분자량이 5,000 내지 300,000g/mol, 바람직하게는 10,000 내지 200,000g/mol, 더욱 바람직하게는 15,000 내지 120,000g/mol 일 수 있다. 본 발명에서 상기 아크릴레이트계 중합체의 중량평균분자량은 이에 특별히 제한되는 것은 아니나, 상기 범위를 만족할 시, 극성 유기용매 상에 상기 아크릴레이트계 중합체를 용해하는 것이 가능하여 용액 상에서 상기 아크릴레이트계 중합체 및 본 발명의 디아민의 축합가교반응이 고르게 발생될 수 있고, 용액공정을 통해 상기 XLPGI를 고내열성 및 고탄성을 가지는 필름으로 제조할 수 있어 바람직하다.The acrylate polymer used in the present invention may have a weight average molecular weight of 5,000 to 300,000 g / mol, preferably 10,000 to 200,000 g / mol, more preferably 15,000 to 120,000 g / mol. In the present invention, the weight average molecular weight of the acrylate-based polymer is not particularly limited thereto, but when satisfying the above range, it is possible to dissolve the acrylate-based polymer in a polar organic solvent, so that the acrylate-based polymer and The condensation crosslinking reaction of the diamine of the present invention can be evenly generated, and the XLPGI can be produced as a film having high heat resistance and high elasticity through a solution process.
본 발명에서 사용되는 상기 디아민 화합물은 모핵에 이소소르비드 구조를 포함하며, 양단에 아민기를 가지는 디아민 화합물이면 제한되지 않고 모두 사용가능하며, 상기 아민 화합물 역시 화학구조의 말단에 1개의 아민기를 가지는 화합물이면 제한되지 않고 모두 사용이 가능하다. The diamine compound used in the present invention includes an isosorbide structure in the mother nucleus, any diamine compound having an amine group at both ends can be used without limitation, the amine compound also has a compound having one amine group at the end of the chemical structure If it is not limited, all can be used.
본 발명의 폴리글루타르이미드의 제조방법에서 사용되는 상기 디아민 화합물은, 본 발명에서 사용되는 아크릴레이트계 중합체를 구성하는 아크릴레이트계 반복단위 : 디아민 화합물로부터 유도된 아민 작용기 = 100,000:1 내지 50:1의 몰 비율을 가지는 함량이 사용될 수 있으며, 본 발명의 제조방법에서 사용되는 상기 아민 화합물(모노아민 화합물)은 상기 아크릴레이트계 중합체를 구성하는 아크릴레이트계 반복단위의 함량에 대하여 과량(100 % 이상)으로 포함될 수 있다. 이 때, 본 발명에서 사용되는 상기 디아민 화합물의 첨가 함량은 이에 특별히 제한되는 것은 아니나, 상기 함량범위를 만족할 시, 본 발명의 아크릴레이트계 중합체와의 반응으로 제조되는 가교된 폴리글루타르이미드(XLPGI)가 겔(Gel)형태를 띄지 않으며, 상기 아크릴레이트계 중합체의 내열성 및 표면강도의 향상 효율이 극대화되어, 기계적강도 및 내열성이 우수한 폴리글루타르이미드를 효과적으로 제조할 수 있어 좋다. 더불어 상기 디아민 화합물의 상기 함량범위를 만족할 경우, 제조되는 가교된 폴리글루타르이미드(XLPGI)의 분자 구조 내에 과도한 가교반응이 발생하지 않아 상기 XLPGI가 열가교성 특성을 가지게 되며, 이를 통해 2차 가공이 가능해짐에 따라 여러 분야에서 다양한 형태로 폭넓게 활용할 수 있어 바람직하다. The diamine compound used in the method for producing the polyglutarimide of the present invention is an acrylate repeating unit constituting the acrylate polymer used in the present invention: an amine functional group derived from a diamine compound = 100,000: 1 to 50: A content having a molar ratio of 1 may be used, and the amine compound (monoamine compound) used in the preparation method of the present invention is excessive (100%) relative to the content of the acrylate repeating unit constituting the acrylate polymer. Or more). At this time, the addition content of the diamine compound used in the present invention is not particularly limited thereto, but when the content range is satisfied, the cross-linked polyglutarimide (XLPGI) prepared by the reaction with the acrylate polymer of the present invention ) Does not exhibit a gel form, and the efficiency of improving the heat resistance and surface strength of the acrylate-based polymer may be maximized, and thus, polyglutarimide having excellent mechanical strength and heat resistance may be effectively produced. In addition, when the content range of the diamine compound is satisfied, the excessive crosslinking reaction does not occur in the molecular structure of the crosslinked polyglutalimide (XLPGI) to be produced, so that the XLPGI has a thermal crosslinking property, and thus secondary processing is performed. As it becomes possible, it is desirable to be widely used in various forms in various fields.
본 발명에서 상기 아크릴레이트계 중합체, 디아민 화합물 및 아민 화합물은 용매 내에 용해되어, 용액 상에서 중합반응을 통하여 폴리글루타르이미드로 제조될 수 있다. 상기 반응을 위하여 사용되는 용매로는, 상기 아크릴레이트계 중합체 및 상기 디아민 화합물을 용해시킬 수 있는 극성 유기용매가 사용될 수 있으며, 바람직하게는 m-크레졸, N-메틸-2-피롤리돈(NMP), 디메틸포름아미드(DMF), 디메틸아세트아미드(DMAc), 디메틸설폭사이드(DMSO), 아세톤 및 디에틸아세테이트 등으로 이루어진 군에서 선택되는 하나 이상을 포함할 수 있으나, 이에 특별히 제한되는 것은 아니다. 이외에도 본 발명에서, 테트라하이드로퓨란(THF) 및 클로로포름 등의 저비점 용매와 γ-부티로락톤 등의 저흡수성 용매에서 선택되는 하나 이상이 반응 용매로써 사용될 수 있다. 상기 반응에서 사용되는 용매의 함량은 특별히 제한되는 것은 아니나, 상기 용매의 함량이 상기 아크릴레이트계 중합체, 디아민 화합물 및 아민 화합물의 총 중량에 대하여 20 내지 100 wt%, 바람직하게는 30 내지 75 wt%일 경우, 상기 아크릴레이트계 중합체 및 상기 디아민 화합물의 축합 중합반응이 원활하게 진행될 수 있으며 동시에 용매의 과다한 사용을 방지할 수 있어, 환경적 및 경제적 측면에서 바람직하다.In the present invention, the acrylate-based polymer, the diamine compound and the amine compound may be dissolved in a solvent, and may be prepared as polyglutarimide through a polymerization reaction in a solution. As the solvent used for the reaction, a polar organic solvent capable of dissolving the acrylate-based polymer and the diamine compound may be used. Preferably, m-cresol and N-methyl-2-pyrrolidone (NMP ), Dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone and diethyl acetate, and the like, but may include one or more selected from the above. Besides, in the present invention, one or more selected from a low boiling point solvent such as tetrahydrofuran (THF) and chloroform and a low absorbing solvent such as γ-butyrolactone may be used as the reaction solvent. The content of the solvent used in the reaction is not particularly limited, but the content of the solvent is 20 to 100 wt%, preferably 30 to 75 wt% based on the total weight of the acrylate-based polymer, diamine compound and amine compound. In one case, the condensation polymerization reaction of the acrylate-based polymer and the diamine compound can proceed smoothly and at the same time can prevent excessive use of the solvent, it is preferable in terms of environmental and economic.
본 발명에서 상기 반응(중합반응)은, 용액을 교반하거나 열처리하는 통상적인 방법을 통하여 진행될 수 있으며, 200 내지 250 ℃의 온도조건 및 10 내지 30 ㎪의 압력조건에서 6 내지 10 시간 동안 교반 또는 열처리하여 수행될 수 있으나, 이에 특별히 제한되는 것은 아니다.In the present invention, the reaction (polymerization reaction) may be carried out through a conventional method of stirring or heat treating a solution, and stirring or heat treatment for 6 to 10 hours at a temperature condition of 200 to 250 ° C. and a pressure condition of 10 to 30 kPa. It may be carried out by, but is not particularly limited thereto.
본 발명의 폴리글루타르이미드의 제조방법으로부터 합성되는 이소소르비드 구조를 포함하는 가교된 폴리글루타르이미드의 중량평균분자량은 50,000 내지 500,000g/mol 일 수 있다. 본 발명을 통하여 제조되는 상기 폴리글루타르이미드의 중량평균분자량은 이에 특별히 제한되는 것은 아니나, 상기 범위를 만족할 경우, 우수한 광학특성 뿐만 아니라 광학부재 및 전기전자 소재 분야의 부재로서 사용되기에 적합한 기계적 물성 및 높은 내열성을 가져, 200 내지 500℃의 고온에서 변형이 일어나지 않으며, 동시에 강도, 탄성도 및 표면경도 등의 기계적 물성 특성을 나타낼 수 있어 바람직하다.The weight average molecular weight of the crosslinked polyglutarimide including the isosorbide structure synthesized from the method for preparing polyglutarimide of the present invention may be 50,000 to 500,000 g / mol. The weight average molecular weight of the polyglutarimide produced through the present invention is not particularly limited thereto, but if the above range is satisfied, not only excellent optical properties but also mechanical properties suitable for use as members in the field of optical members and electrical and electronic materials And it has a high heat resistance, does not cause deformation at a high temperature of 200 to 500 ℃, and at the same time can exhibit mechanical properties such as strength, elasticity and surface hardness is preferred.
상기 본 발명의 폴리글루타르이미드의 제조방법으로부터 제조되는 폴리글루타르이미드는 용액 중에 용해된 상태에서 용액공정, 압출 또는 사출공정 등의 2차 가공을 통하여 광학특성, 기계적 특성 및 열적특성이 우수한 전기, 전자 부품, 자동차용 부품 등의 사출 성형품 및 필름, 모노필라멘트, 섬유 등의 압출 성형품 등 다양한 형태의 성형품으로 제조될 수 있다.The polyglutarimide prepared from the method for producing polyglutarimide of the present invention is excellent in optical, mechanical and thermal properties through secondary processing such as solution process, extrusion or injection process in a dissolved state in a solution. It can be produced in various forms such as injection molded articles, such as electronic components, automotive parts, and extrusion molded articles such as films, monofilaments, and fibers.
더불어, 본 발명은 (1)용매에 폴리글루타르이미드 및 이소소르비드 구조를 포함하는 디아민 화합물을 첨가하여 혼합물을 제조하는 단계; 및 (2)상기 혼합물을 2차 가공하여 성형품을 제조하는 단계;를 포함하는 폴리글루타르이미드 성형품의 제조방법을 포함한다. In addition, the present invention comprises the steps of (1) preparing a mixture by adding a diamine compound comprising a poly glutimide and isosorbide structure to the solvent; And (2) preparing the molded article by secondary processing the mixture.
본 발명의 단계 (1)에서 사용되는 상기 폴리글루타르이미드는 하기 화학식 1로 표시되는 글루타르이미드 반복단위를 포함하는 폴리글루타르이미드; 및 하기 화학식 1로 표시되는 글루타르이미드 반복단위를 포함하며, 상기 글루타르이미드 반복단위의 0.001 내지 1.2 몰%가 하기 화학식 2로 표시되는 가교구조를 형성하는 것인 폴리글루타르이미드;에서 선택되는 하나 이상의 폴리글루타르이미드일 수 있다.The polyglutarimide used in step (1) of the present invention comprises a polyglutarimide comprising a glutarimide repeat unit represented by the following formula (1); And a polyglutarimide comprising a glutarimide repeating unit represented by Formula 1 below, wherein 0.001 to 1.2 mol% of the glutarimide repeating unit forms a crosslinked structure represented by the following Formula 2; It may be one or more polyglutarimides.
[화학식 1][Formula 1]
Figure PCTKR2016012690-appb-I000011
Figure PCTKR2016012690-appb-I000011
[화학식 2][Formula 2]
Figure PCTKR2016012690-appb-I000012
Figure PCTKR2016012690-appb-I000012
상기 화학식 1 및 화학식 2에서, R1 및 R3 는 서로 독립적으로 수소 또는 CH3이고; R2 는 치환 또는 비치환된 직쇄상 또는 분지상의 C1-C20 알킬기, 치환 또는 비치환된 직쇄상 또는 분지상의 C3-C20 알케닐기, 치환 또는 비치환된 C3-C20 알키닐기, 치환 또는 비치환된 C3-C10 사이클로알킬기, 치환 또는 비치환된 C6-C18 아릴기, 직쇄상 또는 분지상의 C1-C20 하이드록시알킬기, 직쇄상 또는 분지상의 C1-C18 에폭시알킬기, 아크릴로일기, 메타크릴로일기 및 아크릴로옥시기 등으로 이루어진 군에서 선택되는 어느 하나이며; Rz 는 치환 또는 비치환된 직쇄상 또는 분지상의 C1-C20 알킬기, 치환 또는 비치환된 직쇄상 또는 분지상의 C3-C20 알케닐기, 치환 또는 비치환된 C3-C10 사이클로알킬기, 치환 또는 비치환된 C6-C18 아릴기, 직쇄상 또는 분지상의 C1-C18 에폭시알킬기, 아크릴로일기, 메타크릴로일기 및 아크릴로옥시기 등으로 이루어진 군에서 선택되는 어느 하나이고; A 및 B는 서로 독립적으로 단일결합 및 R′-X- 형태에서 선택되는 어느 하나이며, 상기 R′은 이미드기와 결합되는 것으로, 치환 또는 비치환된 직쇄상 또는 분지상의 C1-C20 알킬렌, 치환 또는 비치환된 직쇄상 또는 분지상의 C3-C20 알케닐렌, 치환 또는 비치환된 C3-C20 알키닐렌, 치환 또는 비치환된 C3-C10 사이클로알킬렌 및 치환 또는 비치환된 C6-C18 아릴렌 등으로 이루어진 군에서 선택되는 하나 이상이고, 상기 X-는 이소소르비드와 결합되는 것으로, 단일결합, O-, -S-, C(=O)-, -C(=O)O- 또는 SO2- 이며; a 및 b는 서로 독립적으로 1 내지 1,000의 정수이고, 0.001a≤b≤0.33a 일 수 있으나, 이에 특별히 제한되는 것은 아니다. In Formula 1 and Formula 2, R 1 And R 3 Are independently of each other hydrogen or CH 3 ; R 2 Is a substituted or unsubstituted linear or branched C1-C20 alkyl group, a substituted or unsubstituted straight or branched C3-C20 alkenyl group, a substituted or unsubstituted C3-C20 alkynyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, substituted or unsubstituted C6-C18 aryl group, straight or branched C1-C20 hydroxyalkyl group, straight or branched C1-C18 epoxyalkyl group, acryloyl group, methacryloyl group And it is any one selected from the group consisting of acrylooxy group, etc .; R z Is a substituted or unsubstituted linear or branched C1-C20 alkyl group, a substituted or unsubstituted straight or branched C3-C20 alkenyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C 6 -C 18 aryl group, linear or branched C 1 -C 18 epoxyalkyl group, acryloyl group, methacryloyl group, acrylooxy group and the like; A and B are each independently selected from a single bond and R'-X- form, wherein R 'is bonded to an imide group, and substituted or unsubstituted linear or branched C1-C20 alkylene , Substituted or unsubstituted straight or branched C3-C20 alkenylene, substituted or unsubstituted C3-C20 alkynylene, substituted or unsubstituted C3-C10 cycloalkylene and substituted or unsubstituted C6-C18 aryl At least one selected from the group consisting of ene, etc., wherein X- is combined with isosorbide, and is a single bond, O-, -S-, C (= 0)-, -C (= 0) O- or SO 2- ; a and b are each independently an integer of 1 to 1,000, and may be 0.001a ≦ b ≦ 0.33a, but are not particularly limited thereto.
본 발명의 단계 (1)에서 상기 용매로는, 상기 폴리글루타르이미드 및 상기 디아민 화합물을 용해시킬 수 있는 극성 유기용매가 사용될 수 있으며, 상기 이소소르비드 구조를 포함하는 디아민 화합물은, 상기 폴리글루타르이미드의 합성에 사용되는 아크릴레이트계 중합체 내의 아크릴레이트계 반복단위 함량에 대하여 2 내지 100 mol% 이 사용될 수 있으나, 이에 제한되는 것은 아니다.In the step (1) of the present invention, as the solvent, a polar organic solvent capable of dissolving the polyglutarimide and the diamine compound may be used, and the diamine compound including the isosorbide structure may be used as the polyglue. 2 to 100 mol% may be used based on the content of the acrylate repeating unit in the acrylate polymer used to synthesize the tarimide, but is not limited thereto.
본 발명의 단계 (1)을 통하여 제조되는 혼합물은 상기 단계 (2)의 가공 단계를 통하여 성형품으로 제조될 수 있으며, 상기 단계 (2)의 가공은 열가소성 수지에 대하여 일반적으로 사용되는 성형 방법, 구체적으로는 사출 성형, 압출 성형 및 프레스 성형 등의 방법으로 수행될 수 있으나, 이에 특별히 제한되는 것은 아니다.The mixture prepared through step (1) of the present invention may be manufactured into a molded article through the processing step of step (2), and the processing of step (2) is a molding method generally used for thermoplastic resins, specifically As an injection molding, it may be carried out by a method such as extrusion molding and press molding, but is not particularly limited thereto.
본 발명의 단계 (2)를 통하여 제조되는 상기 성형품은, 본 발명의 폴리글루타르이미드에 존재하는 아크릴레이트 반복단위가 2차 공정 시 첨가되는 상기 이소소르비드 구조를 포함하는 디아민 화합물에 의해 모두 가교되어, 상기 화학식 2의 가교된 글루타르이미드 반복단위를 포함하는 완전 가교된(fully-crosslinked) 폴리글루타르이미드(이하, 가교된 폴리글루타르이미드) 성형품으로, 광학특성, 기계적 특성 및 열적특성이 우수한 전기, 전자 부품, 자동차용 부품 등의 사출 성형품 및 필름, 모노필라멘트, 섬유 등의 압출 성형품 등을 포함할 수 있으며, 바람직하게는 디스플레이 광학부재 및 전자 회로용 부재 등을 포함할 수 있다. 본 발명을 통하여 제조되는 폴리글루타르이미드 성형품은 상기 가교된 폴리글루타르이미드를 포함하며, 이외에도 광 안정화제, 충격보강제, 촉매, 가소제, 염료, 착색제, 유기 색소, 무기 색소, 난연제, 대전방지제, 생물 안정화제, 상용화제, 경화제, 윤활제, 열안정화제, 산화방지제, UV안정제 등의 기타 성분을 하나 이상 더 포함할 수 있다.The molded article prepared through step (2) of the present invention is crosslinked by a diamine compound containing the isosorbide structure in which the acrylate repeating unit present in the polyglutarimide of the present invention is added during the secondary process. Thus, a fully-crosslinked polyglutarimide (hereinafter referred to as cross-linked polyglutarimide) molded article including the cross-linked glutarimide repeat unit of Formula 2, wherein the optical, mechanical and thermal properties Injection molded articles such as excellent electrical, electronic components, automotive parts, and extrusion molded articles such as films, monofilaments, fibers, and the like, and preferably, may include display optical members, electronic circuit members, and the like. The polyglutarimide molded article produced through the present invention includes the cross-linked polyglutarimide, in addition to the light stabilizer, impact modifier, catalyst, plasticizer, dye, colorant, organic pigment, inorganic pigment, flame retardant, antistatic agent, It may further comprise one or more other components such as bio-stabilizers, compatibilizers, curing agents, lubricants, heat stabilizers, antioxidants, UV stabilizers.
본 발명을 통하여 제조되는 폴리글루타르이미드 성형품으로써, 상기 디스플레이 광학부재 및 전자 회로용 부재는 상기 가교된 폴리글루타르이미드의 가교도를 조절함으로써, 광학특성, 기계적 특성 및 열적 특성이 조절될 수 있는 것을 특징으로 할 수 있다. 상기 디스플레이 광학부재로는 대표적으로 냉장고, 에어컨, 휴대폰 등의 터치면에 적용되는 창(window), 대형 백라이트 유닛 도광판용 수지 등이 있으며, 상기 전자 회로용 부재로는 라디오, 텔레비전 및 컴퓨터의 전기 배선 코팅(electrical wiring coating), 프린트 배선판, 반도체 및 전기 회로망의 유전체 등이 있으나, 이에 제한되는 것은 아니다.As a polyglutalimide molded article manufactured through the present invention, the display optical member and the electronic circuit member can be adjusted by controlling the degree of crosslinking of the cross-linked polyglutarimide, optical properties, mechanical properties and thermal properties can be adjusted It can be characterized. The display optical member typically includes a window applied to a touch surface of a refrigerator, an air conditioner, a mobile phone, and the like, a resin for a large backlight unit light guide plate, and the electronic circuit member includes electrical wiring for a radio, a television, and a computer. Electrical wiring coatings, printed wiring boards, dielectrics of semiconductors and electrical networks, and the like, but is not limited thereto.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 실시예에 의하여 본 발명의 내용이 한정되는 것은 아니며, 다양한 다른 변형 및 변경이 가능할 수 있다.Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited by the embodiments, and various other modifications and changes may be possible.
먼저, 본 발명에서 실시한 실험의 방법에 대하여 제시한다.First, the method of the experiment conducted in the present invention is presented.
실험 1) 겔화(Gelation) 현상 관찰Experiment 1) Observation of Gelation
실시예 및 비교예의 단계 2)에서 제조되는 각각의 폴리글루타르이미드(Isosorbide crosslinked polyglutarimide, XLPGI)가 합성된 용액을 육안으로 관찰하여 제조되는 폴리글루타르이미드에 겔화 현상이 발생하는지 여부를 관찰하였다. 이때, 겔화가 발생하면 ○, 일부 발생하면 △, 발생하지 않으면 ×로 표기한다. The gel synthesis phenomenon was observed by visually observing a solution synthesized with each of the polyglutarimides (XLPGI) prepared in Example 2 and Comparative Example, step 2). At this time, when gelation occurs, it is indicated by ○, when partially generated by △, and when not generated, by x.
실험 2) 필름의 외관 및 황색도 관찰Experiment 2) Observation of appearance and yellowness of film
실시예 및 비교예를 통하여 제조되는 XLPGI 필름 시료를 육안으로 관찰하여 XLPGI 필름의 형성 여부 및 형성된 XLPGI 필름의 황색도를 관찰하였다.The XLPGI film samples prepared through Examples and Comparative Examples were visually observed to observe the formation of the XLPGI film and the yellowness of the formed XLPGI film.
실험 3) 유리전이온도 측정방법Experiment 3) Glass Transition Temperature Measurement Method
Thermo Scientific사의 DSC를 이용하여, 실시예 및 비교예를 통하여 제조되는 XLPGI 필름 시료의 유리전이온도를 측정하였다. 60℃에서 24시간 진공 건조한 시료를 승온속도 10℃/min으로 하고, 질소분위기 조건에서 유리전이온도를 측정하였다.Using a DSC from Thermo Scientific, the glass transition temperature of the XLPGI film samples prepared in Examples and Comparative Examples was measured. The sample was vacuum dried at 60 ° C. for 24 hours at a heating rate of 10 ° C./min, and the glass transition temperature was measured under nitrogen atmosphere.
[실시예 1]Example 1
단계 1) XLPGI의 제조Step 1) Preparation of XLPGI
톨루엔(Sigma Aldrich, USA) 용매 10 g에 대하여 중량평균분자량이 15,000g/mol인 폴리메틸메타크릴레이트(PMMA;Sigma Aldrich, USA) 4 g, 이소소르비드 디아민(이하, ISBDA) 0.028 g (0.0002 mol) 및 이소프로필아민(이하, IPA) 9.45 g (0.16 mol)을 혼합한 혼합용액을 제조하였다. 상기 혼합용액을 20 ㎪, 230 ℃의 조건에서 8시간 교반하여 부분 가교된 폴리글루타르이미드(Isosorbide crosslinked polyglutarimide, 이하 XLPGI)를 제조하였다. 4 g of polymethyl methacrylate (PMMA; Sigma Aldrich, USA) having a weight average molecular weight of 15,000 g / mol based on 10 g of toluene (Sigma Aldrich, USA) solvent, 0.028 g (0.0002) of isosorbide diamine (hereinafter referred to as ISBDA) mol) and 9.45 g (0.16 mol) of isopropylamine (hereinafter referred to as IPA) were mixed. The mixed solution was stirred at 20 ° C. and 230 ° C. for 8 hours to prepare partially crosslinked polyglutarimide (hereinafter referred to as XLPGI).
단계 2) XLPGI 필름 시료의 제조Step 2) Preparation of XLPGI Film Sample
상기 부분 가교된 XLPGI 1 g을 클로로포름 용매 5 g에 용해시킨 후 유리 기판 위에 코터 갭 200 ㎛, 코팅속도 4㎜/min으로 캐스팅한 후, 50 ℃에서 24 시간 건조하는 과정을 거쳤다. 상기 과정을 통하여 두께가 30 ㎛인 이소소르비드 구조로 부분 가교된 XLPGI 필름 시료를 제조하였다. 제조된 시료의 물성을 측정하여 표 1에 기재하였다.After dissolving 1 g of the partially cross-linked XLPGI in 5 g of chloroform solvent, the coating was cast on a glass substrate at a coating gap of 200 μm and a coating rate of 4 mm / min, followed by drying at 50 ° C. for 24 hours. Through the above process, a partially crosslinked XLPGI film sample having an isosorbide structure having a thickness of 30 μm was prepared. The physical properties of the prepared samples were measured and listed in Table 1.
[실시예 2]Example 2
상기 실시예 1의 단계 1)에서 중량평균분자량이 15,000g/mol인 폴리메틸메타크릴레이트를 대신하여 중량평균분자량이 120,000g/mol인 폴리메틸메타크릴레이트(PMMA;Sigma Aldrich, USA)를 사용하는 것을 제외하고 나머지는 동일한 과정으로 두께가 30 ㎛인 이소소르비드 구조로 부분 가교된 XLPGI 필름 시료를 제조하였다.In step 1) of Example 1, polymethyl methacrylate having a weight average molecular weight of 120,000 g / mol (PMMA; Sigma Aldrich, USA) is used in place of polymethyl methacrylate having a weight average molecular weight of 15,000 g / mol. Except for the rest, XLPGI film samples partially crosslinked with an isosorbide structure having a thickness of 30 μm were prepared in the same process.
[실시예 3]Example 3
상기 실시예 1의 단계 1)에서 이소프로필아민(IPA)을 대신하여 부틸아민(이하, BA; Sigma Aldrich, USA)을 사용하는 것을 제외하고 나머지는 동일한 과정으로 폴리글루타르이미드 필름 시료를 제조하였다.Except for using butylamine (hereinafter, BA; Sigma Aldrich, USA) in place of isopropylamine (IPA) in Example 1 of Example 1, a polyglutalimide film sample was prepared in the same process. .
[실시예 4]Example 4
상기 실시예 2의 단계 1)에서 이소프로필아민(IPA)을 대신하여 부틸아민(BA)을 사용하는 것을 제외하고 나머지는 동일한 과정으로 폴리글루타르이미드 필름 시료를 제조하였다.Except for using butylamine (BA) in place of isopropylamine (IPA) in Example 1 of Example 2, the polyglutalimide film sample was prepared in the same process.
[실시예 5]Example 5
상기 실시예 1의 단계 1)에서 이소소르비드 디아민을 0.0575 g (0.0004 mol) 사용하는 것을 제외하고 나머지는 동일한 과정으로 폴리글루타르이미드 필름 시료를 제조하였다.Except for using 0.0575 g (0.0004 mol) of isosorbide diamine in step 1) of Example 1, a polyglutalimide film sample was prepared in the same process.
[실시예 6]Example 6
상기 실시예 2의 단계 1)에서 이소소르비드 디아민을 0.0575 g (0.0004 mol) 사용하는 것을 제외하고 나머지는 동일한 과정으로 폴리글루타르이미드 필름 시료를 제조하였다.Except for using 0.0575 g (0.0004 mol) of isosorbide diamine in step 1) of Example 2, a polyglutalimide film sample was prepared in the same process.
[실시예 7]Example 7
상기 실시예 3의 단계 1)에서 이소소르비드 디아민을 0.0575 g (0.0004 mol) 사용하는 것을 제외하고 나머지는 동일한 과정으로 폴리글루타르이미드 필름 시료를 제조하였다.Except for using 0.0575 g (0.0004 mol) of isosorbide diamine in step 1) of Example 3, a polyglutalimide film sample was prepared in the same process.
[실시예 8]Example 8
상기 실시예 4의 단계 1)에서 이소소르비드 디아민을 0.0575 g (0.0004 mol) 사용하는 것을 제외하고 나머지는 동일한 과정으로 폴리글루타르이미드 필름 시료를 제조하였다.Except for using 0.0575 g (0.0004 mol) of isosorbide diamine in step 1) of Example 4, a polyglutalimide film sample was prepared in the same process.
[실시예 9 내지 실시예 16][Examples 9 to 16]
상기 실시예 1 내지 실시예 8에서 상기 단계 2)를 대신하여 하기의 단계 2-1)의 과정을 수행하는 것을 제외하고 나머지는 동일한 과정으로 폴리글루타르이미드 필름 시료를 제조하였다.Except for performing the process of step 2-1) in place of the step 2) in Example 1 to Example 8, a polyglutalimide film sample was prepared in the same process.
단계 2-1) XLPGI 필름 시료의 제조Step 2-1) Preparation of XLPGI Film Sample
상기 실시예 1 내지 실시예 8의 단계 1)로부터 제조되는 부분 가교된 XLPGI를 포함하는 혼합용액에 이소소르비드 디아민을 각각 0.115 g (0.0008 mol) 더 첨가한 후 혼합하여 제2혼합용액을 제조하였다. 상기 제2혼합용액을 330 ℃의 사출기를 통하여 두께가 30 ㎛인 이소소르비드 구조로 완전 가교된 폴리글루타르이미드(XLPGI) 필름 시료를 제조하였다.The second mixed solution was prepared by further adding 0.115 g (0.0008 mol) of isosorbide diamine to the mixed solution including partially crosslinked XLPGI prepared in Step 1) of Example 1 to Example 8, respectively. . A polyglutalimide (XLPGI) film sample was prepared by crosslinking the second mixed solution with an isosorbide structure having a thickness of 30 μm through an injection machine at 330 ° C.
[비교예 1]Comparative Example 1
상기 실시예 1의 단계 1)에서 중량평균분자량이 15,000g/mol인 폴리메틸메타크릴레이트를 대신하여 상기 중량평균분자량이 10,000g/mol인 폴리메틸메타크릴레이트를 사용하는 것을 제외하고 나머지는 동일한 과정으로 폴리글루타르이미드 필름 시료를 제조하였다.Except for using the polymethyl methacrylate having a weight average molecular weight of 10,000g / mol in place of the polymethyl methacrylate having a weight average molecular weight of 15,000g / mol in step 1) of Example 1 the rest are the same Polyglutalimide film samples were prepared by the procedure.
[비교예 2]Comparative Example 2
상기 실시예 1의 단계 1)에서 중량평균분자량이 15,000g/mol인 폴리메틸메타크릴레이트를 대신하여 상기 중량평균분자량이 400,000g/mol인 폴리메틸메타크릴레이트를 사용하는 것을 제외하고 나머지는 동일한 과정으로 폴리글루타르이미드 필름을 제조하였다.Except for using a polymethyl methacrylate having a weight average molecular weight of 400,000 g / mol in place of the polymethyl methacrylate having a weight average molecular weight of 15,000 g / mol in step 1) of Example 1 A polyglutarimide film was prepared by the procedure.
[비교예 3]Comparative Example 3
상기 실시예 1의 단계 1)에서 이소소르비드 디아민을 대신하여 사이클로헥산 디아민(이하, CHXDA, Sigma Aldrich, USA)을 사용하는 것을 제외하고 나머지는 동일한 과정으로 폴리글루타르이미드 필름을 제조하였다.Except for using cyclohexane diamine (hereinafter referred to as CHXDA, Sigma Aldrich, USA) in place of isosorbide diamine in step 1) of Example 1, the polyglutalimide film was prepared in the same process.
[비교예 4][Comparative Example 4]
상기 실시예 2의 단계 1)에서 이소소르비드 디아민을 대신하여 사이클로헥산 디아민을 사용하는 것을 제외하고 나머지는 동일한 과정으로 폴리글루타르이미드 필름을 제조하였다.Except for using cyclohexane diamine in place of isosorbide diamine in step 1) of Example 2, a polyglutalimide film was prepared in the same process.
[비교예 5] [Comparative Example 5]
상기 실시예 3의 단계 1)에서 이소소르비드 디아민을 대신하여 사이클로헥산 디아민을 사용하는 것을 제외하고 나머지는 동일한 과정으로 폴리글루타르이미드 필름을 제조하였다.Except for using cyclohexane diamine in place of isosorbide diamine in step 1) of Example 3 to prepare a polyglutarimide film in the same process.
[비교예 6]Comparative Example 6
상기 실시예 4의 단계 1)에서 이소소르비드 디아민을 대신하여 사이클로헥산 디아민을 사용하는 것을 제외하고 나머지는 동일한 과정으로 폴리글루타르이미드 필름을 제조하였다.Except for using cyclohexane diamine in place of isosorbide diamine in step 1) of Example 4 to prepare a polyglutarimide film in the same process.
[비교예 7]Comparative Example 7
상기 실시예 5의 단계 1)에서 이소소르비드 디아민을 대신하여 사이클로헥산 디아민을 사용하는 것을 제외하고 나머지는 동일한 과정으로 폴리글루타르이미드 필름을 제조하였다.Except for using cyclohexane diamine in place of isosorbide diamine in step 1) of Example 5 to prepare a polyglutarimide film in the same process.
[비교예 8]Comparative Example 8
상기 실시예 6의 단계 1)에서 이소소르비드 디아민을 대신하여 사이클로헥산 디아민을 사용하는 것을 제외하고 나머지는 동일한 과정으로 폴리글루타르이미드 필름을 제조하였다.Except for using cyclohexane diamine in place of isosorbide diamine in step 1) of Example 6 to prepare a polyglutarimide film in the same process.
[비교예 9]Comparative Example 9
상기 실시예 7의 단계 1)에서 이소소르비드 디아민을 대신하여 사이클로헥산 디아민을 사용하는 것을 제외하고 나머지는 동일한 과정으로 폴리글루타르이미드 필름을 제조하였다.Except for using cyclohexane diamine in place of isosorbide diamine in step 1) of Example 7 to prepare a polyglutarimide film in the same process.
[비교예 10]Comparative Example 10
상기 실시예 8의 단계 1)에서 이소소르비드 디아민을 대신하여 사이클로헥산 디아민을 사용하는 것을 제외하고 나머지는 동일한 과정으로 폴리글루타르이미드 필름을 제조하였다.Except for using cyclohexane diamine in place of isosorbide diamine in step 1) of Example 8 to prepare a polyglutarimide film in the same process.
이해를 돕기 위하여, 본 발명의 상기 실시예 1 내지 실시예 16 및 비교예 1 내지 10의 실험조건을 하기 표 1에 도시하였다.In order to facilitate the understanding, the experimental conditions of Examples 1 to 16 and Comparative Examples 1 to 10 of the present invention are shown in Table 1 below.
또한, 상기 실시예 1 내지 8 및 비교예 1 내지 10에서, 상기 실험 1)의 방법에 따라 가교된 폴리글루타르이미드(XLPGI)의 겔화 현상의 발생 여부를 관찰한 결과 및 상기 실시예 1 내지 16 및 비교예 1 내지 10에서, 상기 실험 3)의 방법에 따라 XLPGI 필름 시료의 내열분해온도를 측정한 결과를 표 2에 도시하였다. In addition, in Examples 1 to 8 and Comparative Examples 1 to 10, it was observed whether or not the gelation phenomenon of the cross-linked polyglutarimide (XLPGI) according to the method of Experiment 1) and Examples 1 to 16 And in Comparative Examples 1 to 10, the results of measuring the thermal decomposition temperature of the XLPGI film sample according to the method of Experiment 3) is shown in Table 2.
더불어, 상기 실험 2)의 방법에 따라 상기 실시예 1 내지 3, 실시예 6, 실시예 8 및 비교예 1 내지 5를 통하여 제조한 XLPGI 필름의 형성 여부를 관찰한 결과를 도 1 및 도 2에 도시하였다.In addition, the results of observing the formation of the XLPGI film prepared through Examples 1 to 3, Example 6, Example 8 and Comparative Examples 1 to 5 according to the method of Experiment 2 are shown in FIGS. 1 and 2. Shown.
PMMAPMMA 디아민 화합물(함량)Diamine Compound (Content) 아민 화합물(함량)Amine compound (content) 용매(사용량)Solvent (usage)
MwMw 함량content
실시예 1Example 1 15,00015,000 4 g4 g ISBDA 0.028 gISBDA 0.028 g IPA 9.45 gIPA 9.45 g 톨루엔10 g10 g of toluene
실시예 2Example 2 120,000120,000
실시예 3Example 3 15,00015,000 BA 9.45 gBA 9.45 g
실시예 4Example 4 120,000120,000
실시예 5Example 5 15,00015,000 ISBDA 0.0575gISBDA 0.0575 g IPA 9.45 gIPA 9.45 g
실시예 6Example 6 120,000120,000
실시예 7Example 7 15,00015,000 BA 9.45 gBA 9.45 g
실시예 8Example 8 120,000120,000
실시예 9Example 9 15,00015,000 4 g4 g ISBDA 0.143 g(0.028+0.115)ISBDA 0.143 g (0.028 + 0.115) IPA 9.45 gIPA 9.45 g
실시예 10Example 10 120,000120,000
실시예 11Example 11 15,00015,000 BA 9.45 gBA 9.45 g
실시예 12Example 12 120,000120,000
실시예 13Example 13 15,00015,000 ISBDA 0.1725g(0.0575+0.115)ISBDA 0.1725 g (0.0575 + 0.115) IPA 9.45 gIPA 9.45 g
실시예 14Example 14 120,000120,000
실시예 15Example 15 15,00015,000 BA 9.45 gBA 9.45 g
실시예 16Example 16 120,000120,000
비교예 1Comparative Example 1 1,0001,000 4 g4 g ISBDA 0.028 gISBDA 0.028 g IPA 9.45 gIPA 9.45 g
비교예 2Comparative Example 2 400,000400,000
비교예 3Comparative Example 3 15,00015,000 4 g4 g CHXDA 0.028 gCHXDA 0.028 g IPA 9.45 gIPA 9.45 g
비교예 4Comparative Example 4 120,000120,000
비교예 5Comparative Example 5 15,00015,000 BA 9.45 gBA 9.45 g
비교예 6Comparative Example 6 120,000120,000
비교예 7Comparative Example 7 15,00015,000 4 g4 g CHXDA 0.0575gCHXDA 0.0575g IPA 9.45 gIPA 9.45 g
비교예 8Comparative Example 8 120,000120,000
비교예 9Comparative Example 9 15,00015,000 BA 9.45 gBA 9.45 g
비교예 10Comparative Example 10 120,000120,000
겔화 현상 발생Gelation phenomenon occurs 유리전이온도 (Tg) [℃]Glass Transition Temperature (T g ) [℃]
실시예 1Example 1 × (겔화 X)× (gelling X) 138.32138.32
실시예 2Example 2 ×× 144.85144.85
실시예 3Example 3 ×× 136.96136.96
실시예 4Example 4 ×× 142.07142.07
실시예 5Example 5 ×× 150.75150.75
실시예 6Example 6 ×× 152.91152.91
실시예 7Example 7 ×× 148.24148.24
실시예 8Example 8 ×× 150.83150.83
실시예 9Example 9 -- 142.46142.46
실시예 10Example 10 -- 148.27148.27
실시예 11Example 11 -- 141.01141.01
실시예 12Example 12 -- 147.38147.38
실시예 13Example 13 -- 153.20153.20
실시예 14Example 14 -- 155.46155.46
실시예 15Example 15 -- 150.48150.48
실시예 16Example 16 -- 153.72153.72
비교예 1Comparative Example 1 ×× 112.58112.58
비교예 2Comparative Example 2 ○ (겔화)○ (gel) 114.84114.84
비교예 3Comparative Example 3 ×× 118.00118.00
비교예 4Comparative Example 4 △ (일부 겔화)△ (some gelling) 106.72106.72
비교예 5Comparative Example 5 ×× 113.67113.67
비교예 6Comparative Example 6 △△ 115.24115.24
비교예 7Comparative Example 7 ×× 113.76113.76
비교예 8Comparative Example 8 △△ 121.20121.20
비교예 9Comparative Example 9 ×× 125.62125.62
비교예 10Comparative Example 10 △△ 116.72116.72
상기 표 2에서, 본 발명의 실시예 1 내지 16은 가교반응이 진행된 용액 상에 겔화된 폴리글루타르이미드(XLPGI)가 생성되지 않음을 나타내고 있으며, 상기의 결과를 통하여 본 발명의 실시예에 따라 제조되는 가교된 폴리글루타르이미드(XLPGI)는 부분적으로 과도한 가교반응이 발생되지 않고 균일하게 가교반응이 발생하여, 용매 상에 용해됨으로써 2차 가공이 가능한 가교된 폴리글루타르이미드(XLPGI)가 제조됨을 확인할 수 있다. 이에 반해, 본 발명의 비교예에서는 용액 상에서 일부 또는 완전히 겔화된 XLPGI가 생성되는 결과를 나타내어, 생성되는 XLPGI 내 가교 반응이 불균일하게 발생됨을 알 수 있다.In Table 2, Examples 1 to 16 of the present invention shows that the gelled polyglutarimide (XLPGI) is not produced on the crosslinked solution, and according to the embodiment of the present invention through the above results. The crosslinked polyglutarimide (XLPGI) produced is partially crosslinked without excessive crosslinking reaction and uniformly crosslinked, so that crosslinked polyglutalimide (XLPGI) is prepared by dissolving in a solvent to enable secondary processing. It can be confirmed. On the contrary, in the comparative example of the present invention, the result of the formation of the partially or fully gelled XLPGI in the solution, it can be seen that the cross-linking reaction in the resulting XLPGI occurs unevenly.
또한, 상기 표 2의 결과를 통하여, 본 발명의 실시예 1 내지 16을 통하여 제조되는 XLPGI 필름 시료가 현저하게 뛰어난 내열성을 가짐을 확인할 수 있다. 폴리메틸메타크릴레이트와 일반적으로 사용되는 디아민 화합물로써 사이클로헥산디아민을 반응시켜 제조한 비교예 3 내지 비교예 10의 폴리글루타르이미드 필름 시료는 최대 125.62 ℃의 유리전이온도를 가지며, 126 ℃ 이상의 온도에서는 모든 필름 시료의 형태가 변하는 결과를 확인하였다. 반면 본 발명의 실시예 1 내지 실시예 16의 폴리글루타르이미드 필름 시료는 138.32 내지 153.72 ℃의 유리전이온도를 가져 비교예의 필름시료 대비 유리전이온도가 최대 47℃ 상승한 것을 확인할 수 있으며, 이를 통하여 일반적인 디아민 화합물을 사용할 경우에 비해 본 발명의 이소소르비드 모핵을 가지는 디아민 화합물을 사용함으로써 제조되는 폴리글루타르이미드의 내열성을 효과적으로 향상시킬 수 있음을 알 수 있다. 또한, 일반적인 폴리메틸메타크릴레이트 고분자의 유리전이온도(Tg)가 101 내지 118 ℃인 것을 고려할 때, 본 발명의 상기 실시예 1 내지 16에 따라 제조한 폴리글루타르이미드를 통하여 기존의 폴리메틸메타크릴레이트가 가진 낮은 내열 특성을 효과적으로 개선할 수 있으며 이에 따라 고온에서도 안정한 상태를 유지할 수 있음을 알 수 있다.In addition, through the results of Table 2, it can be seen that the XLPGI film sample prepared through Examples 1 to 16 of the present invention has a remarkably excellent heat resistance. Polyglutalimide film samples of Comparative Examples 3 to 10 prepared by reacting polymethylmethacrylate with cyclohexanediamine as a diamine compound generally used have a glass transition temperature of up to 125.62 ° C., a temperature of 126 ° C. or more. In the results of changing the shape of all the film samples were confirmed. On the other hand, the polyglutalimide film samples of Examples 1 to 16 of the present invention have a glass transition temperature of 138.32 to 153.72 ℃, it can be seen that the glass transition temperature is up to 47 ℃ compared to the film sample of the comparative example, through this general Compared with the case of using a diamine compound, it turns out that the heat resistance of the polyglutarimide manufactured by using the diamine compound which has the isosorbide mother nucleus of this invention can be improved effectively. In addition, considering that the glass transition temperature (Tg) of the general polymethyl methacrylate polymer is 101 to 118 ℃, the existing polymethyl methacrylate through the polyglutarimide prepared according to Examples 1 to 16 of the present invention It can be seen that the low heat resistance of the acrylate can be effectively improved, and thus it can maintain a stable state even at high temperatures.
더불어, 도 1의 결과를 통하여 상기 실시예의 폴리글루타르이미드를 통하여 외관상 불량이 없으며 투명한 필름의 제조가 가능함을 확인할 수 있으며, 도 2의 결과를 통하여 상기 비교예의 폴리글루타르이미드는 캐스팅 이후 건조하는 과정에서 갈라지는 현상에 의해 필름으로의 제조가 불가능하며 또한 비교예의 폴리글루타르이미드는 유색을 나타내어 투명한 필름의 제조가 불가능함을 확인할 수 있다. 특히 도 1의 우측 상단에 존재하는 실시예 1의 폴리글루타르이미드 필름 시료와 도 2의 우측 상단에 존재하는 비교예 1의 폴리글루타르이미드 필름 시료의 대비를 통해, 저분자량의 PMMA를 포함하여 제조한 XLPGI의 경우 유연성이 매우 낮아 필름 제조를 위한 건조단계 시 갈라지는 현상이 심하게 발생하여 필름으로의 제조가 불가능함을 알 수 있으며, 도 1의 중앙 상단에 존재하는 실시예 3의 폴리글루타르이미드 필름 시료와 도 2의 우측 하단에 존재하는 비교예 5의 폴리글루타르이미드 필름 시료의 대비를 통해, 디아민화합물로서 본 발명의 이소소르비드디아민을 사용할 경우 투명한 필름을 효과적으로 제조할 수 있음을 확인할 수 있다.In addition, it can be seen through the results of FIG. 1 that there is no defect in appearance through the polyglutarimide of the embodiment, and that a transparent film can be manufactured. Through the result of FIG. 2, the polyglutarimide of the comparative example is dried after casting. Due to the cracking phenomenon in the process, it is impossible to produce a film, and also the polyglutarimide of the comparative example may be colored and thus, it may be confirmed that the production of a transparent film is impossible. In particular, the low-molecular-weight PMMA is included through a contrast between the polyglutalimide film sample of Example 1 present in the upper right side of FIG. 1 and the polyglutarimide film sample of Comparative Example 1 present in the upper right side of FIG. 2. In the case of the manufactured XLPGI, it can be seen that it is impossible to manufacture the film due to the extremely low flexibility due to the severe cracking phenomenon during the drying step for manufacturing the film, the polyglutarimide of Example 3 present in the upper center of FIG. Through the comparison between the film sample and the polyglutarimide film sample of Comparative Example 5 present in the lower right of FIG. 2, it can be confirmed that the transparent film can be effectively produced when the isosorbidediamine of the present invention is used as the diamine compound. have.
상기 실험 1 내지 실험 3의 결과인 표 2 및 도 1 내지 2로부터, 본 발명의 폴리글루타르이미드 제조방법을 통하여 높은 열안정성 및 내열성을 나타낼 수 있으며 우수한 형태의 투명 필름으로 제조될 수 있는, 이소소르비드 구조를 포함하는 가교된 폴리글루타르이미드를 합성할 수 있으며, 상기 폴리글루타르이미드를 통하여 고온에서도 필름으로써 사용될 수 있으며 높은 투명성을 나타내는 디스플레이 광학부재 및 전자 회로용 부재를 제조할 수 있음을 확인하여 본 발명을 완성하였다.From Table 2 and Figures 1 to 2, which are the results of Experiments 1 to 3, it is possible to exhibit high thermal stability and heat resistance through the polyglutalimide production method of the present invention, which can be prepared as an excellent type of transparent film, iso It is possible to synthesize a cross-linked polyglutarimide comprising a sorbide structure, and can be used as a film even at high temperatures through the polyglutarimide and to produce a display optical member and a member for an electronic circuit exhibiting high transparency It confirmed and completed this invention.

Claims (9)

  1. 하기 화학식 1로 표시되는 글루타르이미드 반복단위를 포함하는 폴리글루타르이미드에 있어서,In the polyglutarimide containing a glutarimide repeating unit represented by the following formula (1),
    [화학식 1][Formula 1]
    Figure PCTKR2016012690-appb-I000013
    Figure PCTKR2016012690-appb-I000013
    [화학식 2][Formula 2]
    Figure PCTKR2016012690-appb-I000014
    Figure PCTKR2016012690-appb-I000014
    상기 글루타르이미드 반복단위의 0.001 내지 1.2 몰%는 상기 화학식 2로 표시되는 가교구조를 형성하는 것인 폴리글루타르이미드.0.001 to 1.2 mole% of the glutarimide repeating unit forms a crosslinked structure represented by Formula 2 above.
    (상기 화학식 1 및 화학식 2에서,(In Formula 1 and Formula 2,
    R1 및 R3 는 서로 독립적으로 수소 또는 CH3이고;R 1 and R 3 are independently of each other hydrogen or CH 3 ;
    R2 는 치환 또는 비치환된 직쇄상 또는 분지상의 C1-C20 알킬기, 치환 또는 비치환된 직쇄상 또는 분지상의 C3-C20 알케닐기, 치환 또는 비치환된 C3-C20 알키닐기, 치환 또는 비치환된 C3-C10 사이클로알킬기, 치환 또는 비치환된 C6-C18 아릴기, 직쇄상 또는 분지상의 C1-C20 하이드록시알킬기, 직쇄상 또는 분지상의 C1-C18 에폭시알킬기, 아크릴로일기, 메타크릴로일기 및 아크릴로옥시기로 이루어진 군에서 선택되는 어느 하나이며;R 2 Is a substituted or unsubstituted linear or branched C1-C20 alkyl group, a substituted or unsubstituted straight or branched C3-C20 alkenyl group, a substituted or unsubstituted C3-C20 alkynyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, substituted or unsubstituted C6-C18 aryl group, straight or branched C1-C20 hydroxyalkyl group, straight or branched C1-C18 epoxyalkyl group, acryloyl group, methacryloyl group And acrylooxy group is any one selected from the group consisting of;
    Rz 는 치환 또는 비치환된 직쇄상 또는 분지상의 C1-C20 알킬기, 치환 또는 비치환된 직쇄상 또는 분지상의 C3-C20 알케닐기, 치환 또는 비치환된 C3-C10 사이클로알킬기, 치환 또는 비치환된 C6-C18 아릴기, 직쇄상 또는 분지상의 C1-C18 에폭시알킬기, 아크릴로일기, 메타크릴로일기 및 아크릴로옥시기로 이루어진 군에서 선택되는 어느 하나이고;R z Is a substituted or unsubstituted linear or branched C1-C20 alkyl group, a substituted or unsubstituted straight or branched C3-C20 alkenyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted Any one selected from the group consisting of a C6-C18 aryl group, a straight or branched C1-C18 epoxyalkyl group, an acryloyl group, a methacryloyl group, and an acrylooxy group;
    A 및 B는 서로 독립적으로 단일결합 및 R′-X- 형태에서 선택되는 어느 하나이며, 상기 R′은 이미드기와 결합되는 것으로, 치환 또는 비치환된 직쇄상 또는 분지상의 C1-C20 알킬렌, 치환 또는 비치환된 직쇄상 또는 분지상의 C3-C20 알케닐렌, 치환 또는 비치환된 C3-C20 알키닐렌, 치환 또는 비치환된 C3-C10 사이클로알킬렌 및 치환 또는 비치환된 C6-C18 아릴렌으로 이루어진 군에서 선택되는 하나 이상이고, 상기 X-는 이소소르비드와 결합되는 것으로, 단일결합, O-, -S-, C(=O)-, -C(=O)O- 또는 SO2- 이며;A and B are each independently selected from a single bond and R'-X- form, wherein R 'is bonded to an imide group, and substituted or unsubstituted linear or branched C1-C20 alkylene , Substituted or unsubstituted straight or branched C3-C20 alkenylene, substituted or unsubstituted C3-C20 alkynylene, substituted or unsubstituted C3-C10 cycloalkylene and substituted or unsubstituted C6-C18 aryl At least one selected from the group consisting of lens, wherein X- is combined with isosorbide, a single bond, O-, -S-, C (= 0)-, -C (= 0) O- or SO 2- ;
    a 및 b는 서로 독립적으로 1 내지 1,000의 정수이고, 0.001a≤b≤0.33a 이다.)a and b are each independently an integer of 1 to 1,000 and 0.001a ≦ b ≦ 0.33a.)
  2. 제1항에 있어서,The method of claim 1,
    상기 A 및 B는 서로 독립적으로 단일결합,A and B are each independently a single bond,
    Figure PCTKR2016012690-appb-I000015
    Figure PCTKR2016012690-appb-I000015
    으로 이루어진 군에서 선택되는 어느 하나인 폴리글루타르이미드.Polyglutarimide is any one selected from the group consisting of.
  3. 제1항에 있어서,The method of claim 1,
    상기 폴리글루타르이미드는 중량평균분자량이 50,000 내지 500,000g/mol인 폴리글루타르이미드.The polyglutarimide is a polyglutarimide having a weight average molecular weight of 50,000 to 500,000g / mol.
  4. 아크릴레이트계 중합체 및 이소소르비드를 포함하는 하기 화학식 3으로 표시되는 디아민 화합물 및 하기 화학식 4로 표시되는 아민 화합물을 반응하는 단계를 포함하며, 상기 단계를 통하여 제조되는 하기 화학식 1의 반복단위를 포함하는 폴리글루타르이미드는 총 글루타르이미드 반복단위에 대하여 0.001 내지 1.2 몰%가 하기 화학식 2로 표시되는 가교구조를 포함하는 것인 폴리글루타르이미드의 제조방법.Comprising a step of reacting the diamine compound represented by the formula (3) and the amine compound represented by the formula (4) comprising an acrylate-based polymer and isosorbide, and comprises a repeating unit of the formula (1) The polyglutarimide is a method for producing a polyglutarimide in which 0.001 to 1.2 mol% of the total glutarimide repeating unit comprises a crosslinked structure represented by the following formula (2).
    [화학식 1][Formula 1]
    Figure PCTKR2016012690-appb-I000016
    Figure PCTKR2016012690-appb-I000016
    [화학식 2][Formula 2]
    Figure PCTKR2016012690-appb-I000017
    Figure PCTKR2016012690-appb-I000017
    [화학식 3][Formula 3]
    Figure PCTKR2016012690-appb-I000018
    Figure PCTKR2016012690-appb-I000018
    [화학식 4][Formula 4]
    Figure PCTKR2016012690-appb-I000019
    Figure PCTKR2016012690-appb-I000019
    (상기 화학식 1 및 화학식 2에서, (In Formula 1 and Formula 2,
    R1 및 R3 는 서로 독립적으로 수소 또는 CH3이고; R 1 and R 3 are independently of each other hydrogen or CH 3 ;
    R2 는 치환 또는 비치환된 직쇄상 또는 분지상의 C1-C20 알킬기, 치환 또는 비치환된 직쇄상 또는 분지상의 C3-C20 알케닐기, 치환 또는 비치환된 C3-C20 알키닐기, 치환 또는 비치환된 C3-C10 사이클로알킬기, 치환 또는 비치환된 C6-C18 아릴기, 직쇄상 또는 분지상의 C1-C20 하이드록시알킬기, 직쇄상 또는 분지상의 C1-C18 에폭시알킬기, 아크릴로일기, 메타크릴로일기 및 아크릴로옥시기로 이루어진 군에서 선택되는 어느 하나이며;R 2 Is a substituted or unsubstituted linear or branched C1-C20 alkyl group, a substituted or unsubstituted straight or branched C3-C20 alkenyl group, a substituted or unsubstituted C3-C20 alkynyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, substituted or unsubstituted C6-C18 aryl group, straight or branched C1-C20 hydroxyalkyl group, straight or branched C1-C18 epoxyalkyl group, acryloyl group, methacryloyl group And acrylooxy group is any one selected from the group consisting of;
    Rz 는 치환 또는 비치환된 직쇄상 또는 분지상의 C1-C20 알킬기, 치환 또는 비치환된 직쇄상 또는 분지상의 C3-C20 알케닐기, 치환 또는 비치환된 C3-C10 사이클로알킬기, 치환 또는 비치환된 C6-C18 아릴기, 직쇄상 또는 분지상의 C1-C18 에폭시알킬기, 아크릴로일기, 메타크릴로일기 및 아크릴로옥시기로 이루어진 군에서 선택되는 어느 하나이고;R z Is a substituted or unsubstituted linear or branched C1-C20 alkyl group, a substituted or unsubstituted straight or branched C3-C20 alkenyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted Any one selected from the group consisting of a C6-C18 aryl group, a straight or branched C1-C18 epoxyalkyl group, an acryloyl group, a methacryloyl group, and an acrylooxy group;
    A 및 B는 서로 독립적으로 단일결합 및 R′-X- 형태에서 선택되는 어느 하나이며, 상기 R′은 이미드기와 결합되는 것으로, 치환 또는 비치환된 직쇄상 또는 분지상의 C1-C20 알킬렌, 치환 또는 비치환된 직쇄상 또는 분지상의 C3-C20 알케닐렌, 치환 또는 비치환된 C3-C20 알키닐렌, 치환 또는 비치환된 C3-C10 사이클로알킬렌 및 치환 또는 비치환된 C6-C18 아릴렌으로 이루어진 군에서 선택되는 하나 이상이고, 상기 X-는 이소소르비드와 결합되는 것으로, 단일결합, O-, -S-, C(=O)-, -C(=O)O- 또는 SO2- 이며;A and B are each independently selected from a single bond and R'-X- form, wherein R 'is bonded to an imide group, and substituted or unsubstituted linear or branched C1-C20 alkylene , Substituted or unsubstituted straight or branched C3-C20 alkenylene, substituted or unsubstituted C3-C20 alkynylene, substituted or unsubstituted C3-C10 cycloalkylene and substituted or unsubstituted C6-C18 aryl At least one selected from the group consisting of lens, wherein X- is combined with isosorbide, a single bond, O-, -S-, C (= 0)-, -C (= 0) O- or SO 2- ;
    a 및 b는 서로 독립적으로 1 내지 1,000의 정수이고, 0.001a≤b≤0.33a 이다.a and b are each independently an integer of 1 to 1,000 and 0.001a ≦ b ≦ 0.33a.
    또한, 상기 화학식 3에서, A 및 B는 상기 화학식 2에서 정의한 A 및 B와 동일하며, 상기 화학식 4에서 Rz는 상기 화학식 1에서 정의한 Rz 와 동일하다.)Also, in Chemical Formula 3, A and B are the same as A and B defined in Chemical Formula 2, and R z in Chemical Formula 4 is identical to R z defined in Chemical Formula 1.
  5. 제4항에 있어서,The method of claim 4, wherein
    상기 아크릴레이트계 중합체는 단관능성 또는 다관능성의 알킬 (메타)아크릴레이트, 알케닐 (메타)아크릴레이트, 알키닐 (메타)아크릴레이트, 사이클로알킬 (메타)아크릴레이트, 아릴 (메타)아크릴레이트, 하이드록시알킬 (메타)아크릴레이트, 에폭시알킬(메타)아크릴레이트, 아크릴로일(메타)아크릴레이트, 메타크릴로일(메타)아크릴레이트 및 아크릴로옥시알킬(메타)아크릴레이트로 이루어진 군에서 선택되는 하나 이상의 아크릴레이트 단량체가 중합된 형태의 고분자인 것을 특징으로 하는 폴리글루타르이미드의 제조방법.The acrylate polymer may be monofunctional or polyfunctional alkyl (meth) acrylate, alkenyl (meth) acrylate, alkynyl (meth) acrylate, cycloalkyl (meth) acrylate, aryl (meth) acrylate, Selected from the group consisting of hydroxyalkyl (meth) acrylates, epoxyalkyl (meth) acrylates, acryloyl (meth) acrylates, methacryloyl (meth) acrylates and acrylooxyalkyl (meth) acrylates At least one acrylate monomer is a method of producing a polyglutarimide, characterized in that the polymer of the polymerized form.
  6. 제4항에 있어서,The method of claim 4, wherein
    상기 아크릴레이트계 중합체는 중량평균분자량이 5,000 내지 300,000g/mol인 폴리글루타르이미드의 제조방법.The acrylate-based polymer has a weight average molecular weight of 5,000 to 300,000g / mol polyglutalimide production method.
  7. 제4항에 있어서,The method of claim 4, wherein
    상기 아크릴레이트계 중합체를 구성하는 아크릴레이트계 반복단위 : 상기 디아민 화합물로부터 유도된 아민 작용기의 비율은 100,000:1 내지 50:1인 폴리글루타르이미드의 제조방법. A method of producing a polyglutarimide ratio of the acrylate repeating unit constituting the acrylate polymer: the amine functional group derived from the diamine compound is 100,000: 1 to 50: 1.
  8. 제4항에 있어서,The method of claim 4, wherein
    상기 반응은 200 내지 250℃의 온도 및 10 내지 30㎪의 압력에서 6 내지 10 시간동안 수행되는 것을 특징으로 하는 폴리글루타르이미드의 제조방법.The reaction is a method for producing polyglutarimide, characterized in that carried out for 6 to 10 hours at a temperature of 200 to 250 ℃ and a pressure of 10 to 30 kPa.
  9. 제4항에 있어서,The method of claim 4, wherein
    상기 폴리글루타르이미드는 중량평균분자량이 50,000 내지 500,000g/mol인 폴리글루타르이미드의 제조방법.The polyglutarimide has a weight average molecular weight of 50,000 to 500,000 g / mol of a method for producing polyglutarimide.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR870002178A (en) * 1985-08-27 1987-03-30 윌리엄 이. 램버트 3세 Imide polymer
US20020021883A1 (en) * 1999-08-26 2002-02-21 Takeshi Koyano Optical waveguide made of polymer material and a method of fabricating the same
US20040127057A1 (en) * 2002-12-25 2004-07-01 Tdk Corporation Method for fabricating a patterned thin film and a micro device
CN1616462A (en) * 2004-09-29 2005-05-18 清华大学 Diamine monomer containing di-dehydrated hexitol unit and its preparing method
KR20130140771A (en) * 2011-02-21 2013-12-24 가부시키가이샤 가네카 Acrylic resin film

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR870002178A (en) * 1985-08-27 1987-03-30 윌리엄 이. 램버트 3세 Imide polymer
US20020021883A1 (en) * 1999-08-26 2002-02-21 Takeshi Koyano Optical waveguide made of polymer material and a method of fabricating the same
US20040127057A1 (en) * 2002-12-25 2004-07-01 Tdk Corporation Method for fabricating a patterned thin film and a micro device
CN1616462A (en) * 2004-09-29 2005-05-18 清华大学 Diamine monomer containing di-dehydrated hexitol unit and its preparing method
KR20130140771A (en) * 2011-02-21 2013-12-24 가부시키가이샤 가네카 Acrylic resin film

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