TW200819499A - Preparation of PLA/Clay nanocomposites and its application - Google Patents

Abstract

This invention is about a series of polylactic acid/Clay nanocomposites preparation method and its application. In order to improve crystalline and physical properties of the polymer nanocomposites , the nanoscale inorganic layered silicate (montmorillonite, MMT) were incorporated into biodegradable poly(lactic acid) (PLA) to prepared a series of PLA/organic modified layered silicate (OMLS) nanocomposites and between the polymer and the layered silicate in PLS nanocomposites lead to the organic and inorganic phases being dispersed at the nanometer level. The polylactic acid/Clay nanocomposites have good biological compatibility can apply to the biomedical material extensively, For example: operation seaming twine, medicine releases Carrier...etc. A managed compost unit has the potential to be the effective disposal infrastructure for biodegradable plastics. Quite have industry's utilizing nature.

Description

200819499 IX. Description of the Invention: [Technical Field to Which the Invention Is Applicable] The present invention relates to a lactic acid-based polymer composite material and a lactic acid-based polymer composite material which is modified to be finely modified by money. The organic modifier is _interfacial activity # y ^ & mouth plate), drug release carrier, tissue engineering stent and other materials, paper coating materials, etc., which are quite productive [prior art] In recent years, total plastic products 41% of the output is used in the packaging workers' filial piety, and the beans are used in the packaging of foods, which are made of polyethylene (PGlyH^ propylene (polypropylene, PP), polystyrene (polyst ps); Vinyl chloride, ^ 丄^ fruit naturally becomes undegradable waste. This is also the existence of a full-valve reduction tree. How to deal with these petal wastes has two ways to deal with these wastes. The first one is to bury the waste, but there may be plastics that are not easily decomposed and the site is insufficient. The problem. On the other hand, / =: f is buried today, and future generations will still have to bear the other two methods left by the predecessors to incinerate or recycle to achieve the purpose of reduction, but the incineration of plastic will produce a large number of carbon greenhouses The effect of the body, causing global warming, the resulting high heat will destroy the incinerator, and the service life of the ϋίϊΐ, in addition, the combustion decomposition & toxic reduction and toxic substances ^ also seems to be able to solve this problem, but It takes a lot of manpower and energy: it separates the garbage heap, classifies, cleans, dries and grinds different plastics. ▼ The above steps, and finally get the desired product. Therefore, the cost of recycling is expensive, and the shell 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 amount of total energy cost is reduced. For the above reasons, the current treatment methods have many problems rather than the best choices. It is urgent to develop green 咼 molecular materials (along the knives, avoid using toxic or harmful ingredients in the process of 200819499, and can be natural In the development of materials in the environment, there is still a research in the field of materials science. This is a material that has a degradable decomposability, especially the biodegradability of the technology, in order to meet the needs of the new era. Bekata ^%% of the ecological materials, =, 2i, tt gas exhibition prospects of green materials compared to the plastic, polylactic acid Feng * town 'a few ideal replacement of the valve. And - 1 material source is sufficient ······················································································································ Boundary 4, the record, in the financial and material degradable = various processing 'can be gathered milk 13⁄4 good Juzhong jj 1 j acid j lun. Because d is the production of clothing t fishing, anti-odorous volley Yusu 5 'iijs materials such as bone nails in the stainless steel As a new type of orthopedics, the characteristics of the secondary knives are free of the characteristics of the bitter metabolism of the second knives, so that the small computer parts of the disease can be recorded in the note type. The technology is applied to the Fujitsu brand to gather money. 200819499 ϊ 阻 _ _ ( ( ( ( ( ( ( ( _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 起 起 起This is the green product of the 1τ industry and: 働 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易Nowadays, there is a breakthrough in the technology of 2, and the use of polymer alloy technology and g oil contribution, when the potential of the machine is self-fresh. In addition to 5 good bio-sharpable, high biocompatibility, good, temple quality, but its biggest drawback is that flexibility does not work; ss shadow another; =sSSii=; =:s;: Causes considerable impact. This issue: '?ff modified inorganic materials' such as montmorillonite has a nano-layered, high-rigidity fruit to increase the molecular size stability L, and strengthen the polymer ^ ^ 咼 knife / 彖 彖 奈 复合 composite material In the conventional technology, most of the emphasis is on the conductive substrate such as: acrylic, ^ tree with 14 sub-substrate physical properties, such as: thermal stability, mechanical strength, flame retardant 1: L chaos :, the synthesis method of U-nan molecular/montmorillonite composite can be used in-situ i, two: one liquid poly a, ritual polymerization, suspension polymerization, condensation polymerization and ring-opening polymerization, etc. (meltmtercalation) and a variety of other different ways to achieve the dispersion effect of the exfoliation or intercalation type in the knife substrate. ^ The liquid insert 2 is that the inorganic material used is organically modified and then dissolved, and f is used to increase various physical strengths, especially to solve the problem of soft enthalpy of the lactic acid compound. Further, isothermal heat treatment is further utilized. The program makes the crystallinity even higher. SUMMARY OF THE INVENTION The present invention relates to a lactic acid-based polymer composite material, a preparation method thereof, and a soybean acid-based polymer composite material which are obtained by blending an organically modified inorganic material into a lactic acid hydrazine. It has the dispersibility and compatibility with the polymerization, and the nature of the treatment, in addition, the step-by-step heat treatment process makes the 13⁄4. / The invention of the invention uses a nano-grade inorganic material modified by a surfactant to be uniformly dispersed in a bismuth polymer substrate to prepare a series of biodegradable polylactic acid nano composite materials, which are modified by 200819499 inorganic materials. The addition increases the crystallinity, and further increases the crystallinity by using an isothermal enthalpy treatment procedure. The polylactic acid-based polymer used in the present invention comprises a homopolymer, a copolymer or a derivative thereof. The copolymer thereof may be selected from the group consisting of (1) aliphatic acid poly(Aliphatic polyester). (2) Polyacrylic acid Cyano acrylate. (3) Polyamide (polyamide). (4) Polyorthoester poly(orthoesters) (POE). (5) Polyanhydrides (PAH). (6) A copolymer of a polymer such as polyacetal or (7) polyglycolic acid (p〇iygiyC〇iicacid, pga). Among them, polylactic acid (PLA) and/or copolymer with polyglycolic acid (PGA) (poly[lactide-co-glyc〇lide], PLGA) is the most excellent. Biocompatibility, biodegradability, and appropriate material physicochemical properties are suitable for use in the present invention. The polylactic acid used in the present invention may be a linear, aliphatic thermoplastic polyester (Polyester) having a chemical structure such as Formula 1 in the form of polylactic acid (pDLLA), which is bioresorbable and biological. A polymer material that is biodegradable and biocompatibility.

The physical, chemical and biological properties of the three molecular materials will help to understand the application of this material in medicine. Polymer materials can determine their main physicochemical properties by their stereochemistry, structure, molecular weight and distribution. Polylactic acid has an asymmetric atomic center (asymmetric atom), which contains two optical isomers of r and S; ^:?,,; depending on the monomer molecule, It is divided into 1^ form polylactic acid (1>1^8), polylactic acid (PDLA) and D, L form polylactic acid (PDLLA). PLLA(R) and PDLA(5) f, w ^, in the compound, the crystal region (cryStaiiine) and the amorphous region (am〇rph〇us) have a large crystallinity of about 37%; and PDLLA _ No compensation, polymer sadness. Since PLLA is a crystalline polymer; pLLA is slower than pDLLA in terms of degradation, and PLLA is inferior to PDLLA in terms of capacitance. Therefore, there are four types of polymer types: D-PLA, D, and L-PLA, and the fourth type of meso-PLA is practically used. Polylactic acid has three crystal structures: one is a pseudo-oj^horhombic a structure with a 1〇3 helix chain con ormation, and the other is a less stable 200819499, with 31 The orthorhombic beta structure of the helical chain structure, as well as the epitaxial crystallization? Crystal structure. The PLLA arrangement rule is a crystal of semi-crystalline (crystallinity of up to 4% or more) and a melting point (Tm) of about 170 to 200. The glass transition temperature (Tg) is about 55-65 ° C, PDLLA is amorphous amorphous non-crystalline transparent material 'glass transition temperature Tg, about 5 〇 ~ 60 ° C, and no obvious Tm point, polylactic acid The nature parameters are different due to molecular weight, molecular weight distribution, purity and preparation; the parameters are slightly different in different literatures. PDLLA is soluble in most organic solvents such as tetrahydrofuran (THF), acetone, gas, benzene, etc., while PLLA is only soluble in scent and monochloromethane. Since there is a methyl group in the main chain of polylactic acid, it is less hydrophilic than polyglycolic acid, and the rate of hydrolysis in the body is much slower than that of PGA. Depending on the initial molecular weight, morphology (non-crystalline region or crystalline region) of the polymer, the type and shape of the stereoisomer, etc., the rate of degradation of the polymer can range from a few weeks to several months to one to two years. PLA can be formed into a body by hydrolysis to form lactk acid, which is then metabolized into carbon dioxide and water molecules via the Krebs cycle and excreted. Commercially available polylactic acid (PolyLactide; PLA) uses starch as a raw material, and lactic acid (Lact = Add) is obtained after fermentation, and lactic acid is polymerized into low molecular weight polylactic acid by condensation polymerization, and then J $ ^Kfouplmg Agent} The low molecular weight polylactic acid is joined to form a good mechanical substance, the molecule $polylactic acid. The synthesis of polylactic acid has been polymerized to date, indirect (open-loop polymerization), and copolymerization, such as Formula 2. There is a enthalpy (reduction method is lactic acid aCtic acid) as a monomer, in the case of nitrogen and without any catalyst, ι'η, condensation reaction. This method is relatively simple and inexpensive, but it is difficult to control the molecular weight, molecular weight distribution coefficient and terminal group obtained by the reaction. If the reaction conditions and time are changed: about, the molecular weight is increased to about tens of thousands. Prison and temperature>5 under vacuum conditions, first oxidize lactic acid into Lactide

If 曰), and then use the method of the open-end polymerization, the left-handed cyclic lactide, in the presence of octanoic acid (the molecular weight of the Stannous ^ U 丨ΓΙ ' field, like tens of thousands of social, * to hundreds of thousands or Million ΐit can control the molecular weight of polylactic acid by the kind and amount of catalyst to make polylactic acid versatile and versatile, and can be mass produced to reduce such a 200819499

Glucose, OEgDsacchaiide^ Stomh

Del〇di^sitioii + DistilMoii

Mrljpotici ll*LJLaetid

Me E^EMUHacii mesoiD^Laelid

PoijitLrli^tide) ΡοΙϊ(Ρ^ϋ-1ιοίι4β) Formula 2 Human 轵γ ·.....,>y 丄, 豕 muscle, 母母,石夕酸,石夕石, 二材itf dispersion The mode is mechanical dispersion, only can = machine ί material: inorganic layer 5 points 1 = 3⁄4 phase]! S this larger material: ftr but high cost, and the celestial soil impurity content u potential Si low tssis to: sericulture The soil hodgepodge is easily inflated to increase the distance. However, the body 200819499 ^the bad lipophilicity is poor, so before it is mixed with the oily polymer, the montmorillonite needs to be changed. The original hydrophilic montmorillonite is modified into a lipophilic inhibitor. 1101^) 糸太月=The inorganic substance used is preferably clay or montmorill〇nite, preferably too gasy. In the natural world, the rich inorganic minerals, 趟it in the specific embodiment of the invention, the clay itself is a metal ion with 4 layers of oleic acid, the water can be expanded, the chemical formula of the volume of expandable clay: (Al2 xMgx^(Si4)iv〇iG(〇H)nH2〇

Interlayer storable cation

〇 and • 矽 (a small part of aluminum) spring aluminum, iron, magnesium 〇 oxygen @ -OH

The structure of the clay (montmorillonite, Montmorillonite) is not particularly limited, and any long-chain alkyl/aromatic surfactant can be used in the present invention, including: cationic interface activity Agent, cerium ion type surfactant, nonionic boundary type surfactant, amphoteric surfactant, etc. can be applied & the invention, 1 such as, long chain alkyl quaternary ammonium salt gamma ship] ^ business coffee 111111011 丨1 blood dip 1 〖), long-chain phenyl, quaternary alkyl phenylammonium salt, sodium lauryl sulfate, lauric acid a hard-lined, unified stupid, ^ hard hard 曱 basic methyl know, laurel Trimethylacetoxyacetic acid trimethylcaprolactone, poly-meric acid fatty acid decylamine, coconut oil fatty acid monoethanol decylamine, stearic acid diethanol decylamine, stearic acid 200819499 monoethanol decylamine, (: 121125 wind ( 3 parts, (: 141129 wind 013) 3; 81*, (: 161133 wind 013) 3; 81 ·, [CH3(CH2)n] 2 (CH3) 2NBr ^ C14H29S04Na > C16H33S04Na > C18H37S04Na ^ Ci2H25S 〇4N(C4H9)4 > C12H25S〇4N(CH3)3C12H25 > C12H25CH(COO)N(CH3) > (^HACHCHXOQHAOH and n-CuHWOQI^OH, etc., among which long-chain alkyl quaternary ammonium salts, especially C12H25N(CH3)3Br, C14H29N(CH3)3Br, [CHWCHJnMCHANBr, etc., if used for biomedical materials or packaging For materials, the non-toxic or non-toxic non-ionic surfactant can be used to modify the '^. The active agent is illustrated by the example of a quaternary ammonium salt, which is composed of the hydrophilic end of the quaternary ammonium salt and the clay. The cation exchange ion is carried out in order to make the long-chain alkyl group of the quaternary ammonium salt enter the clay sound, thereby achieving the effect of widening the interlayer distance, and at the same time, the interlayer of the inorganic clay has affinity and affinity, and thus the polymer chain exists in The oleophilic end of the quaternary ammonium salt between the clay layers produces the desired effect. Under the same operating conditions, the X-ray diffraction analysis shows that the change in interlayer distance will vary depending on the type of surfactant. If the polymer material and montmorillonite are to be mixed into a nanocomposite, it is necessary to select a suitable surfactant to modify the surface of the montmorillonite, so that the distance between the montmorillonite layers becomes larger and the height is high. Molecular materials are easy to enter The synthesis method of the lactic acid polymer/inorganic nano composite material of the present invention can be carried out by in_situ polymerization such as solution polymerization, emulsion polymerization, suspension polymerization, condensation polymerization, ring-opening polymerization, etc. or melt intercalation and various other kinds. In the manner of montmorillonite, it is possible to achieve delamination or intercalation in the polymer substrate. Solution intercalation method of solution polymer or prepolymer (intercalation of p〇lymer ^!?〇1^=&〇1118〇11出〇11), this method is based on solvent, its lactic acid polymer Or the pre-% must be dissolved to dissolve, and the layered citrate can be swollen. First use the solvent, such as water, nail, gas, etc., to give the layered sulphate salt to swelli (swelli) and then use it, = or _ add people, mix and mix, at this time, high score / lining in layered citrate The interlayer is present in the interlayer of the layered sulphate, and the solvent is removed to obtain the polymer/layered silicate (p〇1 r/1 d sUic nano composite). In situ intercalative polymerization method, in which a swelled layered citrate is placed in a liquid monomer or a solution monomer, and a polymer is polymerized between layers. It is carried out by heating or free radicals, and a suitable initiator is diffused into the interlayer. The initiator or the catalyst can be first placed in the interlayer by ion exchange and then subjected to a Melt intercalation method. The polymerized softened point polymer and organically modified layered silicates (OMLS) are mixed under anneaing or shearing (Shear). It is more valuable than the first two methods. In order to utilize this method, it can be operated in a general environment without using a solvent. -11- 200819499 [Embodiment] 1. Preparation of a nano composite material Materials used:

(1) Poly L-lactic acid [p〇ly (L-iacticacid^PLLA] Source: SIGMA Weight average molecular weight: 85,00 (Τ160,000) Its molecular structure is as follows:

(2) ΡΚ805 Momtmorillonite Source: Paikong Ion exchange capacity (CEC): 98meq/100g

(3) Organic modifier: DilauryldimethylAmmonium Bromide [CH3(CH2) 1 l]2(CH3)2NBr Source: TCI The molecular structure is as follows:

(4) Tetrahydroftiran (THF) Source: TEDIA -12- 200819499 2. The montmorillonite organic modification A selected Baikang PK805 montmorillonite, the ion exchange capacity (CEC) is 98meqM〇〇g The modified agent uses Dilauryl Dimethyl Ammonium Bromide four-level money, and the sardine miscellaneous method is used to carry out the organic modification of montmorillonite. The following formula calculates the amount of modifier needed = 98/100 X 5g (for Clay) x 1.2 = (XMW of intercalating agent) x 1 χ l〇〇〇., X is the amount of modifier, 98/100 represents ion exchange capacity per OOg of montmorillonite, and is added in excess (1·2) Double) modifier. Experimental procedure: Steaming the turban 'Stirring 24 trees in a room temperature towel, and letting the montmorillonite (2) lean ion exchange capacity (CEC) to calculate the amount of modifier required, the formula is as follows: II ? X 5g (f〇r Clay) x 12 =(X/MW ^intercalating agent) x 1 xi〇〇〇(3) In this experiment, $PK805 montmorillonite, CEC value is 98 (four) one, ▲ by 笪(4) kg^ f·4 g, dissolved into 20 steaming water, stirring for 3 〇V. The bath was added to the swollen aqueous montmorillonite solution and stirred at room temperature for 24 hours. (3) The solution is mixed and stirred uniformly. After filtering, it is washed several times with steaming water until the silver nitrate > valley droplets are timed, and no white sediment is produced. 2: The product obtained was placed at 100. (: In a vacuum oven, after drying, it is ground into a powder. After sifting through a 325 mesh sieve, the modified clay can be obtained, which is about 40 μm. ', $8 only, montmorillonite layer Identification of the spacing Most of the montmorillonite is hydrophilic, because its interlayer is mixed with hydrated cations (such as: **, 2), so it is easy to absorb water, but the polymer is a lipophilic burnt chain structure, so A water-based The compatibility of the demineralized dispersion in the lipophilic polymer substrate is achieved by the y active agent, which is generally called a cationic modifier.

The distance from the 龅 layer f0! is larger than that of the layer _ hydrated ions. Therefore, the S-molecules between the montmorillonite layers are also more suitable for the pure montmorillonite layer, so that the montmorillonite _2 is the same as the Dilamyl dimethyl Ammonium Bromide. The organic modified montmorillonite was prepared as a cation, and the identification of the interlayer spacing of the manganese layers was carried out. * XRD pattern, montmorillonite crystal surface -13- 200819499 4. Polylactic acid mixed with modified montmorillonite will be placed in a vacuum oven to remove water vapor at 6G °c for 48 hours, and set aside. Desaturated, in different proportions (2: 3, 4, 5w 哟 dissolved in tetrahydroanthracene Tr ^ F) Nano complex 'then add people into the 仃 _ layer, prepared into a polylactic acid montmorillonite experimental steps : (1) - Poly-f-acid and 0. Kiss ^ kiss ^ called ^ Qing's modified montmorillonite 'dissolved in 5ml of tetrahydrofuran for 12 hours. ~ Wan, (2) solution, pour the Teflon disc, in the vacuum supply box, to 6 〇. The tetrahydrofuran was removed in 4 hours to prepare a film. Shuang 3, isothermal crystallization sample prepared ii ii = 0 tPlate heating plate, the degree is heated from room temperature to i9 〇〇 c, holding temperature for 3 minutes, the sample is quickly placed in the oven, placed for 12 hours isothermal crystallization , crystal growth of the mouth i, XRD diffraction pattern, infrared, Raman spectroscopy, and do DSC analysis. 4 temperature crystallization temperature (9). C, 110〇c, 12〇〇c, 13〇〇c, 140〇c 160 ° C, 170 ° C, the process is as follows. , Experimental procedure: (1) Set the oven to the desired temperature. (2) After the temperature is raised to the desired temperature, prepare the sample for melting. (3) Take the slide, place the sample on top, and place the coverslip. Heat the plate to 190 ° C and hold the sample for 3 minutes to completely melt the sample. (5) Move the sample quickly to the oven. (6) Take it out after 12 hours of storage. 6 material properties analysis (1) differential, scanning analyzer (Differential Scanning Calorimeter (DSC) surface surface ^ first with indium _ium, mP. = 156.60 〇 c) and words (Zinc, mp.Ml9 · 47.;;) j standard ^ test strips do double-point calibration to correct the nset value of the heat absorption and melting temperature; and in the ΐ ϋ ϋ ϋ ϋ ϋ base base base ; ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为Nitrogen; in order to remove moisture, high purity nitrogen is introduced outside the _er. The operation procedure of the DSC in this experiment is carried out in a nitrogen flow rate of 2 ,, which is divided into six stages, as follows: (A) Isothermal: The tray is placed in Dsc and held at 25 ° C for 1 minute to achieve temperature balance. . 200819499 (B) Temperature Scan: The temperature is raised from 25 ° C to 190 ° C, and the heating rate is 20 ° C / min.亍(C) Isothermal: Hold at 190 °C for 2 minutes to eliminate the thermal history of the material. (D) Temperature Scan: Cool the temperature from 19 °C at a cooling rate of 2 °C/miri To (E) Isothermal: at 25. <: Hold the temperature for 1 minute to reach the temperature balance. (F) Tempemture Scan: The temperature was further raised from 25 ° C to 190 ° C, and the heating rate was 2 ° C / min. (2) Wide-angle X-ray diffraction analysis (WAXD)

Model: ThermoARLX'TRA (a) Using X-ray diffractometer (Cu Ka, ?=1·541Α), compare and modify the layer spacing of montmorillonite, calculate the detachment according to Bragg's law: d=?/2sin? Soil d (001) layer spacing (d-spacing). (b) Polylactic acid and modified montmorillonite were prepared by solvent injection molding into a series of polylactic acid nanocomposites with a scan angle range of 2? = 1. ~1〇. The scanning speed was 1.5 deg/min, and the dispersion of montmorillonite in polylactic acid was observed. (〇) The sample was isothermally crystallized for 12 hours, with a scan angle range of 2?=1〇. ~25. The scanning speed was 1.5 deg/min, and the crystal forms at different temperatures and different montmorillonite contents were observed. (3) Scanning Electron Microscope (SEM) The surface morphology of the polylactic acid series nanocomposite was observed with the aid of SEM. The experimental method is to dry the material sample and fix it on a metal base, and gold plating with a gold plating machine to increase the conductivity of the polymer material. The pattern was then observed under a voltage of 15 kV. (4) Polarizing Optical Microscope (POM). Under different crystallization conditions, the polymer chains will have different f crystal forms depending on the arrangement. Therefore, with the help of POM, the crystal growth rate of the sample and the difference in the state of the state must be observed. The experimental procedure is to heat the sample from a room temperature to 190 using a Hot Stage heating controller. (:, after the temperature is kept for 2 minutes, the sample is completely melted, and then cooled to different temperatures to observe the crystal growth of each sample. Under different crystallization conditions, the polymer chains will have different spherulites depending on the arrangement. Therefore, the crystal growth of each sample must be observed with the help of p〇M. -15- 200819499 Effect of the invention: 1. Organic modification of montmorillonite, a kind of inorganic mineral acid with a layered structure The salt must be ion-exchanged by the hydrophilic end of the quaternary ammonium salt. The purpose is to make the long-chain alkyl group of the quaternary ammonium salt enter the viscous layer and the interlayer to achieve the effect of widening the distance between the layers of Y. Therefore, it has two properties: S5 high gas and the oleophilic end of the quaternary ammonium salt existing between the clay layers. The Fray diffraction analysis map shows that the PK805 layer spacing is U·81 a, and the interface is active [Q2H25N ( C Can: Confirming the interfacial activity _addition can enlarge the layer spacing of the clay. Under the κιΐΐϊίΐΐ, the X-ray diffraction analysis shows that the change in interlayer distance varies depending on the type of surfactant. Did〇decyldimeth, [CH 3 (CH2w door + burnt structure and bond angle, so that double long chain filament and inorganic clay layer A effectively enlarge the interlayer distance to about 22 Α, the distance of the original clay table a different kind of surfactant pair ΡΚ-805 Modified 20 and d_(d-space Α) Surfactant 2? d -space(A) No 7.48 11.81 C12H25N (CH仏Br 5.28 16.73 Ci4H29N(CH3)3Br 4.92 17.95 Ci6H33N(CH,), Br 4.70 18.79 JCH3(CH2)iil2(CHd, NBr 4.02 21 Qfi 2. Nanocomposite 趟, ϋ ϋ ' 系 以 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物Lai Na (four) around ^ column-16- 200819499 Its (J (001) plane diffraction peak appeared in 2? about 4 〇 position 22A, when adding different proportions ... ρκ8 〇 5, has been observed, 卞 distance About the peak of the crystal signal, the distance of the montmorillonite layer is expanded to the knot of the d(001) surface of the phase, and 1 is scattered in the main body of the polylactic acid, and the layer of x-ray is scattered. Dodge __以尨=蒙3, thermal analysis τ to Fig. #聚同比例〇福05 organicized clay, after gamma; Sr* in pure acid ', k' 4, crystal growth quality, inserting montmorillon The degree of layers, the mechanical and various properties, such as single crystal, spherulites, dendrites, etc. in the melting of the growth of the 'crystals on the heterogeneous nucleolus nucleation, and then each J radiation, growth Until the neighbors are joined to each other. The addition of Si骛 and the addition of different proportions of montmorillonite polylactic acid to the polarizing microscope curtain in the lower 'for the polylactic acid crystals, and the crystalline form of 荨ft: tit placed on the hot plate Slide the sample, place the sample on the slide if-like ride, and smooth the sample with a glass rod. After the temperature is controlled in the box, place the sample for 12 hours. With the micro-compliance 5,,, " 曰曰 type, the observation magnification is 125x, with the CCD detector to take the stone, the slide with the sample, cut into about L5xL5cm size, a history, borrow This interpretation of the change in the crystal face, and finally take about 3 mg sample, force analyzer, analysis of the melt and crystallized _. Calculate the crystallinity of the test rubber by the following formula: % Crystallinity ? 1〇〇? -A ugly m /δη: where is the heat of fusion, f is the weight fraction, △ /? is the ideal crystal melting of PLLA-17 - 200819499 When the heat is 94 J/g·, the crystal form obtained by the acid under different isothermal crystallization conditions, 120 ° C 1 曰 "f, and the crystal is smaller, the number of crystal nuclei is scattered, 130 ° C, tit crystal With the increase of crystallization temperature, the crystal crystals also increase by i. The X obtained under isothermal crystallization conditions at different temperatures, the diffraction pattern ΐ, and the isothermal crystallization treatment of polylactic acid have ι〇1,〇 I0,2〇(vi10,203, etc.=3i, rfiff'1〇〇°C, 11〇°C, 12〇°C isothermal crystallization sample has 20 (V110, 203 绕 diffraction peak, 130〇C new Increasing the diffraction peak of 15 crystal planes, 14〇〇c, 15〇〇c have more diffraction peaks of the crystal plane, and the diffraction peak of 015 disappears at 160°C, 170. (: 101 diffraction peak diffraction peak, at the same time The 2 1() crystal plane is split at a larger angle of 2°, and the crystallization temperature affects the formation of the crystal plane. The different temperatures of the ί-like surface and the x_ray diffraction peak 2 are listed in Table 2. Figure 6 is pure polylactic acid Under isothermal crystallization conditions, the temperature rise rate from 2 °C per minute is raised from 25T to the heating curve. It can be seen from the figure that pure polylactic acid grows at different isothermal crystallization temperatures f, if it melts, its melting point will follow When the temperature of the isothermal crystallization increases, there will be a slight increase in the enthalpy, melting point and crystallinity value of the polylactic acid composite material of the different lactic acid and the different content of the organic montmorillonite under the condition of no temperature crystallization. Among them, PLLA2PK805, JJ^3PK805, PLLA4PK805, and PLLA5PK805 represent the f, 3 wt%, 4wt%, and 5 wt% of the mechanical montmorillonite (PK805), respectively. The results show that the crystal after adding the mechanical montmorillonite (PK805) The degree is obviously improved. Figure 7 shows the crystal form obtained by adding polylactic acid composite material (PLLA5PK805) with 5wt% organic montmorillonite. Under different isothermal crystallization conditions, the nucleation rate of crystal nucleation is faster at 120〇c. The crystal is small, the number of crystal nuclei is scattered and crystallized, and it is a Maltese cross-type crystal at 130 ° C and 140 ° C. As the crystallization temperature increases, the crystal crystal also increases, 150 ° C to 170 ° C. The nucleation rate is small and the number of crystal nuclei is small, so that the crystal can grow around. The crystalline form is radiated and is dendritic, 160. (:, 170. (: is a concentric ring-shaped dendritic crystal. Figure 疋, plus 5 wt% of organic montmorillonite polylactic acid composite The χ-ray diffraction pattern obtained by the material (PLLA5pK8〇5) under different temperature crystallization conditions, the graph shows that the polyacid J without isothermal crystallization has 1〇1, 〇1〇, 2〇〇 /11〇, 2〇3, etc. diffraction peak signal, 100〇C, 110oC, 120 C special; ^ Crystallized sample has 200/110, 203 two crystal plane diffraction peaks, i3〇°C added 015 crystal plane diffraction peak, 140 ° C, 150 ° C and 101,010 two crystal face diffraction peak, ι6 〇. When 曰c 〇15 diffraction peak disappears, 17 〇. At the time of 〇101, the diffraction peak disappears, creating a new 211 diffraction peak, while the 200/110 crystal plane splits a small diffraction peak at a larger angle of 2?. The crystal face of the isothermally crystallized sample with different concentrations of 5 wt% organic montmorillonite (PLLA5PK805) and the X-ray diffraction peak 2 values are listed in Table 4. Figure 9 shows the yc/w ^ rate of poly-18 - 200819499 lactic acid composite (PLLA5PK805) with 5 wt% organic montmorillonite added under isothermal crystallization conditions at different temperatures from 25.319 (Dsc obtained twice by rc) Rise

Ik is gradually increased in crystallization temperature, and the melting peak is gradually decreased. Figure 10 and Figure ^^ are respectively at a temperature drop rate of 2〇c/min0 from 19 (TC to WC, 4Wt% obtained, there is; ^ Mongolian depolymerized lactic acid composite material (PLLA4PK805, PLLA5PK805) at different temperatures, etc. ^ Surname 曰i, the temperature curve 'When the temperature rises to 19 (TC, the residual nucleus will still have different crystallization rates. Table 5 is the addition of 4 wt% organic montmorillonite polylactic acid, material (PLLMP circle in The values of isothermal crystallization of different temperatures were significantly improved after heat treatment. Table 6 shows the heat of polylactic acid composite (PLLA5PK805) with added wt% organic montmorillonite under isothermal crystallization conditions at different temperatures. The values of enthalpy, melting point and crystallinity are significantly improved after heat treatment. 'Table 1 The crystal plane of the isothermal crystallization sample at different temperatures and the X-ray diffraction peak 2 crystallization temperature base, 2? (angle CQ 101 010 200/110 203 015 211 Untreated 12.3 14.6 16.5 18.9 _ 100°C I— 16.4 18.7 _ iio°c — — 16.4 18.7 _ 120°C 一16.6 18.8 _ 130°C 一 — 16.5 18.8 22.0 _ 140°C 12.4 14.7 16.6 19.0 22.3 _ 150°C 12.3 14.8 16.6 19.0 22.3 _ 160°C 12.3 14.7 16.6 19.0 — _ 170°C — 14.6 16.6/ 17.0 19.0 a 23.4 Table 3 Thermal enthalpy, melting point and crystallization of pure polylactic acid and polylactic acid composites with different content of organic montmorillonite under isothermal crystallization conditions at different temperatures Degree Tc〇C) △Hc(J/g) Tm^C) Tm2(°C) △Hf (J/g) •?c(%) Pure PLLA 100.9 -22.8 — 172.9 45.7 48.6 PLLA2PK805 121.3 -42.0 168.1 174.8 52.6 56.0 PLLA3PK805 123.3 -44.9 169.1 175.4 52.0 55.3 PLLA4PK805 125.1 -48.1 170.4 175.9 53.5 56.9 PLLA5PK805 125.1 -41.9 170.4 176.3 46.1 49.0 -19- 200819499 Table 4 Adding 5 wt% organic montmorillonite polylactic acid composite (PLLA5PK805) Crystal plane of isothermally crystallized sample at different temperatures and X-ray diffraction ridge 2? value crystallization temperature version (2?), (angle) (°C) ΙΟΙ OlO 200/110 203 015 211 untreated ioo°c _ 16.5 18.8 litre — — 16.5 18.8 — a no°c — 16·5 18.8 — — 130°C — 16.6 18.9 — — I40°c — a 16.8 19.2 I — I50°c 12.4 14.8 16.7 I9.l One by one I60°c 12.3 14.7 16.7 19.0 I—I70°c a 14.9 16.8 I9.l - Table V was added 4wt% of organic montmorillonite composite material of polylactic acid (PLLA4PK805) at different temperatures enthalpy of isothermal crystallization conditions, the melting point, crystallinity values crystallization temperature - (. 〇

TcCC) AHc(J/g) TimCC) Tm2(°C) in g)f ?〇(%) Untreated 125.1 -48.1 100 124.1 -46.2 lio 126.0 -48.4 120 126.2 -48.2 130 128.7 -47.8 140 131.2 -56.5 150 136.9 -58.6 160 135.8 -48.0 170 135.5 -52.9 .4.4.4.2.0.6.5.0.8 0.9.9.0.0.9.6.9.9. 766776666 11 1A 1x lx 1A 1x 11 11 1x 175.9 53.5 56.9 175.1 52.3 55.6 173.9 53.5 56.9 175.0 55.4 58.9 173.8 50.4 53.6 172.9 63.8 67.9 — 72.0 76.6 — 53.4 56.8 — 57.4 6l.l Table 6 Addition of 5wt% organic montmorillonite polylactic acid composite (PLLA5PK805) under isothermal crystallization conditions at different temperatures , melting point, crystallinity value

Crystallization temperature - CQ

TcCC) AHc(J/g) TmiCC) Tm2(°C) △Hf (J/g) ?c(%) Untreated 125.1 -41.9 170.4 176.3 46.1 49.0 100 124.4 -50.5 170.1 175.4 53.8 57.2 lio 125.3 -59.6 170.0 174.9 60.2 64.0 120 126.4 -45.0 170.5 175.4 52.8 56.2 130 126.5 -49.0 170.6 175.3 54.2 57.7 140 128.3 -45.6 170.3 175.0 50.8 54.0 150 128.6 -46.1 170.6 174.9 50.8 54.0 160 131.5 -49.7 167.4 A 54.2 57.7 170 131.8 -46.6 168.9 _ 51.2 54.5 -20- 200819499 ί ί Polymer compound (4), its crystallized crystallinity, 谇 崎 骷 骷 骷 寺 寺 结晶 结晶 结晶 4, its crystallinity can be increased to 76.6%, improve the crystallization of medical materials: for example, the material itself Biocompatibility is excellent, so it can be widely used in the environment. Pollution and injury can be widely applied to the ten laws of 曰常生, and can be obvious (3): Ιϋ _# has the value of industrial use, hopes to get the ambiguity of the early ί ί ί ί, However, this month's monthly limit is not detailed. On the contrary, various changes can be made without departing from the spirit of the invention. =,;月巳-21- 200819499 [Simple description of the diagram] Ξ Γ montmorillonite and - _ 聚纽奈米复合材料 X, diffraction pattern θ I, the addition of the New Zealand is not __ montmorillonite (.固的固一图2, from 190°, 巧^^JLf, adding different proportions of Q_PK8()5 organicized clay, the cooling curve is shown in Figure 4. X_r?v diffraction pattern obtained under isothermal crystallization conditions. Under the isothermal crystallization conditions of different temperatures, the temperature is increased from 25 C to 19 CTC. The DSC secondary heating curve is shown in Fig. 7. It was observed that the polylactic acid compound of 5 wt% organic montmorillonite was added, and the crystal form obtained under different isothermal crystallization conditions (8) 12〇t towel) 13〇tc (d) 150 °c (8) 160 °C (f) 170 °C for 12h Figure 8. X-ray diffraction pattern obtained by adding 5 wt% organic montmorillonite polylactic acid composite material under isothermal and "crystalline conditions" at different temperatures. Figure IX. Adding 5 wt% The polylactic acid composite material of organic montmorillonite is heated from 25 ° C to 19 CTC at 2 ° C / min under isothermal crystallization conditions at different temperatures. The DSC temperature rise curve obtained is 10, and the polylactic acid composite material with 4 wt% organic montmorillonite is reduced from 19 CTC to 25 ° C at a temperature drop rate of 2 ° C/min under isothermal crystallization conditions at different temperatures. The DSC cooling curve is shown in Figure 10. The polylactic acid composite with 5 wt% organic montmorillonite is cooled at a temperature of 2 °C/min from 19 °C to 25 ° under isothermal crystallization conditions at different temperatures. C's DSC cooling curve [main component symbol description] No-22-

Claims (1)

200819499 Patent application scope: 2 4, 5, 6, 7, 8 ' 9, 10, 1 Bu 12, a polylactic acid composite material, which is composed of an organic modified disc composite material, and the organic modified agent is inert Hydrophilic inorganic materials can be hydrophobized to increase their separation from the Sif S51C (2) material, which can be blended with the interface-active shells and the enamel, which can improve the crystallinity and physical properties of the Juyi g-system composites. For example, the polylactic acid composite material of the first application patent scope, the clay material, the montmorillonite, the mica, the Wei salt, the stone stone, the metal, and the 2 stupid materials, the polylactic acid composite material of the first item is selected. The inorganic material is a polylactic acid-based composite material according to the first aspect of the patent, wherein the amount of the inorganic material modified by the surfactant is 0.001 to 15% by weight based on the total amount of the composite. f is a polylactic acid-based composite material according to the first aspect of the patent application, wherein the amount of the inorganic material modified by the surfactant is α1 to iGwt% of the total amount of the composite. The heart of the shell tiff follows the compound of 1 item, and the towel polylactic polymer comprises a homopolymer, a copolymer or a derivative thereof. The polylactic acid-based composite material according to claim 1, wherein the polylactic acid-based ping-ply polymer comprises and is selected from the group consisting of (1) aliphatic acid polyester (Aliphatic P〇lyester), (2) polyacrylic acid, and cyano ester (poly Cyano acrylate), (3) polyamides (polyamides), (4) polyorthoesters (POE), (5) polyanhydrides (PAH), (6) polycondensate 〇1}^61318), (7) Polyglycolate } 1} ^ 〇 1 Record this 丨 (1, 〇 )) and other copolymers of polymers. The polylactic acid-based composite material according to claim 1, wherein the polylactic acid-based copolymer is a polylactic acid (PLA) and/or a copolymer with polyglyc〇lic acid (PGA) (p) 〇ly[lactide-co-glyc〇lide], PLGA). The polylactic acid-based composite material according to claim 1, wherein the surfactant is a surfactant having a long-chain alkyl group or an aromatic group. The polylactic acid-based composite material according to claim 1, wherein the surfactant comprises a surfactant such as a cationic surfactant, an anionic surfactant, a nonionic boundary surfactant, or an amphoteric surfactant. . The polylactic acid-based composite material according to claim 1, wherein the modified surfactant is a quaternary alkylammonium salt, a quaternary alkylphenylammonium salt, or a quaternary alkylphenylammonium salt. Sodium lauryl sulfate, triethanolamine lauryl acid, sodium lauryl sulphate, trimethyl ammonium sulphate, benzyl ammonium chlorate, -23- 13, 200819499 dimethyl benzyl succinate Ammonium, lauryl dimethylamino acetic acid trimethyl ammonium lactone, polyoxyethylene coconut oil fatty acid decylamine, coconut oil fatty acid monoethanol decylamine, stearic acid diethanol decylamine, stearic acid monoethanol amide, C12H25N(CH3)3Br, Ci4H29N(CH3)3Br, C16H33N(CH3)3Br, C14H29S04Na, C16H33S04Na, C18H37S04Na, C12H25S04N(C4H9)4, 14, 15, 16, 17, 18, 19, 20, 2, Ci2H25S〇4N (CH3) 3Q2H25, C12H25CH(CO〇)N(CH3), (C4H9)2CHCH2(OC2H4)9〇H and n-C12H25(〇C2H4)31〇H. The polylactic acid-based composite material according to claim 1, wherein the modified surfactant is a quaternary alkyl ammonium salt and a quaternary phenyl ammonium salt. ), gasified benzene sulphate, C12H25N(CH3)3Br, C14H29N(CH3)3Br, C16H33N(CH3)3Br, [CHXCHJuHCHANBi·, etc. The polylactic acid-based composite material according to claim 1, wherein the modifier is a long-chain alkyl group or a long-chain phenyl quaternary ammonium salt. A method for preparing a polylactic acid-based composite material, wherein an organically modified prosthetic material is blended into a monomer, a prepolymer, or a polymer of the lactic acid-based polymer to form a composite material. The organic modifier is a surfactant. For example, in the preparation method of the polylactic acid-based composite material of claim 16 of the patent application, the method of preparing the human body can be solution polymerization, emulsion polymerization, suspension polymerization, condensation polymerization, and polymerization, in-situ intercalation polymerization, or It is carried out by means of melt intercalation or the like. The method for preparing a polylactic acid-based composite material according to claim 16 of the patent application is a solution polymerization method, an in-situ intercalation polymerization method, or a melt intercalation method. The method for preparing a polylactic acid-based composite material according to claim 16 of the patent application, wherein the solution method is an inorganic material which is modified by a surfactant, and the solvent is used first, and the benefit machine is given for swelling and then used, and then the lactic acid is used. When the polymer or prepolymer is added together, the polymer chain will be intercalated into the inorganic material, and the solvent is also present in the layer of the layered benefit material, and finally the solvent is removed to obtain the polymer/inorganic material. Composite ^ The surfactant hydrophobizes the hydrophilic inorganic material to increase the dispersibility and compatibility of the ruthenium polymer to improve crystallinity and physical properties. /w, σ Β 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如A method for preparing a polylactic acid-based composite material, which comprises an in situ intercalative polymerization method, an inorganic material modified by a κ surfactant, swelled in a liquid monomer or dissolved, and polymerized between polymers The polymerization reaction may be carried out by heating or free i, and a suitable initiator may be diffused into the interlayer, or the initiator may be first aged between the layers and then polymerized. ~μ提取媒利-24- 200819499 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 > 32, the preparation method of the polylactic acid secret material of the 16th item The Melt intercalation method is a polylactic acid secret of the 16th item of the polymer which has reached the softening point and the organically modified layered inorganic material after the annealing is set to β-'. The preparation method of the composite material The inorganic material in the pot may be selected from the group consisting of clay, montmorillonite, mica, silicate, vermiculite, 'U, and the polylactic acid-based composite material of the U, wherein the patent application scope Preparation of 16 polylactic acid composite materials 1 The amount of the inorganic material modified by the surfactant is 0001~15ς^ of the total amount of the composite, and the preparation method of the polylactic acid composite material according to the 16th item of the patent scope of Shenqing The amount of the inorganic material modified by the surfactant is the total amount of the composite 〇1~1〇wtg:,, the preparation method of the polylactic acid composite material of the 16th patent application, the lactic acid polymerization in the basin The composition comprises a homopolymer, a copolymer or a derivative thereof. A method for preparing a polylactic acid-based composite material according to claim 16, wherein the lactic acid-based composite comprises and is selected from the group consisting of (1) aliphatic acid polyester (Aliphatic p()lyestg, (A polyacrylic acid cyano group) Poly cyano acrylate, (3) poly phthalamide p〇iy (amides), (4) polyorthoester poly(orthoesters) (POE), (5) polyanhydride (p〇iyanhydrides) (PAH), (6) Polyacetate (polyacetate), (7) polyglycolic acid (p〇lygl Uc add, copolymer of a polymer, etc. ' ^ Patent Application No. 16 of the polylactic acid-based composite material preparation method, wherein the polylactic acid system The copolymer is a polylactic acid (PLA) and/or a copolymer with polyglycolic acid g^^ycolic acid (PGA) (p〇ly[lactide_C(>glya)'lide], as claimed in claim 16 The method for preparing a polylactic acid-based composite material, wherein the surfactant is a surfactant having a long-chain alkyl group or an aromatic group. The preparation method of the polylactic acid-based composite material according to claim 16 of the patent application, wherein the interface The active agent comprises: a cationic surfactant, an anionic surfactant, a non-ionic boundary A surfactant, such as an active agent, an amphoteric surfactant, etc. The preparation method of the polylactic acid-based composite material according to claim 16 wherein the modified surfactant is a long-chain quaternary ammonium salt (qUartemary alkylammonium salt) ), long-chain phenyl four-stage salt (quartemary alkylphenylammoniumsalt), sodium lauryl sulfate, triethanolamine laurylamine, sodium lauryl amide, trimethylammonium chlorate, chlorinated chlorinated chlorinated Dimethylbenzyl chloride stearate, lauric acid dimethylamine vinegar ^trimethylammonium lactone, polyoxyethylene coconut oil fatty acid decylamine, coconut oil fatty acid monoethanol decylamine, stearic acid diethanol hydrazine Amine, stearic acid monoethanolamine, C12H25N(CH3)3Br, C14H29N(CH3)3Br, C16H33N(CH3)3Br, [CH3(CH2)ii]2(CH3)2NBr-C14H29S〇4Na-C16H33S〇4Na-C18H37S04Na - -25- 200819499 33, 34, 35, c12h25so4n(c4h9)4, c12h25so4n(ch3)3c12h25, C12H25CH(COO)N(CH3), (C4H9)2CHCH n-C12H25(〇C2H4)31〇H, and the like. The preparation method of the polylactic acid-based composite material according to claim 16 wherein the modified surfactant is a quarttemary alkyl ammonium salt and a long-chain phenyl quaternary ammonium salt (qUartemary). Phenyl ammonium salt, gasified ammonium, C^HaNCCHABr, C14H29N(CH3)3Br, C16H33N(CH3)3Br, [CH3(CH2)n]2(CH3)2NBr, and the like. A method for producing a polylactic acid-based composite material according to claim 16 wherein the concentrating agent is a long-chain alkyl group or a long-chain phenyl quaternary ammonium salt. VIII 36, 37, 38, 39, 40, 41, a method for improving the crystallinity of a polylactic acid-based polymer by blending an organically modified inorganic material with a monomer, a prepolymer of the lactic acid-based polymer, Or in the polymer matrix ▲ to improve the crystallinity, wherein the organic modifier is a surfactant. As a method of increasing the crystallinity of a polylactic acid-based polymer according to the 35th patent application, the pot method can be carried out by solution polymerization, emulsion polymerization, suspension polymerization, condensation polymerization, ring-opening polymerization or melt intercalation. The method of improving the crystallinity of the polylactic acid-based polymer, as in the 35th article of the patent application, 1 is a liquid solution polymerization method or a melt intercalation method. For example, in the method of claim 35, the method for improving the crystallinity of the polylactic acid-based polymer, the intermediate solution method is an inorganic material which is modified by the surfactant, and the solvent is used first, and the material is allowed to be inflated for later use, and then the lactic acid is used. The polymer or prepolymer is added together and mixed. At this time, the polymer chain will be intercalated into the inorganic material, and the solvent is also present in the layered helmet, the layers of the material, and finally the solvent is removed to obtain the polymer/ Inorganic tantalum composite material, the surfactant hydrophobizes the hydrophilic inorganic material to increase its dispersibility and compatibility with the polymer to improve crystallinity and physical properties. For example, in the method of claim 35, the method for improving the crystallinity of a polylactic acid-based polymer, wherein one step comprises using an isothermal heat treatment procedure to improve crystallinity and physical properties, such as the application of 35 patents to increase the polylactic acid. a method for crystallinity of a polymer, wherein the in situ intercajative method (In situ intercajative p〇iymerizati〇n meth〇(j) is a swelling of an inorganic material modified by an f interface agent, and is placed in a liquid monomer. Or the solution monomer, = two and the polymer is polymerized between the layers, the polymerization reaction can be carried out by heating or free, and the suitable initiator can be diffused into the interlayer, or the starting catalyst can be ion exchanged. The method of increasing the crystallinity of the polylactic acid-based polymer according to the item % of the patent scope of the invention, wherein the Melt intercalation method is to perform annealing or a shearing Force I" is a mixture of a polymer having a softening point and an organically modified layered inorganic material. The method for increasing the crystallinity of a polylactic acid-based polymer according to claim 35, -26-42, 2008194 99 费中^Inorganic materials may be selected from clay, montmorillonite, mica, silicate, vermiculite, metal oxides. 43, 44, 45, 46, 47, 48, 49, 50, 5 Boli range 35 The method for improving the crystallinity of a polylactic acid-based polymer, wherein the inorganic material is a nano-scale clay. For example, the method for increasing the crystallinity of a polylactic acid-based polymer according to Item 35 of the patent scope is modified by a surfactant. The amount of the inorganic material added is 〜1 to 15% by weight of the total amount of the composite. The method for increasing the crystallinity of the polylactic acid-based polymer according to the 35th item of the patent application, the amount of the inorganic material modified by the surfactant 〇1~1〇wt% of the total amount of the composite. The method of increasing the crystallinity of the polylactic acid-based polymer according to claim 35, wherein the polylactic acid-based polymer comprises a homopolymer, a copolymer thereof or A method for increasing the crystallinity of a polylactic acid-based polymer according to claim 35, wherein the polylactic acid-based copolymer comprises and is selected from the group consisting of (1) aliphatic acid polyester (Aliphatic polyester) (p〇iy Cyan〇acryiate), (3) P〇iy (amides), (4) polyorthoacetes (POE), (5) polyanhydrides (PAH), (6) polyfluoric acid (p〇iy acetais), (7) poly A copolymer of a polymer such as polyglycolic acid (PGA). The method for increasing the crystallinity of a polylactic acid-based polymer according to claim 35, wherein the polylactic acid-based copolymer is polylactic acid (PLA). And/or copolymer with polyglycolic acid (PGA) (p〇iy[iactide-co-glyc〇lide], PLGA), for example, to increase the crystallisation of polylactic acid polymers according to claim 35 The method wherein the surfactant is a surfactant having a long bond group or an aromatic group. The method for improving the crystallinity of a polylactic acid-based polymer according to claim 35, wherein the surfactant comprises: a cationic surfactant, an anionic surfactant, a nonionic boundary surfactant, and an amphoteric surfactant. Etc. A method for increasing the crystallinity of a polylactic acid-based polymer according to claim 35, wherein the modified surfactant is a quaternary alkylammonium salt or a long-chain phenyl quaternary ammonium salt ( Quaternary alkylphenylammonium salt), sodium lauryl sulfate, triethanolamine laurylamine, sodium lauryl sulphate, gasified triammonium stearate, gasified benzene sulphate, gasified dimethyl benzyl ammonium stearate , Laurel dimethylamino-ammonium tridecyl ammonium lactate, polyoxyethylene coconut oil fatty acid decylamine, coconut oil fatty acid monoethanol decylamine, stearic acid diethanol decylamine, stearic acid monoethanol decylamine, 0 :121125:^(〇13)331*, (:141129:^((^3)361·, C16H33N(CH3)3Br > [CH3(CH2)11]2(CH3)2NBr > C14H29S04Na ^ C16H33S04Na, C18H37S04Na , C12H25S04N(C4H9)4, C12H25S04N(CH3)3C12H25, C12H25CH(COO)N(CH3), -27-200819499 (C4H9)2CHCH2(OC2H4)9〇H and n-C12H25(OC2H4)31OH, etc. 52 53, 54 , 55 > 56 > 57, 58 > 59, as in the scope of patent application No. 35 to improve the crystallinity of polylactic acid-based polymers The modified surfactant is a quarttemary alkyl ammonium salt, a long-chain phenyl tetra-salt salt, a benzalkonium chloride, a C12H25N(CH3)3Br, a C14H29N (CH3) 3Br, C16H33N(CH3)3Br, [CHWCHduHCHANBr, etc. • ΐΐ ΐΐ, the scope of the 35th method to improve the crystallinity of polylactic acid-based polymers, the agricultural modified shell is long-chain alkyl or long-chain phenyl four Grade 铍 salt. Less, two's are stipulated in the stipulations of the stipulations of the stipulations of the stipulations of the stipulations of the stipulations of the stipulations of the stipulations of the stipulations Structure, person, t stent, etc.. Continued mouth reading (bone nail plate), drug release carrier, tissue engineering material; 66 to the item of any one of the items such as application for special (four) for the main crane The material of the composite material - ⁄ ⁄ ⁄ ⁄ ⁄ ⁄