TW200923009A - Modified polylactic acid composition - Google Patents

Abstract

A modified polylactic acid composition comprises 100 weight parts of polylactic acid or polylactic acid polymer and 0.1-5 weight parts of a coupling agent, wherein the coupling agent is a compound having at least one functional group capable of reacting with polylactic acid. The functional group is isocynate, oxazoline, epoxy, aziridine, or carbamide. A modified polylactic acid composition of this invention possesses a high heat resistance and tenacity. The forming period of the composition is shorter than that of unmodified polylactic acid. The cost of the raw materials does not increase on a large scale, and the defect to influence the appearance of the product is not easy to occur because of maintaining the dosage of the coupling agent in the appropriate range.

Description

200923009 IX. Description of the invention: [Technical field to which each of the inventions belongs] The present invention relates to a polylactic acid composition which can improve the heat resistance of polylactic acid and a modified polylactic acid group molding cycle. ..., ', dynasty, and shortening the polylactic acid [previous technology] The current oil price 袼 升 古 θ ^ ^ ^ can be 'exhibition of the problem, the benefits are valued, no one is not ambiguous - gasification reduction and calculation The use and development of the raw shellfish has been paid more and more attention in the view of the 4-inch quality plastic harvesting source and environmental protection. The raw plastics (B-- can be divided into the following two categories. Biomass material plastic knee (Bi〇mass p. does not have biodegradable ke, / 々 clothing into finished Α, but used Some or all of the raw materials are the tribute of Tianqiu, and the sputum is smashed... Big ',,) % is the raw material of Shengbei. The application fields are mainly for automobiles, Xunzi and 岫 ;; Decomposable plastic (8) wall (4) Can Pu p-mer): The bio-decomposable function of the mouth-making function is called biodegradable plastic, and the application field is food packaging container and utensils, mainly referring to "one-time Products used" ("玍"" The use of polylactic acid in raw plastics is the largest and the most widely used. The monthly polylactic acid is PLA, which is p〇ly-lactic-acid. For the day of the day, polylactic acid has the following advantages: A. The production of lactic acid can reduce the use of fuel resources by more than 65%, and achieve the reduction standard of 'gas to gas emissions; B' polylactic acid in the composting field It can be decomposed into carbon dioxide and 200923009 water in 47 days; c. polylactic acid in incinerator When the waste treatment system is incinerated, the environmental load is lower than that of traditional plastic teeth. However, the general polylactic acid also has the following shortcomings to be improved: (a) low glass transition point (Tg); (B) slow crystallization rate (C) Low toughness. The current methods for solving the disadvantages of polylactic acid include: A. Low glass transition point: 1. Adding fiber: adding glass fiber (GF), carbon fiber (CF) or kenaf fiber, however the fiber must be added to A certain amount has an effect, which will result in an increase in the proportion of the product, a decrease in fluidity, and a decrease in formability. 2. Nano method: If montmorillonite is added, although a small amount can be added, the cost of montmorillonite is high (per The weight of the treatment is about 4〇〇_8(10) yuan, and the safety of the treatment agent used for the treatment of montmorillonite must also be considered. B. The crystallization rate is slow: 1. Adding filler: it must be added to a certain amount to have an effect, and also Will cause the proportion of products to increase, the fluidity is reduced, and the formability is also declining; 2. Nano method: If adding montmorillonite, but Λ 丄 Γ ii iifi has cost and safety concerns; 3. Crystal nucleating agent addition: usually Not effective, and Some with / color, resulting in poor product selling; Yan C. Low mobility: a ... 々 eight-watt oil to find natural oil, or neighboring _ carboxylic acid dioctyl (DOP) and other plasticizers, but will produce a surface Ke ^ (β 1 ο 〇 ming) problem, and the product heat resistance is also reduced · 200923009 2 . Gluing method: such as adding polycarbonate (pc) or acrylonitrile-butadiene-styrene (ABS) copolymer and other plastics The substrate, however, is not added in a low amount, resulting in a decrease in the raw material composition of the product; 3. Adding an elastomer: However, the amount of the elastomer substrate added is not low, resulting in a decrease in the raw material composition of the product and a decrease in temperature. There is still a deficiency in the method for solving the disadvantages of polylactic acid at this stage. The object of the present invention is to provide a modified polylactic acid composition which can improve the heat resistance and toughness of polylactic acid and shorten the formation of polylactic acid. Cycles without significantly affecting the physical properties of polylactic acid. In order to achieve the above object, the modified polylactic acid composition of the present invention comprises: 100 parts by weight of a polylactic acid or a polylactic acid copolymer; and 0-1 to 5 parts by weight of a coupling agent, the coupling agent is provided with One or more compounds capable of reacting with polylactic acid, and the B thiol group reactive with polylactic acid is isocyanate, oxazolinyl, epoxy, nitrogen Aziridine or ureido (for (10) 丨 seven). Preferably, the modified polylactic acid composition of the present invention comprises 〇.丨 parts by weight of a coupling agent. Preferably, the coupling agent has two or more functional groups reactive with polylactic acid. Preferably, the functional group reactive with polylactic acid is an epoxy group. Preferably, the coupling agent is epoxidized soybean oil or epoxy linseed oil. 0 7 200923009 Preferably, the coupling agent and the pigment are used as a master batch (master_batcher), and then with polylactic acid or polylactic acid. The copolymer forms a composition. The specific efficacies that can be achieved by the present invention include: 1. In July, a coupling agent which can have a functional group reactive with polylactic acid is mixed with polylactic acid, and the mixture can be used to form a chain extension effect of the modified polylactic acid. The modified polylactic acid composition has the characteristics of high heat resistance and the molding cycle is shorter than that of the unmodified polylactic acid. ", 2. In the present invention, since the dose of the coupling agent is maintained in an appropriate range, the raw material cost is not greatly increased, and there is no problem that the conventional additive is added to the polylactic acid or the resulting change of the present invention. The polylactic acid composition is less likely to have defects affecting the appearance of the finished product. [Embodiment] The preferred embodiment of the present invention may comprise 100 parts by weight of a polylactic acid or a polylactic acid copolymer and (M to 5 parts by weight of a coupling agent, The coupling agent is also called a chain extender, which is a compound having more than one functional group capable of reacting with polylactic acid, and the functional group reactive with polylactic acid may be isocyanate or oxazole. The morphyl group (〇xaz〇Hne), the epoxy group (ep〇x^, aziridine, and carbamide); the reaction of the polylactic acid with the coupling agent can be as follows:

+ Η -ο Q^-c CH丨C-H oi- Hi?-C CICH0+ H Agent A

Ho

Hfi? CICH

3C HI CICH <

Ηο士 Η3 HCIC I c=o Iο + H3 HCIC I C 8 200923009 〇 or 3

OF-C-'CH 士 % CICH Η ί 〇 Agent I I Λ + △ Ηο

ο τ CICH

3 V Η ί CICH Δ △

Hc—C i c

i Η Hc—C I cno

0H C-什H as Η ch3 ο ch3 Preferably, the preferred embodiment of the present invention includes a coupling agent of 0 hi, if the coupling agent is low π Λ 里 里 d low table (Μ In the case of parts by weight, the chain extension effect is not king: the molecular weight and the melt viscosity of the compound cannot be improved, and if the coupling agent is 5 parts by weight, the basic physical properties and mechanical strength of the molded article are lowered, and a large amount of fish eyes (gel) are not produced. Defective; s, preferably, the coupling agent has two or more (including two) functional groups which can react with polylactic acid, such as a bifunctional coupling or trifunctional; a coupling agent, the coupling agent It can be used in combination, such as a difunctional group: a mixture of a reagent and a difunctional coupling agent; ^. Preferably, the functional group reactive with polylactic acid is a coupling agent having an epoxy group and a % oxygen group. It can react well with polylactic acid, I use high temperature, use it; if the preferred embodiment is to be applied to food packaging materials, the coupling agent can be made of American food such as epoxy soybean oil or epoxy linseed oil) Approved by the Pharmacist Bureau (FDA); 軚 的 is 'for the coupling agent and polylactic acid Parts of the reaction 'mixture can be mixed with auxiliary agents, such as {200 923 009 pigment master batch prepared (level terbatch), and then forming the composition. ♦ The preferred embodiment of the present invention can be formed into particles and then formed into finished products. It can be used with single or double pumping 贞, 10,000 horsepower machine, kneading machine or heart::竑 丨 丨 π u u ^ * μs & can also be directly made into finished film, sheet, t, foamed products and tubes and so on. The following examples are presented to illustrate the invention. These examples, and the manner in which they are intended to limit the scope of the invention, are intended to indicate how the materials and methods are. Only a. Example: Prepare commercially available polylactic acid (molecular weight: about 180,000) 5 kg, add a little processing oil, stir the sentence, and then put it into the Kyrgyzstan Chemical Co., Ltd." base coupling product EP0LITE4 () E (ring Oxygen equivalent: 135 g (g/y) w g and EPOLITE1_ (epoxy equivalent: 1 ^ (g/eq)) 15 g of stirring evenly, etched field ^ Tianli Μ using Kobe steel twin-screw extruder

1 1, ', dry diameter 43 mm, screw length to diameter ratio of 43, temperature production set to 190 ° C, screw speed is 2 丨 4 丄 勺 勺 母 200 200 rpm (rPm), in the row The gas is empty and is subjected to water-cooled pelletizing, and the (axis-) is the third of the unmodified polylactic acid raw material—, — — —,,, after the “type test piece is shot, the test piece is compared with the lost shell poly hole. For the acid raw material test piece, the molding cycle is shortened by two parts, and the temperature is one plus 50 °c, and after the melting point is raised. : The finished product of the second example has the heat resistance and (4) improvement, and the molding cycle is also shortened.攻200923009 The preferred embodiment of the present invention utilizes a mixture of a and a polylactic acid with a deuterium-g-energy group to form a chain-extension effect and a double-fruit, so that the formed polylactic acid composition has It has high heat resistance and toughness, and has the characteristics of bauxite, and the formed fins are also short of unmodified polylactic acid. In addition, due to the dose retention of the coupling agent /

The proper range, therefore, the raw material cost will not be greatly reduced, and the formed polylactic acid composition is not easy to have defects affecting the appearance of the finished product. The scope of application of the preferred embodiments of the invention includes the following areas: • Packaging field: Packaging films: such as plastic bags, label films, shrink films. Agricultural film: cover film, bagging. Food packaging box: hollow container (bottle), foam cushioning material, fishing box. b • Textile sector: Fiber applications such as clothing, masks, carpets, etc. e · Biomedical areas: artificial bone nails, bone plates, drug release (eg diffusion control), wound dressing (artificial skin), wound closure (surgical suture, surgical supplies). D-Optical/Automotive: Replacing existing plastic materials such as mobile phones, notebook cases, optical discs, and automotive components. [Simple diagram description] None [Main component symbol description] 200923009

Claims (1)

200923009 X. Patent Application Range: 1 - A modified polylactic acid composition comprising: 100 parts by weight of polylactic acid or polylactic acid copolymer; and ow parts by weight of a coupling agent having more than one coupling agent The ::: κ 黾 黾 之 之 之 ' ' 该 ' ' ' ' ' ' ' ' ' ' : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : iso , aziridine or azide ((10) (4). From:: The modified polylactic acid composition as described in claim 1 includes 〇·1 to 1 part by weight of a coupling agent. The modified polylactic acid composition according to item 2 has two or more functional groups capable of reacting with polylactic acid. Item: Medium: modified polylactic acid composition described in claim 3 The functional group reactive with polylactic acid is epoxy. The substance: the modification described in the scope of the patent; the lactic acid composition: ° The agent is epoxy soybean oil or epoxy linseed oil. Where = please modify the composition of polylactic acid described in item 5 of the patent scope with polylactic acid or m / made 枓 bat bat 咖 咖 咖 咖 咖 咖 咖 咖 咖 咖 咖 咖 咖 咖 咖 咖 / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / Two or more of the modified polylactic acid reacting with the polylactic acid, and the g-revalence group of the modified polylactic acid is an epoxy group. 200923009 9 · The modified poly-polymer as described in claim 1 A lactic acid composition, wherein the coupling agent is an epoxidized soybean oil or an epoxy linseed oil. The modified polylactic acid composition according to claim 1, wherein the coupling agent is made of a pigment. Master-batcher, and then form a composition with polylactic acid or polylactic acid copolymer. Η—, pattern: no 14