TW201105738A - Method for preparing thermostable polylactic acid material by using sol-gel process - Google Patents

Abstract

This invention relates to a method for preparing a thermostable polylactic material by using a sol-gel process, in which a silyl polymer or tripentanedione aluminum undergoes hydrolysis and condensation reactions, and polylactic acid and the solvent thereof are added during the reaction process of hydrolysis and condensation. Accordingly, the produced inorganic sol is dispersed uniformly and added into polylactic acid through the sol-gel process. When the inorganic sol is converted into inorganic gel to produce mixed polymers, and the mechanic property of the polylactic acid can be improved, and the thermal expansion coefficient can be reduced, thereby widely applying polylactic acid in industry purposes.

Description

201105738 IV. Designation of the representative representative: (1) The representative representative of the case is as follows: (2) The components of the representative figure The simple explanation: No. 5. If there is a chemical formula in this case,

Please disclose the chemical formula of the most __ characteristics: 6. Description of the invention: [Technical field to which the invention pertains] The invention relates to a preparation method, in particular to a method for utilizing a sol-gel-like polylactic acid material, The properties of the polymer are improved by a sol-gel process. Heat preparation [Prior Art] ° Bay. 201105738 In general, plant and animal products are degradable, and the difference in environmental conditions (especially aerobic or green) will also biodegrade, so there is no degradation by biological reaction, such as metal, glass, resin, etc. The disposal of the composition, not the biodegradable material, is the main source of environmental pollution. The resin composition is applied to an outer casing as a plurality of electrical products. In the case of the deficiencies, when the resin composition is treated as a cockroach, the oxidizing gas such as dioxin is released in the burning _ by the inferior heat tree. Further, when the resin composition is buried in the soil, it is almost impossible to decompose. Therefore, the resin composition has a problem that it is difficult to decompose, and the treatment of the resin composition causes environmental pollution. Therefore, various countries in the world are developing technologies for replacing the resin composition with a non-resin composition, for example, polylactic acid. The monomer of 'PolKLactic acid' is lactic acid. Generally, the composition of lactic acid is made from wheat, rice bran, corn, potato and sugar beet containing wheat, which is fermented by raw materials. The product is a member, so polylactic acid can be biodegraded into lactic acid early body' while lactic acid is a substance that can be decomposed by biological reaction, and biological reaction decomposition usually refers to the decomposition of microbial environmental waste, polylactic acid (pu) is A biodegradable polymer that is also a non-toxic, non-irritating natural substance. Due to the wide range of raw materials for lactic acid, the acid has become the second organic acid in the world, and the final product of polylactic acid degradation is carbon dioxide and water, while carbon dioxide and environmental silk (4), even if it is fiber, is harmless. In the incinerator, there is no toxic gas, so polylactic acid is widely used, especially in the case of Shengxiyun. For example, surgical materials can be made. However, polylactic acid (PLA) materials also have their own disadvantages that cannot be overcome by themselves: (1) Hydrophilicity. The polylactic acid molecule contains a large amount of g-bonds, which are hydrophobic substances, resulting in poor hydrophilicity, which reduces its biocompatibility; and eighty (2) poor mechanical properties. Polylactic acid itself is a linear polymer, and the product obtained by the polymer has a wide content: (4), which makes the strength of the polylactic acid material often fail to meet the requirements, and the impact resistance is poor. At the same time, the polylactate is unstable to heat. The addition of temperature at the melting temperature and thermal decomposition temperature will also cause a significant drop in molecular weight; (3) the degradation rate is difficult to control; and 201105738 (4) the price is high. Therefore, the present invention proposes a method for preparing an enamel polylactic acid material by a sol-gel method in view of the above problems, which not only improves biocompatibility but also improves structural strength. SUMMARY OF THE INVENTION The main object of the present invention is to provide a method for preparing a heat-stable polylactic acid material by a transfer method, which is a mixture of a mixed-use solution and a poly-money solution, and a modified polymer. The second objective of the present invention is to provide a green remedy for preparing a heat-reinforcing polylactic acid material in Lai County, and to form a lyotropic gel by hydrolysis and condensation reaction. Mix polylactic acid. The present invention provides a method for preparing a heat-stable (tetra) polylactic acid material in Lai County, which is capable of preparing a thermal solution by adding a first solvent to a Wei-based polymer to obtain an inorganic sol, and then preparing a solution, which comprises a second dissolution. Interestingly mixing the 'inorganic' and adding the human swab to produce organic, ° thus preparing the organic/inorganic hybrid polymer by a simple process to polymerize the enemy aircraft by the sol, and by Wei Sihe (4) The stability of the heteropolymer. 2There is to provide another method for preparing the thermal stability of the polylactic acid material by the melt-melting method. First, a solvent dissolves the polylactic acid to form a solution, and then sequentially adds the three-dimensional two. Outline: Mixture 'to carry out hydrolysis and condensation reaction to form organic/inorganic sol, and to make organic/inorganic hybrid polymer by simple process, to temporarily smash the machine'. The polymer is coated to improve the mechanical properties of the polymer, and the stability of the polymer is improved by the Wei-based polymer or the triamethylene ruthenium. The preparation of the heat-sensitive polylactic acid material by the method, the seeding and the transfer method The prescription is dissolved in seconds to prepare 彡, ☆ agent> pain polylactic acid Form-the first solution, and take care of the second solution through the spear. In the r* two "field into - the second solution and carry out hydrolysis and condensation reaction, and in the solution of the second two-two dioxin, then add the first solution and The hybrid polymer was prepared by a simple process to produce an organic/non-ruthotropic sol-gel method to improve the stability of the polymer by 201105738 base polymer or tris-gallium. In order to give your reviewers a better understanding and understanding of the structural features and efficacies of the present invention, the following is a description of the preferred embodiment and the detailed description of the following: [Embodiment] First, please refer to The first figure is a flow chart of a preferred embodiment of the present invention. As shown in the drawing, the present invention is a method for preparing a thermally stable polylactic acid material by a sol-gel method, which comprises dispersing and mixing a fluorenyl polymer on a polylactic acid particle by a sol-gel method. According to the step S110, a one second siiane polymer is added by using a first solvent to carry out hydrolysis and condensation reaction to form an inorganic;: a binder, the reaction efficiency of the present embodiment for increasing hydrolysis and condensation reaction Further, a catalyst is further added, which comprises hydrochloric acid to cause hydrolysis and condensation reaction in an acidic environment to have a pH of 2-4' to catalyze hydrolysis and condensation reaction, wherein the first solvent of the embodiment comprises water and ethanol. The sulfonyl polymer of the present embodiment is selected from the group consisting of tetraethyl decane, tetramethyl oxalate, and a combination thereof, and the inorganic sol of the present embodiment is cerium oxide (Si 〇 2). The inorganic sol is a linear network structure. According to the above, as shown in step S120, a second solvent is used to dissolve polylactic acid (plyly (lactic acid)) to form a solution, wherein the second solvent comprises tetrahydropyran (tetrahydjOf coffee n, Lu THF); weaving, as shown in step S13G, dissolving the inorganic sol into the solution containing polylactic acid, taking the organic/non-observable polymer, and the organic/inorganic hybrid polymer of the present embodiment comprises polylactic acid and oxidation Hey. In addition, for a more complete reaction, the present embodiment further includes the steps s14 and =, as shown in step S140, 'putting the solution containing the inorganic sol on a doctor blade and circulating it to complete the reaction to generate the An organic/inorganic hybrid polymer, wherein the cyclic baking system uses a circulating oven to bake the second solution containing the inorganic sol at different temperatures; if the step is not to vacuum-bake the organic/inorganic hybrid polymer to remove Solvent and moisture were removed, and the vacuum was supplied to the baking system using a vacuum oven to bake the organic/inorganic hybrid polymer at a temperature of 7 degrees Celsius. In the above, the present invention prepares an organic/inorganic hybrid polymer by a sol-gel method, and the hydrolytic condensation reaction generated by the sol-gel reaction mechanism causes the inorganic sol particles to be dispersed in the poly-201105738 acid. Improve the mechanical properties and stability of polylactic acid. Please refer to the second figure, (iv) a flow chart of another preferred embodiment of the present invention. As shown in the figure, it is difficult to reduce the concentration of the tripentanedione to the polylactic acid particles to improve the polylactic acid machine. In the first step _, the _th-solvent dissolves the polylactic acid, and the first solvent of the present embodiment contains tetrahydro hydrazine, and the first solvent of the present embodiment is dissolved in four (four) Lactic acid; it is difficult to show the addition of the triterpenoid solution to the solution, wherein the dipentanedione aluminum solution contains aluminum trietone (Isu pentanedi_at (0 aluminum (m)) and tetranitrogen The second solvent is included in the solution, and the second solvent comprises water and ethanol, as shown in step S230, wherein the second solvent comprises water and ethanol. As shown, the hydrolysis and condensation reactions are carried out to form the polymer 3 of the inorganically converted polymer. In order to increase the reaction efficiency of the hydrolysis and the condensation reaction, a catalyst is further added, which contains Wei, and the hydrolysis and condensation reaction are carried out. In an acidic environment, the acid value (PH) is 2-4' to catalyze hydrolysis and condensation reaction. The polymer of this embodiment contains polylactic acid and bismuth. In addition, for a more complete reaction, this embodiment further includes steps. S25〇 and S260', as shown in step S25 The solution containing the organic/inorganic sol is placed on a doctor blade and cyclically baked to completely react to form the mixed silk compound, and the towel circulation baking system utilizes: the ring-ring oven is baked at different temperatures to contain the inorganic sol. The second solution; as shown in step s26, vacuum baking the polymer to remove solvent and moisture, wherein the vacuum is baked using a true two oven at a temperature of 70 degrees Celsius to bake the organic/inorganic mixture The present invention is a flow chart of another preferred embodiment of the present invention. As shown in the figure, the present invention can be uniformly dispersed to a poly group by a ruthenium alkyl polymer and aluminum trietone. In lactic acid, to improve the mechanical saltiness and t疋 property of the t-milk. First, according to the step s3i, the first solvent is used to dissolve the polylactic acid (Poly (lactic acid)) to form a first solution, wherein the first solution A solvent comprises tetrahydrofuran; as shown in step S320, the ruthenium alkyl polymer is dissolved by the second solvent to form a second solution and subjected to hydrolysis and condensation reaction. This embodiment is further added in order to increase the reaction efficiency of hydrolysis and condensation reaction. Urge a reagent comprising hydrochloric acid to hydrolyze and condense in an acidic environment having a pH of 2-4 to catalyze hydrolysis and condensation, wherein the second solvent comprises 201105738 water and ethanol. Reaction mechanism hydrolysis reaction ( Hydrolysis): Si(OR)4 + H20; (HO)Si(OR)3 + H20 ; (HO)2Si(OR)2 + H20 ; (H0)3Si(0R) + H20 Condensation reaction: Alcoxolation :

(HO)Si(OR)3 + ROH (HO)2Si(OR)2 + ROH (HO)3Si(OR), + ROH Si(OR)4 + ROH =Si-OR + HO-Si == .. fw · =ς;——〇-Si: Water condensation (Oxolation): +

ROH : Si-^-〇H + HO-Si: three Si—〇—Si;

HOH Network Crosslink Reaction (Net Reaction):

Si H20, solvent

Si(OR)4 H+ , OH'

Si, a 0 Si-〇-Si 〇 I I , Ϊ 0 '〇-Si —〇—Si — I I Ϊ ? 0 , 〇—Ψ—0—$—o—Si—

Si.

O

Si '〇-Si-〇- "Si-〇--Si-; as shown in step S33G, the 'addition-triple bis solution' is carried out to carry out the hydrolysis and condensation of the second spray, wherein the tripentane _ The solution contains tri-erythrone to tetranitron. The bismuth-bismuth solution contains the organic/inorganic clear 201105738 polymer, wherein the mixed polymer comprises polylactic acid, gasification and oxidized stone, and the inorganic sol comprises oxidized oxidized Ming, the inorganic sol is a linear network structure. In addition, in order to achieve a more complete reaction, the present embodiment further includes steps s and S36G, wherein the inclusion of the money, as shown in step s35G, is performed on the knife mold and the eucalyptus, to completely react to form the mixed polymer. , wherein the circulating baking system-circulating oven bakes the second solution containing the inorganic sol at different temperatures; as shown in the step, the mixed polymer is baked to remove the solvent and moisture 'which is vacuum baked The vacuum oven was baked at a temperature of 7 G Celsius. Coefficient of thermal expansion (ppm/°C) 30 ～80°C Pure polylactic acid 4062 Inorganic content 1 w. t% PLA/Al2〇3 1485 Inorganic content 4 w. t% PLA/Al2〇3 961 Inorganic content 7 w. t% PLA/AI2O3 253 Inorganic content 1 w. t% PLA/Si〇2 348 Inorganic content 4 w. t% PLA/Si〇2 942 Inorganic content 7 w. t% PLA/Si〇2 55 PLA-5w. t%- S4Al 18 PLA-5w. t%-S4Al 96 PLA-5w. t%-S4Al 46 Table 1 As shown in Table 1 above, 'PLA/Si〇2, PLA/ΑΙΑ of the present invention, the inorganic content is adjusted by 1 wt% to 7 wt% , PLA / Al2 〇 3 / Si 〇 2 content ratio is PLA-5%-S4Al, PLA-5%-SlA4, PLA-5%-S2 · 5A2. 5, wherein PLA is polylactic acid, S is inorganic weight percentage, a is the weight percentage of aluminum trielenone. In summary, the present invention is a method for preparing a thermally stable polylactic acid material by a sol-gel method, which utilizes a sol-gel method to uniformly disperse a mixture of triamethylene or sulphate, or The method for preparing a thermally stable polylactic acid material by a sol-gel method can significantly reduce the CTE (thermal expansion coefficient) by adding a small amount of inorganic metal oxide oxide (see Table 1 below), and the rigidity is also improved a lot and is progressive. . , 201105738 Base polymers, such as: tetraethyl sill, tetramethyl sulphur, etc. The purpose is to improve the mechanical properties and reduce the coefficient of thermal expansion 'effectively replace other general-purpose plastics, such as poly (four) ( PET), polypropylene (PP)··^. Progressiveness means that the users in the industry can apply for invention patents according to law, and the prayers should be in accordance with the earlier inventions given by the bureau. The invention is a patent application for a patent law with a novelty. For prayer. However, the above description is only for the present invention - the preferred embodiment has been applied to the Fan®, so the invention according to the invention "patent lang" #, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In this form, structure, features and fine

Τ May patent scope. [Simple description of the diagram] The first picture is a flow chart of one of the inventions _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The other figure is the flow chart of the other __ and the filial piety of the invention. [Main component symbol description]

Claims (1)

201105738 VII. Patent application scope: 1. A method for preparing a thermal stability polylactic acid material by a sol-gel method, which comprises: adding a mono-alkyl polymer by using a first solvent to carry out hydrolysis and condensation reaction to form an inorganic a sol; a polylactic acid (p〇ly (lac1: ic acid)) is dissolved in a second solvent to form a first solution; and the inorganic sol is dissolved in the second solution to obtain the organic/inorganic hybrid polymer. 2. The method of claim 1, wherein the decylalkyl polymer is selected from the group consisting of tetraethyl decane, tetramethyl decane, and combinations thereof. 3. The method of claim i, wherein the first solution comprises water and ethanol. 4. The method of claim 4, wherein the inorganic sol comprises cerium dioxide. 5. The method of claim 1, wherein the inorganic sol is a linear network structure. The method of claim 1, wherein the step of hydrolyzing and condensing further comprises: adding a catalyst to the first solution. 7. The method of claim 6, wherein the catalyst comprises hydrochloric acid. ' & If you apply for the _ _ 丨 丨 , , , , , , 该 该 该 第二 第二 第二 第二 第二 tetra tetra tetra tetra tetra tetra tetra tetra tetra tetra tetra 9. Such as the application of the δ month patent encirclement! The method of the present invention, after the step of obtaining the mixed polymer, further comprises: placing the second solution containing the inorganic sol on a doctor blade and circulating baking to completely react to form the mixed polymer And vacuum baking the mixed polymer. The method of claim 9, wherein in the step of baking, the second solution containing the inorganic sol is baked at a different temperature using a circulating oven. The method of claim 9, wherein in the step of vacuum baking the mixed composition, the mixed polymer is baked at a temperature of 7 degrees Celsius using a vacuum oven. A method for preparing a thermally stable polylactic acid by using a sol-gel method, which comprises: using a solvent-dissolving polylactic acid (PQly (lactie _)) to form a solution; adding 201105738 plus tripentane ketone aluminum The solution is hydrolyzed into the solution; the hydrolysis and the reaction are carried out to form a ruthenium-to-heap liquid, and I3. The method of the invention is as described in the patent application. The mixed polymer with alumina - A comprises polylactic acid, wherein the first solvent comprises tetrahydrofuran. 14. The method of claim 12, (tetrahydrofuran, THF). Wherein the second solvent comprises water or ethanol. Wherein the tripentanedione aluminum solution comprises tripentane 15. The method of claim 12, 16. The method of claim 12, Dimensional and tetrahydro-sigma. In the step of performing the hydrolysis and the condensation reaction, the method further comprises: adding a catalyst to the first solution. The team applies the method described in Item 17 of the patent scope, wherein: 19. The method of claim 12, wherein the method of taking the second item; wherein after the step L, further comprises: setting the solution to the - doctor blade molding The mixture is baked in a loop and completely reacted to form a Chengcheng polymer' and the mixed polymer is vacuum baked. 20. The method of claim 19, wherein in the step of circulating baking, the solution is baked at a different temperature using a circulating oven. 21. The method of claim 19, wherein the mixed polymer is vacuum-baked and the mixed polymer is baked at a temperature of 7 degrees Celsius using a vacuum oven. 22. A method for preparing a thermally stable polylactic acid material by using a sol-gel method, which comprises: dissolving a polylactic acid (10) y with a first solvent to form a first/complex liquid utilization 帛- Reading the lyophilized foot compound silk compound 'clear silk two solution and performing hydrolysis and shrinking, should, add -tripentane solution to the second solution towel; and adding the first solution = to the second solvent _ 'To produce a spectroscopic polymer with an inorganic sol. The method of claim 22, wherein the modified polymer comprises polylactic acid, aluminum oxide and cerium oxide. 24. The method of claim 22, wherein the first solvent comprises tetrahydrofuran (THF). 25. The method of claim 22, wherein the ketone is aluminum and tetrahydrofuran. The method of claim 2, wherein the method of claim 22, wherein the method further comprises: wherein the second solvent system Contains water and ethanol. The method of adding a catalyst to the first solution in the hydrolysis and the condensation reaction. The method of claim 27, wherein the method of claim 22, wherein the method of claim 22, wherein Contains hydrochloric acid. 30. If the method of claim 22 is applied for, the medium=, machine's glue contains magnet dioxide. Media. , the inorganic sol is a linear network junction 31. The method of claim 22, further comprising: ', placing the second solution on a doctor blade and circulating the baked compound in the step of obtaining the modified polymer; And modifying the reformed polymer to form the modified polymer in a complete reaction. The method of claim 31, wherein in the step of circulating baking, the solution is baked at a different temperature using a circulating oven. 33. The method of claim 31, wherein in the step of vacuum buffing the modified polymer, the modified polymer is baked at a temperature of 70 degrees Celsius using a vacuum oven: Eight, schema: 12