TW201522417A - Aliphatic polycarbonate-polyurethane composition and aliphatic polycarbonate-polyurethane resin - Google Patents

Abstract

Provided are an aliphatic polycarbonate-polyurethane composition and an aliphatic polycarbonate-polyurethane polymer using the same.

Description

Aliphatic polycarbonate-polyurethane composition and aliphatic polycarbonate-polyurethane B Ester resin

The following disclosure relates to an aliphatic polycarbonate-polyurethane composition and the use of the same aliphatic polycarbonate-polyurethane polymer.

Recently, industrial use of aliphatic polycarbonates has been carried out in a manner that reduces the production of carbon dioxide as a means of combating global warming. The aliphatic polycarbonate is a rubbery plastic having a soft texture, has excellent processability, and is easily controlled in terms of its degradation properties, and thus has been studied as a biodegradable polymer. However, since aliphatic polycarbonates have a low glass transition temperature (T _g ) and are easily degraded at about 200 ° C, they are considered to have weak heat resistance properties. In addition, its mechanical and physical properties have a low modulus of elasticity, and the film product prepared therefrom has fragile properties, so its application in various fields is limited. Therefore, there is a need for a technique for increasing the glass transition temperature or heat resistance, or by blending with various types of resins to improve mechanical strength. For example, U.S. Patent No. 4,946,884 discloses the use of a melt-kneading propylene carbonate with polymethyl methacrylate (PMMA) or a binder or metal for a ceramic molding process. A resin composition produced by the powder, and an improvement in mechanical properties by melt-kneading polyvinyl chloride acetate is disclosed in U.S. Patent No. 4,912,149. However, since these inventions are limited to improving mechanical physical strength only by blending with another resin, a structural improvement is required.

[Related technical literature] [Patent Literature]

(Patent Document 1) U.S. Patent Registration No. 4,946,884

(Patent Document 2) U.S. Patent Registration No. 4,912,149

One embodiment of the present invention is directed to various methods of applying aliphatic polycarbonate resins.

More specifically, an embodiment of the present invention relates to an aliphatic polycarbonate-polyuric acid which can be used in various fields of application by mixing an aliphatic polycarbonate resin with polyurethane. Ethyl ester composition, and an aliphatic polycarbonate-polyurethane polymer prepared therefrom.

In a general aspect, an aliphatic polycarbonate-polyurethane polymer comprises an aliphatic polycarbonate (A) consisting of carbon dioxide and one or two or more selected from the group consisting of Manufactured by reacting different epoxy compounds: unsubstituted or halogenated, (C1-C20) alkoxy, (C6-C20) aryloxy, or (C6-C20) aryl (C1-C20) alkane (aralkyl) An oxy-substituted (C2-C20) alkylene oxide; unsubstituted or halogenated, (C1-C20) alkoxy, (C6-C20) aryloxy, or (C6-C20) aryl (C1-C20) alkane (aralkyl)oxy substituted (C4-C20) epoxycycloalkane (cycloalkylene oxide); and unsubstituted or halogenated, (C1-C20) alkoxy, (C6-C20) aryloxy, (C6-C20) aryl (C1-C20) alkane (aralkyl)oxy, Or (C1-C20)alkyl-substituted (C8-C20) styrene oxide; and polyurethane (B).

In another general aspect, an aliphatic polycarbonate-polyurethane composition comprises an aliphatic polycarbonate (A) by combining carbon dioxide with one or two or more selected from the group consisting of Manufactured by reacting different epoxy compounds: unsubstituted or halogenated, (C1-C20) alkoxy, (C6-C20) aryloxy, or (C6-C20) aryl (C1-C20) alkane (C2-C20) alkylene oxide; unsubstituted or halogenated, (C1-C20) alkoxy, (C6-C20) aryloxy, or (C6-C20) aryl (C1- C20) an alkane (aralkyl)oxy-substituted (C4-C20) epoxycycloalkane; and unsubstituted or halogenated, (C1-C20) alkoxy, (C6-C20) aryloxy, (C6- C20) an aryl (C1-C20) alkane (aralkyl)oxy group, or a (C1-C20) alkyl-substituted (C8-C20) epoxyethylbenzene; and a polyurethane (B).

Other features and aspects will be apparent from the following detailed description and claims.

Hereinafter, exemplary embodiments will be described in detail.

The inventors have found that the use of chemically or physically mixed aliphatic polycarbonate resins and polyurethanes results in resistance to flexing, tensile strength, as compared to the use of aliphatic polycarbonate resins alone. The present invention has been completed with dramatic improvements in mechanical strength such as elongation, elasticity, and the like.

In particular, the present invention is discovered by the use of aliphatic polycarbonate resins and poly The fact that the urethane forms an interpenetrating polymer network structure will greatly improve the mechanical and physical properties.

An embodiment of the invention relates to an aliphatic polycarbonate-polyurethane polymer, wherein the aliphatic polycarbonate (A) resin and the polyurethane (B) resin are capable of forming a blend ( Blending), compounding, hybrid, or interpenetrating polymer network (IPN) structures.

The aliphatic polycarbonate (A) may have a weight average molecular weight of 1,000 to 300,000 g/mole.

In the present invention, the weight average molecular weight is obtained by dissolving a powder sample in THF and then using gel permeation chromatography (GPC; agilent Technologies 1260 infinity type) (with PLgel mixed B (7.5 mm × 300) Millimeter) was measured as a column and made of polystyrene (Agilent EasyCal) as a standard sample.

In more detail, the aliphatic polycarbonate (A) used in the preparation of the blended, composite, and hybrid structure aliphatic polycarbonate-polyurethane polymer of the present invention may have 1,000 to 300,000 Weight average molecular weight of grams per mole. Further, the aliphatic polycarbonate (A) used in the preparation of the interpenetrating polymer network (IPN) structure aliphatic polycarbonate-polyurethane polymer of the present invention may have 1,000 to 300,000 g/ The weight average molecular weight of the mole. However, the invention is not limited thereto.

The polyurethane (B) may have a weight average molecular weight of 10,000 to 1,000,000 g/mole.

The aliphatic polycarbonate (A) resin and the polyurethane (B) resin may be melt-kneaded by an extruder at 80 to 200 ° C for doping. Combination and compounding. In the extrusion process, simple extrusion can be used to pass a simple melt-kneading step, and reactive extrusion techniques can be used to effect crosslinking and chain extension reactions. In the case of reactive extrusion, the surface interface can be lowered to avoid phase separation and form a uniform phase, thus providing physical properties and organic/"organic polycarbonate-polyurethane composition" Improvement in dispersion of inorganic additives.

Heterozygous and interpenetrating polymer network structures refer to a network structure formed by the inclusion of a solvent.

An interpenetrating polymer network is a multicomponent polymer in which at least one component has a network structure and at least one component is polymerized or crosslinked in the presence of another component, thereby producing a polymer chain. Interpenetration between. Due to the network structure, the polymer has a high chain degree, so that phase separation which occurs frequently during polymer blending can be suppressed, and by having two-phase continuity in which two components form a continuous phase (dual Phase continuity), various physical properties can be expected to be improved.

In order to form an interpenetrating polymer network structure, an aliphatic polycarbonate (A) resin, an urethane prepolymer produced by reacting a polyol with an isocyanate compound, and a curing agent are reacted to prepare Aliphatic polycarbonate-polyurethane polymer.

Alternatively, in order to form an interpenetrating polymer network structure, an aliphatic polycarbonate, a polyhydric alcohol compound, and a hydroxyl group equivalent of 0.9 to 1.2 equivalents of the hydroxyl group in the polyol compound are dissolved in, for example, methyl ethyl group. The solvent of the ketone is then allowed to react at 80 ° C for a period of time or it is subjected to reaction extrusion at 120 to 200 ° C.

Alternatively, the aliphatic polycarbonate and the epoxy compound may be dissolved in a solvent, and then a curing agent may be equivalently added to form a network structure; or an aliphatic polycarbonate or an epoxy compound. And a curing agent can be used at 120 to 200 ° C The reaction is extruded under the reaction.

Alternatively, the aliphatic polycarbonate and the acrylic compound may be dissolved in a solvent, and a reactive initiator or a catalyst may be equivalently added thereto to form a network structure; or The aliphatic polycarbonate, the acrylic acid compound, and a starter or a catalyst may be subjected to reaction extrusion at 120 to 200 °C.

The aliphatic polycarbonate-polyurethane polymer may comprise from 5 to 95% by weight of the aliphatic polycarbonate (A) and from 5 to 95% by weight of the polyurethane based on the total weight of the polymer. Ester (B). In more detail, the polymer may include 20 to 80% by weight of the aliphatic polycarbonate (A), and 20 to 80% by weight of the polyurethane (B). The desired physical properties can be satisfied by the foregoing ranges.

Further, another embodiment of the present invention relates to an aliphatic polycarbonate-polyurethane composition comprising an aliphatic polycarbonate (A) and a polyurethane (B) for use in the preparation. An aliphatic polycarbonate-polyurethane polymer.

The first embodiment of the aliphatic polycarbonate-polyurethane composition of the present invention may be a composition wherein the aliphatic polycarbonate (A) and the polyurethane (B) are blended or complex.

Further, the second embodiment of the aliphatic polycarbonate-polyurethane composition of the present invention may be a composition in which an aliphatic polycarbonate (A) and a polyurethane (B) are used together. The solvent of the resins is dissolved to form a hybrid or interpenetrating polymer network. As the solvent, any one selected from the group consisting of a ketone system, an acetate system, and an ether solvent, or a mixture of two or more thereof may be used, but is not limited thereto.

Here, the solid content of the aliphatic polycarbonate-polyurethane composition The amount may be from 30 to 50% by weight, and varies depending on the use of the molded article to be manufactured or the method of producing the same.

In the case of the first and second embodiments of the aliphatic polycarbonate-polyurethane composition of the present invention, the aliphatic polycarbonate (A) may have a weight average molecular weight of 1,000 to 300,000 g/mole. And the polyurethane (B) may have a weight average molecular weight of 10,000 to 1,000,000 g/mole, but is not limited thereto. From the foregoing range, the composition can be applied to various fields.

Further, the aliphatic polycarbonate-polyurethane composition may include 5 to 95% by weight of the aliphatic polycarbonate (A) and 5 to 95% by weight of the polyamine based on the total weight of the composition. Ethyl formate (B). From the foregoing content range, the composition can have an effect of excellent mechanical physical properties.

Further, a third embodiment of the aliphatic polycarbonate-polyurethane composition of the present invention may be a composition comprising an aliphatic polycarbonate (A) resin and reacting a polyol with an isocyanate compound. The urethane prepolymer produced, and a curing agent.

Further, the fourth embodiment of the aliphatic polycarbonate-polyurethane composition of the present invention may be a composition comprising an aliphatic polycarbonate (A) resin, a polyol, and a curing agent.

Further, a fifth embodiment of the aliphatic polycarbonate-polyurethane composition of the present invention may be a composition, wherein the composition of the third and fourth embodiments further comprises a group selected from the group consisting of Any of the group: an epoxy compound, and an acryl compound, or a mixture thereof.

Further, the sixth embodiment of the aliphatic polycarbonate-polyurethane composition of the present invention may be a composition in which the third, fourth, and fifth embodiments are The composition also includes a solvent.

Further, the seventh embodiment of the aliphatic polycarbonate-polyurethane composition of the present invention may be a composition, wherein the composition of the third, fourth, and fifth embodiments further includes An initiator or a catalyst.

Hereinafter, the respective components used in the aliphatic polycarbonate-polyurethane polymer and the aliphatic polycarbonate-polyurethane composition will be described in detail.

The aliphatic polycarbonate (A) of the present invention can be produced by copolymerization of carbon dioxide with an epoxy compound different from one or two or more of the following groups: unsubstituted or halogenated, (C1- C20) alkoxy, (C6-C20) aryloxy, or (C6-C20) aryl(C1-C20)alk(aralkyl)oxy substituted (C2-C20) alkylene oxide; unsubstituted or via Halogen, (C1-C20) alkoxy, (C6-C20) aryloxy, or (C6-C20) aryl(C1-C20)alkane(aralkyl)oxy substituted (C4-C20) epoxycycloalkane And unsubstituted or halogenated, (C1-C20) alkoxy, (C6-C20) aryloxy, (C6-C20) aryl (C1-C20) alkane (aralkyl)oxy, or (C1- C20) alkyl-substituted (C8-C20) epoxyethylbenzene.

Here, the epoxy compound may be selected from one or two or more of the following groups: ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, epoxy octane Alkane, epoxy decane, epoxy dodecane, epoxytetradecane, epoxy hexadecane, epoxy octadecane, butadiene monoxide, 1,2-epoxy-7-octane 1,2-epoxide-7-octene, epifluorohydrin, epichlorohydrin, epibromopropane, glycidyl methyl ether, epoxypropylethyl Ether, glycidyl n-propyl ether, epoxypropyl secondary butyl ether, glycidyl n- or isopentyl ether, epoxypropyl n-hexyl ether, Epoxypropyl n-heptyl ether, epoxypropyl n-octyl or 2-ethylhexyl ether (glycidyl n-octyl or 2-ethyl-hexyl ether), glycidyl n- or isononyl ether, glycidyl n-decyl ether, epoxy propyl Di-ether ether, glycidyl n-tetradecyl ether, glycidyl n-hexadecyl ether, glycidyl n-octadecyl ether, epoxypropyl n-hexyl ether, isopropyl epoxide Ether, butyl epoxypropyl ether, tert-butyl butyl epoxide, 2-ethylhexyl epoxypropyl ether, allyl epoxypropyl ether, epoxy cyclopentane, epoxy ring Hexane, epoxy cyclooctane, epoxycyclododecane, alpha-pinene oxide, 2,3-epoxide norbornene, epoxy lemon Limonene oxide, dieldrin, 2,3-epoxide propyl benzene, epoxy ethylbenzene, phenyl propylene oxide, epoxy diphenylethane (stilbene oxide), chlorostilbene oxide, epoxy dichlorodiphenylethane, 1,2-epoxy-3-phenoxypropane, Benzyloxymethyl oxirane, epoxypropyl-methylphenyl ether, chlorophenyl-2,3-ring Chlorophenyl-2,3-epoxide propyl ether, epoxypropyl methoxyphenyl ether, biphenyl epoxypropyl ether, epoxypropyl naphthyl ether, propylene oxide Glycidyl acetic acid ester, glycidyl propionate, glycidyl butyrate, glycidyl n-pentanoate, glycidyl n-hexanoate, glycidyl heptanoate , n-octyl epoxidate, 2-ethylhexanoate propyl acrylate, n-decyl epoxidate, n-decyl epoxidate, n-dodecyl epoxidate, n-tetradecanoate epoxide Propyl ester, n-hexadecanoate, propyl propyl hexadecanate, and glycidyl octadecanoate.

In one embodiment of the present invention, the aliphatic polycarbonate (A) may be a polyalkylene carbonate, wherein the alkylene includes an ethylene group, a propylene group, and 1 - 1-butylene, epoxycyclohexane, alkyl Epoxypropyl ether, n-butyl, and n-octyl, but are not limited thereto.

The aliphatic polycarbonate of the present invention may be polypropylene carbonate or polyethylene carbonate.

An aliphatic polycarbonate according to an exemplary embodiment of the present invention is characterized by having a weight average molecular weight (Mw) of 1,000 to 300,000 g/mole, and the weight average molecular weight may range depending on the preparation method and the material to be prepared. And change. It is preferably a weight average molecular weight of 30,000 to 250,000 g/mole. Further, the polyalkylene carbonate resin may have a glass transition temperature (Tg) of 20 to 105 ° C and a melt index (150 ° C / 5 kg) of 0.01 to 350. The polyalkylene carbonate resin in the foregoing range can be advantageously applied to a pelletization process.

A composition for preparing an aliphatic polycarbonate-polyurethane polymer having an interpenetrating polymer network structure according to an exemplary embodiment of the present invention, based on 100 parts by weight of an aliphatic polycarbonate, The polyol compound may be contained in an amount of from 5 to 950 parts by weight, and from 0.9 to 1.2 equivalents of the hydroxyl group equivalent of the polyol. Beyond the foregoing range, the composition may have remaining unreacted polyisocyanate or insufficient degree of crosslinking due to curing.

In the composition having an interpenetrating polymer network structure according to an exemplary embodiment of the present invention, as the curing agent, any one or two or more of the following groups may be used: isocyanate type, melamine type, amine A system, an acid anhydride system, an imidazole system, and a thiol compound.

Here, it is more preferable to react an isocyanate-based compound and subsequently a melamine-based compound as a curing agent. If two or more curing agents are in the same crosslinking reaction When introduced, the structure of the IPN may vary depending on the reaction rates of the two or more curing agents, and thus, it is difficult to control the reaction to obtain a desired structure. Therefore, the reaction can be carried out by using a curing agent, followed by introduction of another curing agent to obtain an IPN having a uniform structure.

The isocyanate curing agent of the present invention may be selected from any one or more of the following groups: 2,4-trilene diisocyanate, 2,6-trichloroethylene diisocyanate ( 2,6-trilene diisocyanate), hydrogenated trilene diisocyanate, 1,3-xylene diisocyanate, 1,4-dimethylbenzene diisocyanate, diphenylmethane-4,4-diisocyanate, 1 ,3-bisisocyanate methyl cyclohexane, tetramethylxylene diisocyanate, 1,5-naphthalene diisocyanate, 2,2,4-trimethylexylene Isocyanate (2,2,4-trimethyl hexamethylene diisocyanate), 2,4,4-trimethylhexyldiisocyanate, and triphenylmethane triisocyanate.

The melamine-based compound of the present invention may be selected from any one or more of the following groups: hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl Melamine, hexaethoxyoxymethyl melamine, and hexahexyloxymethyl melamine.

The polyol compound of the present invention may be selected from any one or more of the group consisting of polyester polyols, polyether polyols, and polycarbonate polyols.

Here, the polyol may be a low molecular weight polyol having a weight average molecular weight of 200 to 30,000. Outside of the foregoing range, crosslinking by the curing reaction is not easy. If the polyol has an excessively low molecular weight, the polymer produced by the curing reaction hardly has a molecular weight of 50,000 or more; and if the polyol has a molecular weight of 30,000 or more, it is difficult to produce effective penetration of the polyalkylene carbonate molecule. And Therefore, it may be difficult to have an effective IPN structure after the curing reaction.

In an embodiment of the present invention, the isocyanate compound may be any one or two or more compounds selected from the group consisting of 2,4-trichloroethylene diisocyanate, 2,6-trichloroethylene diisocyanate, hydrogenation Trichloroethylene diisocyanate, 1,3-xylene diisocyanate, 1,4-dimethylbenzene diisocyanate, diphenylmethane-4,4-diisocyanate, 1,3-bisisocyanate methylcyclohexane, four Methyl xylene diisocyanate, 1,5-naphthalene diisocyanate, 2,2,4-trimethylhexyl diisocyanate, 2,4,4-trimethylhexyl diisocyanate, and triphenylmethane triisocyanate .

In an embodiment of the present invention, the curing agent may be any one or two or more compounds selected from the group consisting of isocyanate, melamine, amine, acid anhydride, imidazole, and thiol compounds.

In an embodiment of the present invention, the epoxy compound may be any one or two or more compounds selected from the group consisting of glycidyl ether, glycidyl ester, epoxy. A propylamine, a linear aliphatic, and a cycloaliphatic compound.

In an embodiment of the present invention, the acrylic compound may be any one or two or more compounds selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, heptyl acrylate, acrylic acid. 2-Ethylhexyl ester, octyl acrylate, methyl methacrylate, ethyl methacrylate, decyl methacrylate, and 2-ethylbutyl methacrylate.

In one embodiment of the present invention, as the initiator or catalyst, any initiator or catalyst which is conventionally used in the art can be used without limitation. Specifically, for example, any one or more selected from the group consisting of organotin compounds such as tin octylate, monobutyltin triacetate, monobutyltin trioctoate, monooctanoic acid may be used. Monobutyltin, monobutyltin maleate (monobutyltin maleate), dibutyltin diacetate, dibutyltin dioctoate, dibutyltin distearate, dibutyltin dilaurate, and dibutyltin maleate; organotitanium compounds such as tetraisopropyl titanate And tetra-n-butyl titanate; and tert-amine, such as: triethylamine, N,N-diethylcyclohexylamine, N,N,N',N'-four Base ethyl diamine, and tri-ethyl diamine.

An aliphatic polycarbonate-polyurethane polymer according to an exemplary embodiment of the present invention may have an interpenetrating polymer network structure comprising an aliphatic polycarbonate; an epoxy compound , selected from the group consisting of a glycidyl ether system, a glycidyl ester system, a glycidylamine system, a linear aliphatic group, and a cycloaliphatic compound; and a polymerizable, crosslinked, or reacted with the compound The curing agent is obtained, wherein the epoxy compound may be a low molecular weight compound having a weight average molecular weight of 100 to 10,000, so that effective penetration in the aliphatic polycarbonate molecule can be produced, and a good IPN structure is formed after the curing reaction.

An aliphatic polycarbonate-polyurethane polymer according to an exemplary embodiment of the present invention may have an interpenetrating polymer network structure by including an aliphatic polycarbonate; a plurality of acrylic compounds selected from the group consisting of alkyl acrylates or alkyl methacrylates, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, heptyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, decyl methacrylate, and 2-ethylbutyl methacrylate; and one can be polymerized, cross-linked And a curing agent which reacts with the compounds, wherein the acrylic compound can be a low molecular weight compound having a weight average molecular weight of from 100 to 10,000, so that effective penetration in the aliphatic polycarbonate molecule can be produced, while curing A good IPN structure is formed after the reaction.

By including an aliphatic polycarbonate; any one or more compounds selected from the group consisting of polyol compounds, epoxy compounds, and acrylic compounds; and one that can be polymerized, crosslinked, or otherwise The polyalkylene carbonate resin composition having an interpenetrating polymer network structure obtained by curing the compound reaction agent preferably has an interpenetrating polymer network structure by reaction extrusion, and the interpenetrating polymerization The mesh structure can be formed by solution reaction, but is not limited thereto.

The aliphatic polycarbonate-polyurethane polymer having an interpenetrating polymer network structure according to an exemplary embodiment of the present invention may further comprise any one or two or more additives selected from the group below : pigments, dyes, fillers, antioxidants, sunscreens, antistatic agents, anti-caking agents, slip agents, inorganic fillers, kneading agents, stabilizers, tackifying resins, A modified resin, a leveling agent, an optical brightener, a dispersant, a heat stabilizer, a light stabilizer, a UV absorber, and a lubricant.

The aliphatic polycarbonate-polyurethane composition according to the present invention, and the aliphatic polycarbonate-polyurethane polymer prepared using the composition, can be applied to various industrial fields.

More specifically, the aliphatic polycarbonate-polyurethane composition according to an exemplary embodiment of the present invention can be used to manufacture a molded article by a method such as extrusion, injection, casting, or the like. The method can be selected according to the type of molding to be manufactured.

Molds made using an aliphatic polycarbonate-polyurethane composition according to an exemplary embodiment of the present invention may include artificial leather, film, expandable foam, and sheet. (sheet), etc., but is not limited to this.

Further, the aliphatic polycarbonate-polyurethane composition according to an exemplary embodiment can be used in various fields such as an ink composition, a paint composition, a binder composition and the like.

In the following, the invention will be more completely understood from the following examples, which are intended to illustrate the invention and not to limit the scope of the invention.

[Example 1]

100 parts by weight of polycarbonate diol (G3452, Asahi Kasei) having a weight average molecular weight of 2,000 g/mole, 23 parts by weight of 4,4-diphenylmethane diisocyanate (MDI) and 0.1 weight A portion of dibutyltin dilaurate (DBTDL) was added to the reactor, and the reaction was carried out for 1 hour while stirring at 60 rpm and 120 ° C using a Brabender mixer to obtain a urethane prepolymer. Things. To the urethane prepolymer, 1,4-butanediol (BD) was added, and the reaction was carried out for 5 minutes while stirring at 60 rpm and 190 ° C to obtain a polyurethane resin. Here, the isocyanate index (NCO index, ie, the equivalent ratio between isocyanate and diol) is 1.2, and polyol, methyl diphenyl isocyanate (MDI), and 1,4-butanediol (BD) The molar ratio is 1.3:4.8:2.7. The polyurethane and a poly(propyl propylene carbonate) having a weight average molecular weight of 30,000 g/mole were blended in a weight ratio of 70:30 to prepare a poly(propyl carbonate)-polyuric acid. Ethyl ester composition.

[Embodiment 2]

100 parts by weight of polycarbonate diol (G3452, Asahi Kasei) having a weight average molecular weight of 2,000 g/mole, 23 parts by weight of 4,4-diphenylmethane diisocyanate (MDI) and 0.1 part by weight of dilaurin Dibutyltin acid (DBTDL) was added to the reactor and used at a temperature of 60 rpm and 120 °C using a Brabender mixer The reaction was carried out for 1 hour with stirring to obtain an ethyl carbamate prepolymer. 70 parts by weight of the urethane prepolymer, 30 parts by weight of poly(propylcellulose) having a weight average molecular weight of 30,000 g/mole (SK New Technology), and 50 parts by weight of 1,4-butane Alcohol (BD) was added to the reactor. Here, the isocyanate index (NCO index, ie, the equivalent ratio between isocyanate and diol) is 1.2, and polyol, methyl diphenyl isocyanate (MDI), and 1,4-butanediol (BD) The molar ratio is 1.3:4.8:2.7. The reaction mixture was subjected to a reaction under stirring at 60 rpm and 190 ° C for 5 minutes to prepare a hybrid polymerized poly-propyl carbonate-polyurethane composition.

[Comparative Example 1]

100 parts by weight of a polycarbonate diol (G3452, Asahi Kasei) having a weight average molecular weight of 2,000 g/mole, 23 parts by weight of 4,4-diphenylmethane diisocyanate (MDI), and 0.1 part by weight of two Dibutyltin laurate (DBTDL) was charged into the reactor, and the reaction was carried out for 1 hour while stirring at 60 rpm and 120 ° C using a Brabender mixer to obtain an ethyl urethane prepolymer. To the urethane prepolymer, 1,4-butanediol (BD) was added, and the reaction was carried out for 5 minutes while stirring at 60 rpm and 190 ° C to obtain a polyurethane resin.

(assessment)

The products prepared in the foregoing examples and comparative examples were coated on a PET film, and then the film was dried to prepare a sample having the thickness shown in Table 1 below. The various physical properties of the samples were measured by methods in accordance with ASTM standards. Here, the measurement is performed in the machine direction (MD) and the transverse direction (TD) directions, respectively. In addition, adhesion and hydrolysis resistance are evaluated in the following ways:

(1) Adhesion

The prepared sample was pressurized at a pressure of 50 bar and under the temperature conditions shown in Table 1 for 30 seconds, and then cooled at room temperature for 5 seconds, at 180 ° C and 200 mm / min. The highest adhesion of the sample was measured using a peel tester.

(2) Resistance to hydrolysis

After the sample was hung on a water bath and placed in a furnace at 60 ° C for 5 days, the rate of change was measured by comparing the tensile strength before and after the test.

As shown in Tables 1 and 2 above, it can be seen that Example 1 and Example 2 according to the present invention exhibit excellent mechanical physical properties such as tensile strength, elongation, tear strength, and hardness; in achieving these excellent mechanical physical properties. At the same time, the rate of change in tensile strength and elongation is low, and thus the hydrolysis resistance is improved; and, the excellent adhesion of up to 87.75 (Newton/cm) is exhibited. Conversely, it can be confirmed that Comparative Example 1 using polyurethane alone (instead of blending or hybrid polymerization with polyalkylene carbonate according to the present invention) is significantly inferior to the examples. Mechanical and physical properties, hydrolysis resistance, and adhesion.

The aliphatic polycarbonate-polyurethane polymer according to the present invention has an effect of excellent resistance such as flex resistance, hydrolysis resistance, printability, etc. compared to the aliphatic polycarbonate alone. .

Further, the aliphatic polycarbonate-polyurethane composition according to the present invention can be used as an environmentally friendly polyurethane by containing an aliphatic polycarbonate.

While the invention has been described in detail, the preferred embodiments of the present invention may be Therefore, the present invention is not limited to the foregoing embodiments.

Claims (27)

An aliphatic polycarbonate-polyurethane polymer comprising an aliphatic polycarbonate (A) consisting of carbon dioxide and one or two or more selected from the group below Manufactured by reacting different epoxy compounds: unsubstituted or halogenated, (C1-C20) alkoxy, (C6-C20) aryloxy, or (C6-C20) aryl (C1-C20) alkane (aralkyl) An oxy-substituted (C2-C20) alkylene oxide; unsubstituted or halogenated, (C1-C20) alkoxy, (C6-C20) aryloxy, or (C6-C20) aryl (C1-C20) alkane (aralkyl)oxy substituted (C4-C20) cycloalkylene oxide; and unsubstituted or halogenated, (C1-C20) alkoxy, (C6-C20) An aryloxy group, a (C6-C20) aryl (C1-C20) alkane (aralkyl)oxy group, or a (C1-C20) alkyl-substituted (C8-C20) styrene oxide; Ethyl carbamate (B). The aliphatic polycarbonate-polyurethane polymer according to claim 1, wherein the aliphatic polycarbonate (A) resin is blended with the polyurethane (B) resin. , compounding, hybrid, or interpenetrating polymer network (IPN) structures. The aliphatic polycarbonate-polyurethane polymer according to claim 1, wherein the aliphatic polycarbonate (A) has a weight average molecular weight of 1,000 to 300,000 g/mol (g/mol). The aliphatic polycarbonate-polyurethane polymer of claim 1, wherein the polyurethane (B) has a weight average molecular weight of from 10,000 to 1,000,000 g/mole. The aliphatic polycarbonate-polyurethane polymer according to claim 1, wherein the aliphatic polycarbonate (A) is contained in an amount of 5 to 95% by weight based on the total weight of the polymer, and 5 is contained. Up to 95% by weight of the polyurethane (B). The aliphatic polycarbonate-polyurethane polymer according to claim 1, wherein the aliphatic polycarbonate (A) is a polypropylene carbonate or a polyethylene carbonate ( Polyethylene carbonate). An aliphatic polycarbonate-polyurethane composition comprising an aliphatic polycarbonate (A) by reacting carbon dioxide with an epoxy compound different from one or two or more selected from the group below And manufactured: unsubstituted or substituted by halogen, (C1-C20) alkoxy, (C6-C20) aryloxy, or (C6-C20) aryl (C1-C20) alkane (aralkyl)oxy ( C2-C20) alkylene oxide; unsubstituted or halogenated, (C1-C20) alkoxy, (C6-C20) aryloxy, or (C6-C20) aryl (C1-C20) alkane (aralkyl) Oxy-substituted (C4-C20) epoxycycloalkane; and unsubstituted or halogenated, (C1-C20) alkoxy, (C6-C20) aryloxy, (C6-C20) aryl (C1-C20 An alkane (aralkyl)oxy group, or a (C1-C20)alkyl-substituted (C8-C20) epoxyethylbenzene; and a polyurethane (B). The aliphatic polycarbonate-polyurethane composition according to claim 7, wherein the aliphatic polycarbonate (A) resin is blended or compounded with the polyurethane (B) resin. The aliphatic polycarbonate-polyurethane composition according to claim 7, wherein the aliphatic polycarbonate (A) and the polyurethane (B) are used together to dissolve the resins. The solvent forms a heterozygous or interpenetrating polymer network (IPN) structure. The aliphatic polycarbonate-polyurethane composition according to claim 9, wherein the solvent is selected from any one of the group consisting of a ketone system, an acetate system, and an ether system. a solvent, or a mixture of two or more thereof. The aliphatic polycarbonate-polyurethane composition according to claim 8 or 9, wherein the aliphatic polycarbonate (A) has a weight average molecular weight of 1,000 to 300,000 g/mole, and the poly The urethane (B) has a weight average molecular weight of 10,000 to 1,000,000 g/mole. The aliphatic polycarbonate-polyurethane composition according to claim 8 or 9, wherein the aliphatic polycarbonate (A) is contained in an amount of 5 to 95% by weight based on the total weight of the composition, and Containing 5 to 95% by weight of the polyurethane (B). The aliphatic polycarbonate-polyurethane composition according to claim 7, which comprises the aliphatic polycarbonate (A) resin, an amine produced by reacting a polyol with an isocyanate compound. Ethyl formate prepolymer, and a curing agent. The aliphatic polycarbonate-polyurethane composition according to claim 7, which comprises the aliphatic polycarbonate (A) resin, a polyol, and a curing agent. The aliphatic polycarbonate-polyurethane composition of claim 14, further comprising any one selected from the group consisting of epoxy compounds, and acryl compounds, or mixtures thereof. The aliphatic polycarbonate-polyurethane composition of claim 14 or 15, further comprising a solvent. The aliphatic polycarbonate-polyurethane composition of claim 14 or 15, further comprising a starter or a catalyst. The aliphatic polycarbonate-polyurethane composition of claim 13 or 14, wherein the polyol is selected from any one or more of the group consisting of polyester polyols, polyether polyols And polycarbonate polyols. An aliphatic polycarbonate-polyurethane composition as claimed in claim 13 The isocyanate compound is selected from any one or two or more of the following groups: 2,4-trilene diisocyanate, 2,6-trichloroethylene diisocyanate (2) ,6-trilene diisocyanate), hydrogenated trilene diisocyanate, 1,3-xylene diisocyanate, 1,4-dimethylbenzene diisocyanate, diphenylmethane-4,4-diisocyanate, 1, 3-bisisocyanate methyl cyclohexane, tetramethyl xylene diisocyanate, 1,5-naphthalene diisocyanate, 2,2,4-trimethylhexyl diisocyanate (2,2,4-trimethyl hexamethylene diisocyanate), 2,4,4-trimethylhexyldiisocyanate, and triphenylmethane triisocyanate. The aliphatic polycarbonate-polyurethane composition according to claim 13 or 14, wherein the curing agent is selected from any one or two or more of the following groups: isocyanate, melamine, An amine system, an acid anhydride system, an imidazole system, and a thiol compound. The aliphatic polycarbonate-polyurethane composition according to claim 15, wherein the epoxy compound is selected from any one or two or more of the following groups: epoxypropyl ether ( a glycidyl ether system, a glycidyl ester system, a glycidylamine system, a linear aliphatic group, and a cycloaliphatic compound, and the acrylic compound is selected from any one or two or more of the following groups : methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, heptyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, bismuth methacrylate Ester, and 2-ethylbutyl methacrylate. The aliphatic polycarbonate-polyurethane composition according to claim 13 or 14, wherein the aliphatic polycarbonate (A) has a weight average molecular weight of 2,000 to 10,000 g/mole. A molded article using the aliphatic polycarbonate-polyurethane composition of any one of claims 7 to 9 and 13 to 15. The molded article of claim 23, which is selected from the group consisting of artificial leather, film, expandable foam, and sheet. An ink composition using the aliphatic polycarbonate-polyurethane composition according to any one of claims 7 to 9 and 13 to 15. A paint composition using the aliphatic polycarbonate-polyurethane composition of any one of claims 7 to 9 and 13 to 15. A binder composition using the aliphatic polycarbonate-polyurethane composition of any one of claims 7 to 9 and 13 to 15.