TWI486373B - Polyalkylene glycol-lactic acid based nano-composite and preparation method thereof - Google Patents

Description

Polyalkylene glycol lactic acid-based nano composite material and preparation method thereof

The present invention relates to a nano composite material, and more particularly to a polyalkylene glycol lactic acid based nano composite material and a preparation method thereof.

In recent years, 41% of the total output of plastic products has been used in the packaging industry, of which 47% is used in food packaging, which is made of polyethylene (Polyethylene, PE) and polypropylene (PP). Made of polystyrene (Polystyrene, PS), polyvinyl chloride (PVC), etc., the raw material is made of petroleum. If it is disposed of in the environment, it will naturally become undegradable. Waste. This means that about 40% of plastic waste will always exist on Earth, and how to deal with these plastic wastes becomes a global environmental problem.

There are two ways to deal with these wastes. The first one is to dispose of plastic waste in a buried manner, but there may be problems in that the plastic is not easily decomposed and the site is insufficient. On the other hand: burying today's problems, future generations will still have to bear the thorny problems left by the predecessors. Another way is to incinerate or recycle to achieve the purpose of reduction, but incinerating plastics will produce a large amount of greenhouse gases, As a result of global warming, the high heat generated will destroy the incinerator, and the service life of the incineration equipment will be damaged. In addition, the toxic gases and toxic substances decomposed by combustion are also harmful to human health.

Recycling seems to solve this problem, but it takes a lot of manpower and energy: separating the plastic from the garbage, sorting, cleaning, drying and grinding the different plastics, repeating the above steps, and finally getting what you want. The product. Therefore, the cost of recycling is expensive and the quality is poor. As for the recycling and recycling of waste plastics that are generally encouraged or promoted, it is difficult to make rapid growth if the total energy cost is considered.

For the above reasons, the current treatment methods have many problems rather than the best choices. It is urgent to develop green polymeric materials to avoid the use of toxic or harmful components in the process, and in the natural environment. Decomposable material. To this day, the development of biodegradable materials remains a challenging research topic in the field of materials science. Therefore, the search for materials with waste decomposability, especially biodegradable plastics, has received increasing attention.

The invention provides a preparation method of a polyalkylene glycol lactic acid-based nano composite material, a polyalkylene glycol lactic acid-based nano composite material prepared by the method, and a living organism using the polyalkylene glycol lactic acid-based nano composite material Decomposable materials, biomedical materials, packaging materials and paper. The polyalkylene glycol lactic acid-based nano composite material of the invention has excellent biodegradability, biocompatibility, hydrophilicity and thermal stability, and has Has a wide range of applications.

The preparation method of the polyalkylene glycol lactic acid-based nano composite material of the invention comprises mixing the inorganic nano material modified by the organic modifier into the monomer of the polyalkylene glycol lactic acid polymer, and the polyalkylene glycol lactic acid. Formed in a prepolymer of a polymer or a polyalkylene glycol lactic acid based polymer matrix, wherein the organic modifier comprises a surfactant having a C ₆ -C ₄₀ long chain alkyl group or a C ₆ -C ₄₀ aromatic group The inorganic nanomaterial is hydrophilic, and the polyalkylene glycol lactic acid-based polymer includes a polyalkylene glycol lactic acid polymer, a homopolymer of a polyalkylene glycol, a polylactic acid-based polymer or a derivative thereof.

In one embodiment of the present invention, the polyalkylene glycol lactic acid-based polymer includes a polyethylene glycol lactic acid polymer or a polypropylene glycol lactic acid polymer.

In an embodiment of the invention, the polylactic acid-based polymer comprises polylactic acid (PLA) or a copolymer of polylactic acid and polyglycolic acid (PGA) (lactide-co-gycolide, PLGA). ), wherein the polylactic acid is classified into L-form polylactic acid (PLLA), D-form polylactic acid (PDLA), and D, L form polylactic acid (PDLLA).

In an embodiment of the invention, the organic modifying agent hydrophobizes the inorganic nanomaterial to increase dispersibility and compatibility between the inorganic nanomaterial and the polyalkylene glycol lactic acid polymer.

In an embodiment of the invention, the organic modifier is at least one selected from the group consisting of a cationic surfactant, an anionic surfactant, a nonionic boundary surfactant, and an amphoteric surfactant. By.

In an embodiment of the invention, the above organic modifying agent comprises a C ₆ -C ₄₀ long chain alkyl quaternary ammonium salt, a C ₆ -C ₄₀ long chain phenyl quaternary ammonium salt (quaternary) Alkylphenylammonium salt), sodium lauryl sulfate, triethanolamine laurylamine, sodium lauryl amide, phenylammonium chloride, polyoxyethylene coconut oil fatty acid decylamine, coconut oil fatty acid monoethanol guanamine, stearic acid diethanol hydrazine Amine, stearic acid monoethanolamine, C ₁₄ H ₂₉ SO ₄ Na, C ₁₆ H ₃₃ SO ₄ Na, C ₁₈ H ₃₇ SO ₄ Na, C ₁₂ H ₂₅ SO ₄ N(C ₄ H ₉ ) ₄ , C ₁₂ H ₂₅ SO ₄ N(CH ₃ ) ₃ C ₁₂ H ₂₅ , C ₁₂ H ₂₅ CH(COO)N(CH ₃ ), (C ₄ H ₉ ) ₂ CHCH ₂ (OC ₂ H ₄ ) ₉ OH and nC ₁₂ H ₂₅ (OC ₂ H ₄ ) ₃₁ OH or a mixture thereof.

In an embodiment of the invention, the inorganic nanomaterial is at least one selected from the group consisting of clay, montmorillonite, mica, silicate, vermiculite, and metal oxide.

In an embodiment of the present invention, the amount of the inorganic nano-material modified by the organic modifier is from 0.01% by weight to 10% by weight based on the total weight of the polyalkylene glycol lactic acid-based nano composite.

In one embodiment of the present invention, the polymerization method of the above polyalkylene glycol lactic acid polymer includes a condensation polymerization method, a ring-opening polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, and an in-situ intercalation polymerization method. Or melt intercalation polymerization.

In an embodiment of the invention, the inorganic nano material modified by the organic modifier is mixed with the monomer of the polyalkylene glycol lactic acid polymer and the prepolymerization of the polyalkylene glycol lactic acid polymer. The method in the article, or the polyalkylene glycol lactic acid based polymer matrix, comprises the following steps. First, the inorganic nanomaterial modified by the organic modifier is swollen with a solvent. Next, the polyalkylene glycol lactic acid polymer or its prepolymer is mixed and swelled. The inorganic nanomaterial in which the polymer chain of the oxyalkylene glycol lactic acid polymer or its prepolymer is intercalated into the inorganic nano material, and the solvent is present between the layers of the inorganic nano material. After that, the solvent is removed.

In an embodiment of the invention, the inorganic nano material modified by the organic modifier is mixed with the monomer of the polyalkylene glycol lactic acid polymer and the prepolymerization of the polyalkylene glycol lactic acid polymer. The method in the article, or the polyalkylene glycol lactic acid based polymer matrix, comprises the following steps. First, the inorganic nanomaterial modified by the organic modifier is swollen. Next, the swollen inorganic nano material is placed in a monomer of a liquid polyalkylene glycol lactic acid polymer or a solution of a monomer containing a polyalkylene glycol lactic acid polymer, wherein the polyalkylene glycol lactic acid is The monomers of the polymer are polymerized between the layers.

In an embodiment of the invention, the inorganic nano material modified by the organic modifier is mixed with the monomer of the polyalkylene glycol lactic acid polymer and the prepolymerization of the polyalkylene glycol lactic acid polymer. The method in the article, or the polyalkylene glycol lactic acid based polymer matrix, comprises the following steps. First, a monomer and a prepolymer of a polyalkylene glycol lactic acid polymer are heated to form a molten polyalkylene glycol lactic acid-based polymer. Next, the molten polyalkylene glycol lactic acid-based polymer is cooled or the molten polyalkylene glycol lactic acid-based polymer is subjected to a shearing force to melt the polyalkylene glycol lactic acid-based polymer and The inorganic modifier material modified by the organic modifier is mixed.

In an embodiment of the present invention, the method for preparing the polyalkylene glycol lactic acid-based nano composite material further comprises using an isothermal heat treatment procedure to increase the crystallinity and physical properties of the polyalkylene glycol lactic acid-based polymer.

The polyalkylene glycol lactic acid-based nano composite material of the present invention is composed of the aforementioned polyalkane It is prepared by a method for preparing a glycol lactic acid-based nano composite.

The biodegradable material of the present invention includes the aforementioned polyalkylene glycol lactic acid-based nano composite material.

The biomedical material of the present invention includes the aforementioned polyalkylene glycol lactic acid-based nano composite material.

The packaging material of the present invention includes the aforementioned polyalkylene glycol lactic acid-based nanocomposite.

The paper of the present invention is composed of the above-mentioned polyalkylene glycol lactic acid-based nano composite material coated on a fibrous base material.

Based on the above, the method for preparing a polyalkylene glycol lactic acid-based nano composite material according to the present invention, by uniformly dispersing an inorganic nano-material modified by an organic modifier in a polyalkylene glycol lactic acid-based polymer matrix, A series of nanocomposites with excellent biodegradability, biocompatibility, hydrophilicity and thermal stability can be prepared.

The above described features and advantages of the invention will be apparent from the following description.

Figure 1 is a schematic view of a clay structure.

2 is a TGA analysis result of Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, Experimental Example 1-4, and Comparative Example 1.

3 is a melting graph of Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, Experimental Example 1-4, and Comparative Example 1.

4 is a crystallization graph of Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, Experimental Example 1-4, and Comparative Example 1.

5a to 5d are TEM images of Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, and Experimental Example 1-4, respectively.

6a and 6b are a crystallization start diagram and a crystallization completion diagram of Comparative Example 1, respectively.

7a and 7b are a crystallization start diagram and a crystallization completion diagram of Experimental Example 1-1, respectively.

8a and 8b are a crystallization start diagram and a crystallization completion diagram of Experimental Example 1-2, respectively.

9a and 9b are a crystallization start diagram and a crystallization completion diagram of Experimental Example 1-3, respectively.

10a and 10b are a crystallization start diagram and a crystallization completion diagram of Experimental Example 1-4, respectively.

Fig. 11a is a WXRD chart of Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, and Experimental Example 1-4 and Comparative Example 1 at the crystallization peak onset temperature.

Fig. 11b is a WXRD chart of Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, and Experimental Example 1-4 and Comparative Example 1 at the highest point temperature of the crystallization peak.

Fig. 12 shows the results of TGA analysis of Experimental Example 2-1, Experimental Example 2-2, Experimental Example 2-3, and Comparative Example 2.

Fig. 13 is a graph showing the melting curves of Experimental Example 2-1, Experimental Example 2-2, Experimental Example 2-3, and Comparative Example 2 after non-isothermal crystallization.

14 is a crystal graph of the non-isothermal crystallization of Experimental Example 2-1, Experimental Example 2-2, Experimental Example 2-3, and Comparative Example 2.

Fig. 15a is a graph showing the melting curve of isothermal crystallization at different crystallization temperatures of Comparative Example 2.

Fig. 15b is a graph showing the melting curve of the experimental example 2-1 after isothermal crystallization at different crystallization temperatures.

Fig. 15c is a graph showing the melting curve of the experimental example 2-2 after isothermal crystallization at different crystallization temperatures.

Fig. 15d is a melting curve of the experimental example 2-3 after isothermal crystallization at different crystallization temperatures.

16a to 16c are TEM images of Experimental Example 2-1, Experimental Example 2-2, and Experimental Example 2-3, respectively.

17a and 17b are POM crystal diagrams of Comparative Example 2 at the crystallization temperature T ₁ and the crystallization temperature T ₅ , respectively.

18a and 18b are POM crystal diagrams of Experimental Example 2-1 at the crystallization temperature T ₁ and the crystallization temperature T ₅ , respectively.

19a and 19b are POM crystal diagrams of Experimental Example 2-2 at the crystallization temperature T ₁ and the crystallization temperature T ₅ , respectively.

20a and 20b are POM crystal diagrams of Experimental Example 2-3 at the crystallization temperature T ₁ and the crystallization temperature T ₅ , respectively.

Fig. 21a is a WXRD chart of Experimental Example 2-1, Experimental Example 2-2, and Experimental Example 2-3 and Comparative Example 2 at a crystallization temperature T ₁ .

21b is a WXRD pattern of Experimental Example 2-1, Experimental Example 2-2, and Experimental Example 2-3 and Comparative Example 2 at a crystallization temperature T ₂ .

21c is a WXRD pattern of Experimental Example 2-1, Experimental Example 2-2, and Experimental Example 2-3 and Comparative Example 2 at a crystallization temperature T ₃ .

21d is a WXRD pattern of Experimental Example 2-1, Experimental Example 2-2, and Experimental Example 2-3 and Comparative Example 2 at a crystallization temperature T ₄ .

21e is a WXRD pattern of Experimental Example 2-1, Experimental Example 2-2, and Experimental Example 2-3 and Comparative Example 2 at a crystallization temperature T ₅ .

The invention provides a preparation method of a polyalkylene glycol lactic acid-based nano composite material, which comprises mixing an inorganic nano material modified by an organic modifier into a monomer of a polyalkylene glycol lactic acid polymer, and a polyalkane A prepolymer of a alcoholic lactic acid polymer or a polyalkylene glycol lactic acid polymer matrix. That is, in the preparation method, the inorganic nanomaterial may be added during the polymerization of the polyalkylene glycol lactic acid-based polymer or may be added after the polyalkylene glycol lactic acid-based polymer has been polymerized.

In addition, the inorganic nano-material modified by the organic modifier can be blended into the monomer, prepolymer or polyalkylene glycol lactic acid polymer matrix of the polyalkylene glycol lactic acid polymer through a variety of different methods. The following will be explained in detail by various embodiments.

In one embodiment, the method of blending an organic modifier-modified inorganic nanomaterial into a monomer, a prepolymer or a polyalkylene glycol lactic acid polymer matrix of a polyalkylene glycol lactic acid polymer comprises The following steps. First, the inorganic nanomaterial modified by the organic modifier is swollen with a solvent. Next, a polyalkylene glycol lactic acid-based polymer or a prepolymer thereof and a swelled inorganic nano-material, wherein the polyalkylene glycol lactic acid-based polymer is mixed The polymer chains of the prepolymers thereof or the prepolymers are intercalated in the inorganic nanomaterial, and the solvent is present between the layers of the inorganic nanomaterial. After that, the solvent is removed.

In detail, the above preparation method is a solvent system, and therefore the polyalkylene glycol lactic acid-based polymer or its prepolymer must be dissolved by a solvent, and the inorganic nano-material can be swollen by a solvent. The solvent is, for example, water, toluene or chloroform. More specifically, in the above production method, the polymerization method of the polyalkylene glycol lactic acid-based polymer is carried out by a solution polymerization method.

In this embodiment, the polyalkylene glycol lactic acid-based polymer includes, for example, a polyalkylene glycol lactic acid polymer, a homopolymer of a polyalkylene glycol, a polylactic acid-based polymer or a derivative thereof, wherein a polyalkylene glycol is used. Lactic acid polymers are dominant. Further, in this embodiment, the polyalkylene glycol lactic acid-based polymer is, for example, a polyethylene glycol lactic acid polymer or a polypropylene glycol lactic acid polymer. That is, when the polyalkylene glycol lactic acid-based polymer is a polyethylene glycol lactic acid-based polymer, it includes a polyethylene glycol lactic acid polymer, a homopolymer of polyethylene glycol, or a polylactic acid-based polymer. Similarly, when the polyalkylene glycol lactic acid-based polymer is a polypropylene glycol lactic acid-based polymer, it includes a polypropylene glycol lactic acid polymer, a polypropylene glycol homopolymer or a polylactic acid-based polymer.

Further, the polylactic acid-based polymer includes polylactic acid or a copolymer of polylactic acid and polyglycolic acid. In detail, polylactic acid or a copolymer of polylactic acid and polyglycolic acid has excellent biocompatibility, biodegradability, and appropriate material physicochemical properties. However, the present invention is not limited thereto. In other embodiments, the polylactic acid-based polymer may also be a polylactic acid, an aliphatic polyester, a polycyano acrylate, or a poly Poly(amides), polyorthoesters (Poly(orthoesters, POE), polyanhydrides (PAH) or polyacetal copolymers. Further, polylactic acid has an asymmetric carbon atom to provide an optically active center, which contains R and S two kinds of optical isomer configuration stereoisomers, so depending on the monomer molecules, polylactic acid can be divided into L-form polylactic acid (PLLA), D-form polylactic acid (PDLA) and D, L form poly Lactic acid (PDLLA).

From another point of view, the polymerization method of the polyalkylene glycol lactic acid-based polymer is achieved, for example, by a ring-opening polymerization method or a condensation polymerization method. For example, when the polyalkylene glycol lactic acid-based polymer is a polyethylene glycol lactic acid-based polymer, the polymerization reaction of the polyalkylene glycol lactic acid-based polymer can be carried out at a higher temperature and under vacuum conditions. The alcohol is mixed with Lactide as a monomer, and is catalyzed by stannous octoate, as shown in the following formula 1, wherein x and y are from 1 to 2,000.

Similarly, when the polyalkylene glycol lactic acid-based polymer is a polypropylene glycol lactic acid-based polymer, the polymerization of the polyalkylene glycol lactic acid-based polymer can be carried out by passing polypropylene glycol as a monomer at a relatively high temperature under vacuum. The lactide is mixed and catalyzed by stannous octoate, as shown in the following formula 2, wherein x and y are from 1 to 2,000.

Specifically, the polymerization methods of the above formulas 1 and 2 are carried out by a ring-opening polymerization method. However, the invention is not limited thereto. For example, the polymerization reaction of the polyalkylene glycol lactic acid-based polymer can also be carried out by a condensation polymerization method using lactic acid as a monomer and polyethylene glycol or polypropylene glycol. As another example, it is understood from the above that the polymerization reaction of the polyalkylene glycol lactic acid-based polymer can be carried out by mixing a copolymer of polylactic acid and polyglycolic acid with polyethylene glycol or polypropylene glycol.

In this embodiment, the amount of the inorganic nano-material modified by the organic modifier is, for example, 0.01% by weight to 10% by weight, preferably 0.5, based on the total weight of the polyalkylene glycol lactic acid-based nano composite material. Wt% to 2wt%.

Further, in this embodiment, the inorganic nanomaterial is a hydrophilic inorganic nanomaterial. In detail, since the polymer and its monomer or prepolymer are mostly lipophilic, it is usually subjected to modification treatment before the inorganic nano material and the lipophilic polymer and its monomer or prepolymer are mixed. In view of this, in the preparation method of the polyalkylene glycol lactic acid-based nano composite material of the present invention, the inorganic nano material is hydrophobized by using an organic modifier to polymerize the inorganic nano material and the polyalkyl glycol lactic acid. The dispersibility and compatibility between the substances increases.

In this embodiment, the organic modifier is, for example, a surfactant having a C ₆ -C ₄₀ alkyl group or a C ₆ -C ₄₀ aromatic group. The type of the surfactant is not particularly limited, and is, for example, at least one selected from the group consisting of a cationic surfactant, an anionic surfactant, a nonionic boundary surfactant, and an amphoteric surfactant. For example, examples of the organic modifier include a C ₆ -C ₄₀ alkyl quaternary ammonium salt such as trimethylammonium citrate, lauryl dimethylaminoacetate trimethyl acetate. Ammonium lactone, C ₁₂ H ₂₅ N(CH ₃ ) ₃ Br, C ₁₄ H ₂₉ N(CH ₃ ) ₃ Br, C ₁₆ H ₃₃ N(CH ₃ ) ₃ Br, (C ₂ H ₂₅ ) ₂ (CH _{3 2} NBr, C ₁₂ H ₂₅ SO ₄ N(C ₄ H ₉ ) ₄ or C ₁₂ H ₂₅ SO ₄ N(CH ₃ ) ₃ C ₁₂ H ₂₅ ; C ₆ -C ₄₀ alkylphenyl quaternary ammonium salt ( Quaternary alkylphenylammonium salt), such as dimethylbenzylammonium chloride stearate; benzalkonium chloride; sodium lauryl sulfate; triethanolamine lauryl acid; sodium lauryl sulfate; polyoxyethylene coconut oil fatty acid guanamine ; coconut oil fatty acid monoethanol decylamine; stearic acid diethanol decylamine; stearic acid monoethanol decylamine; C ₁₄ H ₂₉ SO ₄ Na; C ₁₆ H ₃₃ SO ₄ Na; C ₁₈ H ₃₇ SO ₄ Na; ₁₂ H ₂₅ CH(COO)N(CH ₃ ); (C ₄ H ₉ ) ₂ CHCH ₂ (OC ₂ H ₄ ) ₉ OH; nC ₁₂ H ₂₅ (OC ₂ H ₄ ) ₃₁ OH or a mixture thereof, preferably Is a C ₆ -C ₄₀ alkyl quaternary ammonium salt, and especially C ₁₂ H ₂₅ N(CH ₃ ) ₃ Br, C ₁₄ H ₂₉ N(CH ₃ ) ₃ Br, C ₁₆ H ₃₃ N (C H ₃ ) ₃ Br or (C ₂ H ₂₅ ) ₂ (CH ₃ ) ₂ NBr.

Further, in this embodiment, the inorganic nanomaterial is, for example, at least one selected from the group consisting of clay, montmorillonite, mica, silicate, vermiculite, and metal oxide, and is preferably clay or Montmorillonite. For example, referring to FIG. 1, the clay used in the present invention is an inorganic substance having a niobate, and has a layered structure formed by sandwiching a layer of Al ₂ O ₃ octahedron with two layers of SiO ₂ tetrahedron. . Further, there are metal ions (i.e., cations) which are replaceable and easy to carry out water and reaction between the layers of the clay. In view of this, as described above, the method of the present embodiment can swell the inorganic nano material by a solvent such as water to increase the interlayer distance of the inorganic nano material and expand the volume by several tens of times.

Further, in the present embodiment, in addition to the above-described effect of increasing the interlayer distance by the characteristics of the inorganic nanomaterial itself, the organic modifier can further enlarge the interlayer distance of the inorganic nano material to facilitate the interlayer distance. The polyalkylene glycol lactic acid-based polymer and its monomer or prepolymer enter its interlayer. That is to say, in addition to hydrophobizing the inorganic nanomaterial, the organic modifier can also increase the interlayer distance of the inorganic nanomaterial.

Hereinafter, an organic modifying agent will be described as an example of a C ₆ -C ₄₀ alkyl quaternary ammonium salt. By ion exchange of the hydrophilic end of the C ₆ -C ₄₀ alkyl quaternary ammonium salt with the cation in the inorganic nano material, the alkyl portion of the C ₆ -C ₄₀ alkyl quaternary ammonium salt enters the inorganic nano material The effect of expanding the interlayer distance of the inorganic nanomaterial is achieved between the layers. At this time, the alkyl portion passing through the C ₆ -C ₄₀ alkyl quaternary ammonium salt enters the interlayer of the inorganic nano material, and the interlayer of the inorganic nano material may thus have lipophilicity. As a result, in the method of the present embodiment, the polymer chain of the polyalkylene glycol lactic acid-based polymer or its prepolymer and the alkyl moiety (lipophilic end) existing between the layers of the inorganic nanomaterial are phase-produced. The capacity is increased to increase the dispersibility and compatibility between the inorganic nanomaterial and the polyalkylene glycol lactic acid polymer. In addition, since the change in the interlayer distance of the inorganic nanomaterial may vary depending on the type of the organic modifier under the same operating conditions, it is understood by those having ordinary knowledge in the field that, depending on the actual preparation conditions, A suitable organic modifier can be used to modify the surface of the inorganic nanomaterial to increase the interlayer distance.

In general, the reinforcing effect of inorganic materials is determined by the degree of dispersion in organic materials. However, the traditional mechanical dispersion has limited effect and can only disperse inorganic materials to the micron order (~10 ^-6 m). Based on this, in order to achieve a good reinforcing effect to improve the physical properties of the organic material, a better dispersion effect can be produced for the characteristics of the inorganic material itself, that is, dispersed to a nanometer (nanometer, 10 ^-7 to 10 ^-9 m). In general, the smaller the size of the inorganic material, the better the dispersion effect and the interfacial force in the organic material, and the better the reinforcing effect. In view of the above, in the present embodiment, the inorganic nano material is modified by using an organic modifier, so that the polyalkylene glycol lactic acid polymer or its prepolymer enters the interlayer of the inorganic nano material due to compatibility. In order to achieve the nanometer-level dispersion effect, the physical properties of the polyalkylene glycol lactic acid-based polymer, such as thermal stability, mechanical strength, and the like, are further improved.

From another point of view, in the present embodiment, the inorganic nano material is sufficient to act as a crystal as the inorganic nanomaterial reaches a nano-scale dispersion effect in the polyalkylene glycol lactic acid-based polymer or its prepolymer matrix. At the time of the crystal nucleus, the crystallization rate and crystallinity of the polyalkylene glycol lactic acid-based polymer are increased.

In another embodiment, the inorganic modifier material modified by the organic modifier is blended into a monomer, a prepolymer or a polyalkylene glycol lactic acid polymer matrix of a polyalkylene glycol lactic acid polymer. Includes the following steps. First, the inorganic nanomaterial modified by the organic modifier is swollen. Next, the swollen inorganic nanomaterial is placed in a monomer of a liquid polyalkylene glycol lactic acid polymer or a solution of a monomer containing a polyalkylene glycol lactic acid polymer, wherein the polyalkane Monomer of diol lactic acid polymer in layer The polymerization was carried out. In detail, in the above production method, the polymerization reaction of the polyalkylene glycol lactic acid-based polymer is carried out by an in-situ intercalation polymerization method. From another point of view, it is understood from the above that in the present embodiment, the polymerization reaction of the polyalkylene glycol lactic acid-based polymer can be carried out in the manner of the above formula 1 or formula 2. Further, in the present embodiment, the explosive force excited by the polymerization reaction of the monomer of the polyalkylene glycol lactic acid polymer can further increase the interlayer distance of the inorganic nano material to intercalation or Dispersion effect of the effusion type. In addition, the materials, formation methods, characteristics, contents, and the like of the respective compositions in the preparation method have been described in detail in the above embodiments, and thus will not be described herein.

In still another embodiment, the inorganic modifier material modified by the organic modifier is blended into the monomer, prepolymer or polyalkylene glycol lactic acid polymer matrix of the polyalkylene glycol lactic acid polymer. Includes the following steps. First, a monomer and a prepolymer of a polyalkylene glycol lactic acid polymer are heated to form a molten polyalkylene glycol lactic acid-based polymer. Next, after the molten polyalkylene glycol lactic acid-based polymer is cooled or the molten polyalkylene glycol lactic acid-based polymer is melted, the polyalkylene glycol is melted. The lactic acid-based polymer is mixed with the inorganic nano-material modified by an organic modifier. Specifically, the above production method is carried out in a solvent-free state, and therefore the temperature must be equal to or higher than the melting temperature of the polyalkylene glycol lactic acid-based polymer. More specifically, in the above production method, the polymerization method of the polyalkylene glycol lactic acid-based polymer is carried out by a melt intercalation polymerization method. From another point of view, it is understood from the above that in the present embodiment, the polymerization reaction of the polyalkylene glycol lactic acid-based polymer can be carried out in the manner of the above formula 1 or formula 2. In addition, the materials of the respective components in the preparation method Materials, formation methods, characteristics or contents, etc. have been described in detail in the above embodiments, and thus will not be described again.

Further, the method for producing a polyalkylene glycol lactic acid-based nanocomposite of the present invention further comprises an isothermal heat treatment procedure to further increase the crystallinity and physical properties of the polyalkylene glycol lactic acid-based polymer.

Further, in the above, although the preparation method of the polyalkylene glycol lactic acid-based nano composite material of the present invention is explained by the method of the three examples, the present invention is not limited thereto. In other embodiments, the method for preparing the polyalkylene glycol lactic acid-based nanocomposite of the present invention can also be carried out by a suitable polymerization method such as a suspension polymerization method or an emulsion polymerization method.

The present invention also provides a polyalkylene glycol lactic acid-based nanocomposite which is produced by the above-described method for producing a polyalkylene glycol lactic acid-based nanocomposite of the present invention. In detail, since polylactic acid has good biodegradability, biocompatibility and mechanical properties, and polyalkylene glycol has good hydrophilicity, is soluble in water and many organic solvents, and is non-toxic, The polyalkylene glycol lactic acid-based nanocomposite of the present invention has excellent biodegradability, biocompatibility and hydrophilicity. Further, since the polyalkylene glycol lactic acid-based nano composite material of the present invention is in a form in which an inorganic nano-material modified by an organic modifier is uniformly dispersed in a polyalkylene glycol lactic acid-based polymer matrix, The polyalkylene glycol lactic acid-based nanocomposite of the invention has good physical properties and crystallinity.

Therefore, the polyalkylene glycol lactic acid-based nano composite material based on the present invention has excellent biocompatibility, and thus can be widely applied to biomedical materials, for example, surgical sutures; Absorbable fracture fixation devices, such as bone nails, bone plates; carriers for drug release; or tissue engineering stents. In addition, the polyalkylene glycol lactic acid-based nano composite material based on the invention has good biodegradability and does not cause pollution and damage to the environment, so it can be widely applied to daily necessities, and can also be applied to packaging materials or paper. The coating materials and the like are quite industrially useful.

<experiment>

Various features and effects of the present invention will be more specifically described below with reference to Experimental Example 1-1 to Experimental Example 1-4 and Experimental Example 2-1 to Experimental Example 2-3. Although the following experimental examples are described, the materials used, the amounts and ratios thereof, the processing conditions, the details of the flow, and the like can be appropriately changed without departing from the scope of the invention. Therefore, the present invention is not limited to the following experimental examples.

Experimental Example 1-1 to Experimental Example 1-4

The information on the main materials used in the preparation of polyalkylene glycol lactic acid-based nanocomposites is as follows.

Polyalkyl glycol-lactic acid copolymer (PLLA-PEG copolymer)

Source: Self-synthesis, the molecular weight of the polyethylene glycol used is 600

Weight average molecular weight: 10,000 to 1000000

Molecular structure: as shown in the above formula 1.

Inorganic nanomaterial: PK805 montmorillonite

Source: manufactured by Paikong

Ion exchange capacity (CEC): 98meq/100g

Organic modifier: DilaurylDimethyl Ammonium Bromide (DMAB)

Source: TCI Manufacturing

Chemical formula: (C ₁₂ H ₂₅ ) ₂ (CH ₃ ) ₂ NBr

Solvent: chloroform

Source: Japan Pharmaceutical Manufacturing

<Preparation of Inorganic Nanomaterials Modified by Organic Modifiers>

The steps for preparing the inorganic nanomaterial modified by the organic modifier are as follows:

1. Take 5 g of PK805 montmorillonite in 800 ml of distilled water and stir at room temperature for 24 hours to completely swell the montmorillonite.

2. The amount of DMAB required to calculate the ion exchange capacity of PK805 montmorillonite was 6.4 g, and the formula was as follows: 98/100 x 5g x 1.2 = (weight average molecular weight of X/DMAB) x 1 x 1000.

3. 6.4 g of DMAB was dissolved in 20 mL of distilled water and stirred for 30 minutes.

4. Add the DMAB aqueous solution of step 3 to the swollen PK805 montmorillonite aqueous solution of step 1, and stir at room temperature for 24 hours to uniformly mix the DMAB aqueous solution with the PK805 montmorillonite aqueous solution.

5. After filtering the aqueous solution of the step 4, it was washed several times with distilled water until the white nitrate solution was titrated, and no white precipitate was produced.

6. The product obtained in step 5 was placed in a vacuum oven at 100 ° C, dried and ground to a powder.

7. The powder obtained in the step 6 was sieved through a 325 mesh sieve to obtain a modified PK805 montmorillonite having a particle size of about 40 μm.

<Preparation of polyalkylene glycol lactic acid-based nanocomposites>

First, the polyethylene glycol lactic acid polymer was placed in a vacuum oven and baked at a set temperature of 80 ° C for 12 hours to remove moisture. Next, the modified PK805 montmorillonite was dissolved in chloroform at a ratio of 0.5% by weight to carry out swelling and dispersion. Thereafter, the baked polyethylene glycol lactic acid polymer was added to the above solution, and stirred at room temperature for 6 hours. After stirring uniformly, the above solution containing polyethylene glycol lactic acid polymer was poured into a Teflon disk, and placed in a vacuum oven, and dried at 80 ° C for 12 hours to completely remove chloroform to obtain an experimental example. A polyalkylene glycol lactic acid-based nanocomposite of 1-1, that is, a polyethylene glycol lactate nano composite.

For the polyethylene glycol lactate nanocomposite of Experimental Example 1-1, Thermogravimetry Analysis (TGA, TA-Q500) and Differential Scanning Calorimeter (DSC, Perkin-Elmer series) were used. 6 DSC) and other analytical instruments for thermal properties analysis, and using polarized optical microscopy (POM, OLYMPUS BX51), Wide-Angle X-ray Diffraction (WXRD, Thermo Electron ARL X'TRAS) ), an analytical instrument such as a Transmission Electron Microscope (TEM, JEOLJEM2010) for dispersion, Identification of crystalline properties and forms. The steps, experimental conditions, and test results of these tests are detailed below.

The polyethylene glycol lactic acid nanocomposites of Experimental Example 1-2, Experimental Example 1-3 and Experimental Example 1-4 were prepared in the same manner, and the difference was only in the amount of modified PK805 montmorillonite, wherein the experimental example The addition amount of 1-2 was 1 wt%, the addition amount of Experimental Example 1-3 was 1.5 wt%, and the addition amount of Experimental Example 1-4 was 2 wt%.

<Thermal property analysis - thermogravimetric analysis>

10 mg of polyethylene glycol lactic acid polymer (Comparative Example 1) and Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, and Experimental Example 1-4 were respectively weighed by a thermogravimetric analyzer. Alcoholic lactate nanocomposites were placed in a platinum plate and placed in the instrument to record changes in temperature and weight. Experimental conditions: N ₂ flow rate was 20 mL / min; detection temperature range was 30 ~ 500 ° C; heating rate was 20 ° C / min. The test results are shown in Figure 2. 2 shows that the thermal cracking temperature of the polyethylene glycol lactic acid polymer (Comparative Example 1) was about 274.1 ° C, and the polymerization of Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, and Experimental Example 1-4. The ethylene glycol lactate nanocomposite gradually increased with the addition of the modified PK805 montmorillonite. That is to say, blending with the modified PK805 montmorillonite helps to improve the thermal stability of the polyethylene glycol lactic acid polymer.

<Thermal property analysis - differential thermal scanning analysis>

10 mg of polyethylene glycol lactic acid polymer (Comparative Example 1) and Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, and Experimental Example 1-4 were respectively weighed by a differential thermal scanning analyzer. Glycol lactate nanocomposites were placed in aluminum pans. Then, two temperature rise and fall cycles (first cycle and second cycle) are performed, and the temperature rise curve (Tm ₁ , Tm ₂ ) of each of the above is obtained by the temperature rise curve and the temperature drop profile detected by the second cycle. And melting enthalpy (ΔHm, ΔHm ₁ , ΔHm ₂ ), crystallization temperature (Tc), and crystallization enthalpy (ΔHc), wherein Tm ₁ and Tm ₂ are respectively the first melting peak and the second melting peak of each of the above The temperature, and ΔHm ₁ and ΔHm ₂ are the melting enthalpy when each of the above is heated to the temperature of the first melting peak and the second melting peak, and ΔHm is the sum of ΔHm ₁ and ΔHm ₂ . The experimental conditions are as follows. The first cycle: after setting the temperature at 25 ° C for 1 min, the temperature is raised to 190 ° C at 20 ° C / min and then fixed for 3 min, and then cooled to 25 ° C at 10 ° C / min; the second cycle: after fixing at 25 ° C for 3 min, The temperature was raised to 190 ° C at 20 ° C / min and then fixed for 3 min, and then cooled to 25 ° C at 5 ° C / min. The test results are shown in Figure 3, Figure 4 and Table 1.

3 and Table 1 show Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, and the melting temperature (Tm ₁ , Tm ₂ ) of the polyethylene glycol lactic acid polymer (Comparative Example 1). The melting temperatures of the polyethylene glycol lactic acid nanocomposites of Experimental Examples 1-4 were all increased, and the melting temperature Tm _{2 was} more pronounced.

4 and Table 1 show that the crystallization temperature of the polyethylene glycol lactic acid polymer (Comparative Example 1) was 127.74 ° C, and Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, and Experimental Example 1 The crystallization temperature of the polyethylene glycol lactic acid nanocomposite of 4 falls within the range of 106 ° C to 108 ° C. That is, compared with the polyethylene glycol lactic acid polymer (Comparative Example 1), when different proportions of the modified PK805 montmorillonite were added, the crystallization temperature of the polyethylene glycol lactic acid polymer was lowered and the possession was more It is a temperature zone with a broad crystallization. 4 and Table 1 show the crystallization peaks of Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, and Experimental Example 1-4 as compared with the polyethylene glycol lactic acid polymer (Comparative Example 1). They are all sharp, and the crystallization peaks of Experimental Examples 1-3 and Experimental Examples 1-4 are sharper, which means that the addition of modified PK805 montmorillonite can improve the crystallization rate and crystallinity of the polyethylene glycol lactic acid polymer. .

In addition, the relationship between the melting point change and the crystalline form can be analyzed by the DSC detection result. The crystallinity of Comparative Example 1, Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, and Experimental Example 1-4 was calculated by the following Formula 3 (indicated as Xc in Table 1): Where ΔHm is the heat of fusion and f is the weight fraction. It is ideal crystal heat of fusion 94J/g. As is clear from Table 1, the crystallinity of Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, and Experimental Example 1-4 was higher than that of the modified PK805 montmorillonite as compared with Comparative Example 1. The more you rise. In addition, FIG. 3 shows that the second melting peaks of Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, and Experimental Example 1-4 were significantly higher than Comparative Example 1, in which Experimental Examples 1-3 and The second melting peak of Experimental Example 1-4 is particularly obvious, and it can be seen that the ratio of ΔHm2/ΔHm1 in Table 1 shows that the second melting peak is more and more obvious due to the increased proportion of modified PK805 montmorillonite. It indicates that the addition of the modified PK805 montmorillonite contributes to the growth of crystal nuclei at the melting temperature Tm ₂ .

<Dispersion situation - transmission electron microscope>

The modified PK805 montmorillonite in the polyethylene glycol lactic acid nanocomposite of Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, and Experimental Example 1-4 was observed using a transmission electron microscope. Whether the soil is evenly dispersed. Experimental conditions: The lamp source is lanthanum hexaboride, the acceleration voltage is 200kv, and the magnification is 10000x~50000x. The results are shown in Figures 5a to 5d. Figures 5a to 5d show that the modified PK805 montmorillonite is uniformly dispersed in the polyethylene glycol lactic acid polymer matrix and thus exhibits a cloud-like distribution.

<Crystal Properties and Types - Polarizing Microscope>

The polyethylene glycol lactic acid polymer (Comparative Example 1) and the polyethylene glycol lactate nanocomposites of Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, and Experimental Example 1-4 were observed by a polarizing microscope. The situation and time of spherulite growth. First, about 3 mg of polyethylene glycol lactic acid polymer (Comparative Example 1) and polyethylene glycol lactic acid of Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, and Experimental Example 1-4 were separately weighed. Nano composites. Then, each of the above was placed on a glass slide, covered with a cover glass, placed in a high temperature stage and heated to 190 ° C, and then cooled to a crystallization temperature (Tc) and kept at a constant temperature for 5 minutes, and the crystal was observed and photographed. And record the time when the crystal is complete. The shooting results are shown in Figures 6a, 6b, 7a, 7b, 8a, 8b, 9a, 9b, 10a and 10b. 6a is a crystallization start diagram of Comparative Example 1; FIGS. 7a, 8a, 9a, and 10a are Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, and Experimental Example 1-4. FIG. 6b is a crystallization completion diagram of Comparative Example 1 and FIG. 7b, FIG. 8b, FIG. 9b and FIG. 10b, Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, and Experimental Example The crystallization of 1-4 is completed.

6a to 10b show polyethylene glycol of Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, and Experimental Example 1-4 as compared with polyethylene glycol lactic acid polymer (Comparative Example 1). The crystal nucleus of the lactic acid nanocomposite material is increased and the crystal ball is small. In addition, Figures 6a to 10b also show that the more the modified PK805 montmorillonite addition ratio, the more crystal nuclei, the faster the crystallization rate and the shorter the crystallization time. This means that the addition of modified PK805 montmorillonite contributes to the improvement of crystalline properties, and the modified PK805 montmorillonite acts as an efficient nucleophilic group to enhance the crystallization rate of the polyethylene glycol lactic acid polymer.

<Dispersion, Crystal Properties and Types - Wide-angle X-ray Diffraction Analysis>

First, the wide-angle X-ray diffraction analyzer (CuKα, λ = 1.541 Å) is used to determine the layer spacing of Clay, and the interlayer distance of the modified PK805 montmorillonite is calculated according to Bragg's law: d = λ/2 sin θ (d-spacing). ). Next, the polyethylene glycol lactic acid polymer after completion of isothermal crystallization (Comparative Example 1) and Experimental Example 1-1 were scanned by a wide-angle X-ray diffraction analyzer at the crystallization peak starting temperature and the crystallization peak highest temperature, respectively. , Experimental Example 1-2, Experimental Example 1-3, and Experimental Example 1-4 of polyethylene glycol lactate nanocomposite, observed modified PK805 montmorillonite in Comparative Example 1 and Experimental Example 1-1, experiment The dispersion of the polyethylene glycol lactic acid polymer of Example 1-2, Experimental Example 1-3, and Experimental Example 1-4, and the degree of observation of the crystal form and crystal plane displacement. Experimental conditions: The scanning angle range is 2θ=10°~25°; the scanning speed is 1.5deg/min. Scanning results are shown in 11a, Fig. 11b and Table 2, where in Table 2 T ₁ is the initial crystallization peak temperature, T ₂ is the highest crystallization peak temperature.

11a, 11b, and 2, polyethylene glycol lactic acid polymer (Comparative Example 1) and Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, and Experimental Example 1 were observed at different temperatures. The -4 polyethylene glycol lactic acid nanocomposite produces sharp diffraction peaks (diffraction peaks of crystal planes (200)/(110) and crystal planes (203)) at about 2θ of 16.79 and 19.15. Corresponding means that the interlayer distance is 0.53 and 0.46 nm. These results indicate that the modified PK805 montmorillonite is completely dispersed in the organic material and the structure is unchanged.

Further, as is clear from Table 2, although the diffraction peak signal of Comparative Example 1 is similar to the diffraction peak signals of Experimental Example 1-1, Experimental Example 1-2, Experimental Example 1-3, and Experimental Example 1-4, However, the diffraction peak signal of the crystal face (101) of Experimental Example 1-2 disappeared, and the diffraction peak signal of the crystal face (203) of Experimental Example 1-3 and Experimental Example 1-4 was slightly shifted to the right, and the crystal face was crystallized. The diffraction peak signal of (101) is slightly shifted to the left, and the diffraction peak signal of the crystal plane (015) is slightly shifted to the right. This means that the addition of different proportions of the modified PK805 montmorillonite only slightly affects the crystal plane displacement of the crystal plane (101) and the crystal plane (015). That is to say, the addition of the modified PK805 montmorillonite does not completely affect the original crystal form of the polyethylene glycol lactic acid polymer, and even increases its crystallinity.

Experimental Example 2-1 to Experimental Example 2-3

The information on the main materials used in the preparation of polyalkylene glycol lactic acid-based nanocomposites is as follows.

Polyalkyl glycol-lactic acid copolymer (PLLA-PPG copolymer)

Source: Self-synthesis, the polypropylene glycol used has a molecular weight of 1000

Weight average molecular weight: 10,000 to 1000000

Molecular structure: as shown in the above formula 2.

Inorganic nanomaterial: montmorillonite

Source: manufactured by Paikong

Ion exchange capacity (CEC): 98meq/100g

Organic modifier: DilaurylDimethyl Ammonium Bromide (DMAB)

Source: TCI Manufacturing

Chemical formula: (C ₁₂ H ₂₅ ) ₂ (CH ₃ ) ₂ NBr

Solvent: chloroform

Source: Japan Pharmaceutical Manufacturing

<Preparation of Inorganic Nanomaterials Modified by Organic Modifiers>

The steps for preparing the inorganic nanomaterial modified by the organic modifier are as follows:

1. 5 g of montmorillonite was placed in 800 ml of distilled water and stirred at room temperature for 24 hours to completely swell the montmorillonite.

2. The amount of DMAB required to calculate the ion exchange capacity of montmorillonite is 6.4 g, and the formula is as follows: 98/100 x 5g x 1.2 = (weight average molecular weight of X/DMAB) x 1 x 1000.

3. 6.4 g of DMAB was dissolved in 20 mL of distilled water and stirred for 30 minutes.

4. The DMAB aqueous solution of the step 3 is added to the swollen montmorillonite aqueous solution of the step 1, and stirred at room temperature for 24 hours to uniformly mix the DMAB aqueous solution with the montmorillonite aqueous solution.

5. After filtering the aqueous solution of the step 4, it was washed several times with distilled water until the white nitrate solution was titrated, and no white precipitate was produced.

6. The product obtained in step 5 was placed in a vacuum oven at 100 ° C, and baked for 12 hours and then ground into a powder.

7. The powder obtained in step 6 is passed through a 325 mesh sieve. Sieve to obtain a modified montmorillonite having a particle size of about 40 μm.

<Preparation of polyalkylene glycol lactic acid-based nanocomposites>

First, the polypropylene glycol lactic acid polymer was placed in a vacuum oven and baked at a set temperature of 80 ° C for 12 hours to remove moisture. Next, the modified montmorillonite was dissolved in chloroform at a ratio of 0.5% by weight to carry out swelling and dispersion. Thereafter, a polypropylene glycol lactic acid polymer was added to the above solution, and stirred at 60 ° C for 24 hours. After stirring uniformly, the above solution containing the polypropylene glycol lactic acid polymer was poured into a Teflon disk, and placed in a vacuum oven, and dried at 60 ° C for 24 hours to completely remove chloroform to obtain Experimental Example 2 A polyalkylene glycol lactic acid-based nanocomposite of -1, that is, a polypropylene composite of polypropylene glycol lactic acid polymer/montmorillonite.

The polyalkylene glycol lactic acid-based nanocomposite of Experimental Example 2-1 was subjected to an analytical instrument such as a thermogravimetric analyzer (TGA, TA-Q500) and a differential thermal scanning analyzer (DSC, Perkin-Elmer DSC 4000). Analysis of thermal properties, and dispersion using a polarizing microscope (POM, OLYMPUS BX51), wide-angle X-ray diffraction analyzer (WXRD, Thermo Electron ARL X'TRAS), and transmission electron microscope (TEM, JEOL JEM2010) Identification of crystalline properties and forms. The steps, experimental conditions, and test results of these tests are detailed below.

The polyalkylene glycol lactic acid-based nanocomposites of Experimental Example 2-2 and Experimental Example 2-3 were prepared in the same manner except that the amount of modified montmorillonite was added, and the amount of the experimental example 2-2 was added. The amount added was 1 wt% and Experimental Example 2-3 was 1.5 wt%.

<Thermal property analysis - thermogravimetric analysis>

10 mg of the polypropylene glycol lactic acid polymer (Comparative Example 2) and the polypropylene glycol lactic acid nanocomposites of Experimental Example 2-1, Experimental Example 2-2 and Experimental Example 2-3 were separately weighed by a thermogravimetric analyzer and separately placed. Place the platinum plate in the instrument to record changes in temperature and weight. Experimental conditions: N ₂ flow rate was 20 mL / min; detection temperature range was 30 ~ 500 ° C; heating rate was 20 ° C / min. The test results are shown in Figure 12. Figure 12 shows that as the proportion of modified montmorillonite is increased, the thermal cracking temperature of the polypropylene glycol lactic acid polymer tends to increase. Further, at about 330 ° C, it can be seen that the residual weight also increases with the addition ratio of the modified montmorillonite. This means that the blending with the modified montmorillonite helps to increase the thermal stability of the polypropylene glycol lactic acid polymer.

<Thermal property analysis - differential thermal scanning analysis>

10 mg of the polypropylene glycol lactic acid polymer (Comparative Example 2) and the polypropylene glycol lactic acid nanocomposites of Experimental Example 2-1, Experimental Example 2-2 and Experimental Example 2-3 were respectively weighed by a differential thermal scanning analyzer, and Place them in an aluminum pan. Next, non-isothermal crystallization experiments and isothermal crystallization experiments were carried out, and detailed steps and descriptions thereof are as follows.

Non-isothermal crystallization experiment: heat from 25 ° C to 190 ° C at a temperature increase rate of 20 ° C per minute, then thermostat for 1 minute, then from 190 ° C at a rate of 1 degree per minute to 25 ° C, constant temperature for one minute, and then 20 minutes per minute The temperature was raised to 190 ° C at °C. The test results are shown in Fig. 13 and Table 3, and Fig. 14 and Table 4, wherein Tm ₁ , Tm ₂ , ΔHm, ΔHm ₁ , ΔHm ₂ , Xc, Tc and ΔHc are defined in the above experimental examples. The definition of each is the same.

Here, the crystallinity (Xc) is also calculated using Equation 3: Where ΔHm is the heat of fusion and f is the weight fraction. The ideal crystal melting heat of the polypropylene glycol lactic acid polymer is 94 J/g.

13 and Table 3 show that the polypropylene glycol lactic acid polymer (Comparative Example 2) and the polypropylene glycol lactic acid nanocomposites of Experimental Example 2-1, Experimental Example 2-2 and Experimental Example 2-3 exhibited a double when molten. The melting peak, and the shape of the double melting peak changes as the proportion of the modified montmorillonite is different. This indicates that the addition of modified montmorillonite affects the crystallinity of the polypropylene glycol lactic acid nanocomposite.

As can be seen from Table 3, the ΔHm values of Experimental Example 2-1, Experimental Example 2-2, and Experimental Example 2-3 first decreased and then increased with the addition of different proportions of modified montmorillonite, and the melting temperature (Tm) ₁ and Tm ₂ ) and ΔHm ₁ and ΔHm ₂ are reduced. The crystallinity was related to the change in the ΔHm value. Compared with Comparative Example 2, the ΔHm of Experimental Example 2-1 and Experimental Example 2-2 decreased, but the crystallinity of Experimental Example 2-3 began to rise.

From the above-mentioned enthalpy change situation, the addition of the modified montmorillonite does change the crystallinity of the polypropylene glycol lactic acid nanocomposite, and the crystallinity will increase as the proportion of the modified montmorillonite increases. Improved.

In addition, FIG. 14 shows that the crystallization peak of Comparative Example 2 is relatively smooth and wide, and the crystallization peaks of Experimental Example 2-1, Experimental Example 2-2, and Experimental Example 2-3 are relatively sharp. Further, as is clear from Table 4, the crystallization temperature (Tc) increases as the proportion of the modified montmorillonite is increased, and t _1/2 and the crystallization time are shortened, especially the polypropylene glycol of Experimental Example 2-1. Lactic acid nanocomposites have the most significant decline. This phenomenon indicates that the modified nucleophilic group is modified to enhance the crystallization rate of the polypropylene glycol lactic acid polymer.

Isothermal crystallization experimental procedure: heating from 25 ° C to 190 ° C at a temperature increase rate of 20 ° C per minute, then thermostating for 1 minute, and then rapidly cooling at a rate of 40 ° C per minute to the crystallization temperature (T ₁ , T ₂ , T _{3 )} , T ₄ , T ₅ ), wherein the five temperatures are the average five points taken from the low to the high in the first half of the melting peak in the non-isothermal crystallization experiment. After the crystallization was completed, the temperature was raised to 190 ° C at a rate of 5 ° C per minute. The test results are shown in Figures 15a to 15d and Tables 5 to 8.

15a to 15d and Tables 5 to 8 show that the melting temperatures (Tm1 and Tm2) of the polypropylene glycol lactic acid polymer vary with the crystallization temperature, and ΔHm1 and ΔHm2 exhibit a change in temperature. Trend: The higher the crystallization temperature, the lower the ΔHm2 value; the opposite ΔHm1 value increases with increasing crystallization temperature, which means that the crystalline form of the polypropylene glycol lactic acid polymer is different at different crystallization temperatures.

In addition, the reason for the change in the ratio of the double melting peak is that the nucleation rate is fast at a low temperature, and the crystal growth is limited. The time required for crystallization to approach the high temperature section is prolonged, and the crystal has a driving force for recombination and thickening. As time and temperature increase, the crystal also approaches stability, and the melting temperature increases as the crystal temperature increases, and the melting peak at a high temperature is replaced by a melting peak located at a low temperature.

Further, from the viewpoints of ΔHm value and crystallinity, as shown in Tables 5 to 8, the ΔHm of Experimental Example 2-1 and Experimental Example 2-2 was decreased as compared with Comparative Example 2, but Experimental Example 2-3 The crystallinity began to rise. In view of this, the modified montmorillonite is a good nucleating agent for the polypropylene glycol lactic acid polymer, which can increase the crystallinity thereof.

<Dispersion situation - transmission electron microscope>

The modified montmorillonite in the polypropylene glycol lactic acid composite material of Experimental Example 2-1, Experimental Example 2-2, and Experimental Example 2-3 was uniformly observed by a transmission electron microscope to determine whether or not the modified montmorillonite was uniformly dispersed. Experimental conditions: The lamp source is lanthanum hexaboride, the acceleration voltage is 200kv, and the magnification is 10000x~50000x. The results are shown in Figures 16a to 16c. Figures 16a to 16c show that the modified montmorillonite is uniformly dispersed in a polypropylene glycol lactic acid polymer matrix Inside, it presents a cloud-like distribution.

<Crystal Properties and Types - Polarizing Microscope>

The spherulite growth of the polypropylene glycol lactic acid polymer (Comparative Example 2) and the polypropylene glycol lactic acid nanocomposite of Experimental Example 2-1, Experimental Example 2-2, and Experimental Example 2-3 was observed by a polarizing microscope. The experimental conditions are the crystal growth process under the crystallization temperature (T ₁ , T ₂ , T ₃ , T ₄ , T ₅ ) taken in the isothermal crystallization experiment of differential thermal scanning analysis, and the temperature rise and fall rate is the same as that of the isothermal crystallization experiment. . The results of the photographing are shown in Figs. 17a, 17b, 18a, 18b, 19a, 19b, 20a and 20b, wherein Fig. 17a is a POM crystal diagram of Comparative Example 2 at the crystallization temperature T ₁ ; 19a and 20a are POM crystal diagrams of Experimental Example 2-1, Experimental Example 2-2, and Experimental Example 2-3 at the crystallization temperature T ₁ ; and FIG. 17b is a POM crystal diagram of Comparative Example 2 at the crystallization temperature T ₅ 18b, 19b, and 20b are POM crystal diagrams of Experimental Example 2-1, Experimental Example 2-2, and Experimental Example 2-3 at a crystallization temperature T ₅ .

17a to 20b show that at a lower temperature (crystallization temperature T ₁ ), the nucleation rate of the crystal nucleus is faster, but the crystal is smaller and the number of crystal nuclei is more scattered and crystallized; and as the temperature increases (crystallization temperature T ₅ ), the crystal is a Maltese cross-type crystal, and as the crystallization temperature increases, the number of crystal nuclei decreases, and the crystal growth space increases. In addition, Figures 17a to 20b also show that as the proportion of modified montmorillonite increases, the number of crystals increases at the crystallization temperature T ₅ , which means that the nucleus after the modified montmorillonite is added The number is increased, which increases the crystalline properties of the polypropylene glycol lactic acid polymer.

<Dispersion, Crystal Properties and Types - Wide-angle X-ray Diffraction Analysis>

First, the wide-angle X-ray diffraction analyzer was used to determine the layer spacing of Clay, and the interlayer distance of the modified montmorillonite was calculated according to Bragg's law:d=λ/2sinθ. Then, under the crystallization temperature (T ₁ , T ₂ , T ₃ , T ₄ , T ₅ ) taken in the isothermal crystallization experiment of the differential thermal scanning analysis, the isothermal crystallization is completed by scanning with a wide-angle X-ray diffraction analyzer. The polypropylene glycol lactic acid polymer (Comparative Example 2) and the polypropylene glycol lactic acid nanocomposite of Experimental Example 2-1, Experimental Example 2-2 and Experimental Example 2-3 were used. Experimental conditions: CuKα, λ = 1.541 Å; scanning angle range is 2θ = 10 ° ~ 25 °; scanning speed is 1.5 deg / min. The scanning results are shown in Figures 21a to 21e and Tables 9 to 13.

Table 11: Crystallization temperature T ₃

From Fig. 21a to Fig. 21e and Tables 9 to 16, it can be seen that the 2θ value, the interlayer distance (d) and the strength of the polypropylene glycol lactic acid nanocomposite change after adding different proportions of the modified montmorillonite. The n value can be calculated using the formula nλ=2dsinθ. In addition, the size and shape of the crystals will affect the 2θ value of the diffraction peak. Therefore, it can be seen from Table 9 to Table 16 that the polypropylene glycol composite material of modified montmorillonite is added at different crystallization temperatures and different ratios. The crystallization behavior will also change.

Although the present invention has been disclosed above by way of example, it is not intended to limit the present invention. The scope of the present invention is defined by the scope of the appended claims, which are defined by the scope of the appended claims, without departing from the spirit and scope of the invention. quasi.

Claims (10)

A method for preparing a polyalkylene glycol lactic acid-based nano composite material, comprising mixing an inorganic nano-material modified by an organic modifier into a monomer of a polyalkylene glycol lactic acid polymer, and a polyalkylene glycol lactic acid system Formed in a prepolymer of a polymer or a polyalkylene glycol lactic acid based polymer matrix, wherein the organic modifier comprises a surfactant having a C ₆ -C ₄₀ alkyl group or a C ₆ -C ₄₀ aryl group, The inorganic nano-material is hydrophilic, and the polyalkylene glycol lactic acid-based polymer includes a polyalkylene glycol lactic acid polymer or a derivative polymer of a polyalkylene glycol lactic acid polymer. The method for producing a polyalkylene glycol lactic acid-based nano composite according to claim 1, wherein the polyalkylene glycol lactic acid polymer comprises a polyethylene glycol lactic acid polymer or a polypropylene glycol lactic acid polymer. Things. The method for preparing a polyalkylene glycol lactic acid-based nano composite material according to claim 1, wherein the organic modifying agent hydrophobizes the inorganic nano material to make the inorganic nano material and The dispersibility and compatibility between the polyalkylene glycol lactic acid-based polymers are increased. The method for preparing a polyalkylene glycol lactic acid-based nano composite according to claim 1, wherein the organic modifier comprises a C ₆ -C ₄₀ alkyl quaternary ammonium salt, a C ₆ -C ₄₀ alkane. Phenyl quaternary ammonium salt, sodium lauryl sulfate, triethanolamine laurylamine, sodium lauryl amide, phenylammonium chloride, polyoxyethylene coconut oil fatty acid decylamine, coconut oil fatty acid monoethanol amide, hard fat Acid diethanolamine, stearic acid monoethanolamine, C ₁₄ H ₂₉ SO ₄ Na, C ₁₆ H ₃₃ SO ₄ Na, C ₁₈ H ₃₇ SO ₄ Na, C ₁₂ H ₂₅ SO ₄ N (C ₄ H _{9 4} , C ₁₂ H ₂₅ SO ₄ N(CH ₃ ) ₃ C ₁₂ H ₂₅ , C ₁₂ H ₂₅ CH(COO)N(CH ₃ ), (C ₄ H ₉ ) ₂ CHCH ₂ (OC ₂ H ₄ ) ₉ OH and nC ₁₂ H ₂₅ (OC ₂ H ₄ ) ₃₁ OH or a mixture thereof. The method for preparing a polyalkylene glycol lactic acid-based nano composite material according to claim 1, wherein the organic modifier is modified by the total weight of the polyalkylene glycol lactic acid-based nano composite material. The inorganic nano material is added in an amount of from 0.01% by weight to 10% by weight. The method for preparing a polyalkylene glycol lactic acid-based nano composite material according to claim 1, wherein the inorganic nano-material modified by an organic modifier is blended with the polyalkylene glycol lactic acid The method of the polymer monomer, the polyalkylene glycol lactic acid polymer prepolymer, or the polyalkylene glycol lactic acid polymer matrix comprises: modifying the organic modifier with a solvent Swelling the inorganic nano material; mixing the polyalkylene glycol lactic acid polymer or a prepolymer thereof, and the swelled inorganic nano material, wherein the polyalkylene glycol lactic acid polymer or prepolymerization thereof The polymer chain of the substance will be intercalated into the inorganic nanomaterial, and the solvent is present between the layers of the inorganic nanomaterial; and the solvent is removed. The method for preparing a polyalkylene glycol lactic acid-based nano composite material according to claim 1, wherein the inorganic nano-material modified by an organic modifier is blended with the polyalkylene glycol lactic acid The polymer monomer, the polyalkylene glycol lactic acid polymer prepolymer, or the polyalkylene glycol lactic acid polymer matrix method includes: modifying the organic modifier Inflating the inorganic nano material; placing the swollen inorganic nano material in a monomer of the liquid polyalkylene glycol lactic acid polymer or a monomer containing the polyalkyl glycol lactic acid polymer Dissolve In the liquid, the monomer of the polyalkylene glycol lactic acid polymer is polymerized between the layers of the inorganic nanomaterial. The method for preparing a polyalkylene glycol lactic acid-based nano composite material according to claim 1, wherein the inorganic nano-material modified by an organic modifier is blended with the polyalkylene glycol lactic acid The monomer of the polymer, the prepolymer of the polyalkylene glycol lactic acid polymer, or the method of the polyalkylene glycol lactic acid polymer matrix comprises: the polyalkylene glycol lactic acid polymer Heating the monomer and the prepolymer to form the molten polyalkylene glycol lactic acid polymer; after cooling the molten polyalkylene glycol lactic acid polymer or melting the polyalkane The alcoholic lactic acid-based polymer mixes the molten polyalkylene glycol lactic acid-based polymer and the inorganic nano-material modified with an organic modifier by a shearing force. The method for preparing a polyalkylene glycol lactic acid-based nanocomposite according to claim 1, further comprising using an isothermal heat treatment procedure to increase the crystallinity of the polyalkylene glycol lactic acid-based polymer. A polyalkylene glycol lactic acid-based nano composite material prepared by the method for producing a polyalkylene glycol lactic acid-based nano composite material according to any one of claims 1 to 9.