TW201231492A - Polylactic acid compatibilizer - Google Patents

Abstract

A polylactic acid compatibilizer has the following chemical formula (I), wherein R1 and R2 individually represent the C2-C10 alkyl; n1 and n2 individually represent an integer of 55 to 208; and A represents a bivalent group derived from an epoxy compound, wherein the epoxy compound contains two terminal epoxide groups and at least one unsubstituted or substituted phenylene on the main chain, and the epoxy equivalent of the epoxy compound ranges from 180 to 5000.

Description

201231492 VI. Description of the Invention: [Technical Field] The present invention relates to a polylactic acid compatibilizer, and more particularly to a polylactic acid compatibilizer for a copolymer of lactic acid and epoxy resin applied to a polymer composite material. . [Prior Art], the king's milk force, the trapped polylactic acid (four) y丨actic acid; referred to as pLA) materials have received much attention from the industry, but due to its own mechanical properties and poor stability, currently only It is used in the field of people's livelihood, such as sanitary cups, tableware and cup lids. : Expanded the applicability of PLA's industry, and tried to be widely used by the industry by blending other resins with the problem of poor mechanical use of PLA. '(R/"S"SI(P〇lyCar^: One of the materials, 'When the PLA and PC are blended alone, the phase separation phenomenon will occur due to poor phase-to-grain. The current blending of different polymers will be more or less incompatible. After all, the properties of these polymers are not exactly the same, and a compatibilizer for polylactic acid-based composite materials has been developed. The emerging plastic additives can improve the disadvantages of poor properties. The knives are compatible during blending, and at the time of mixing, the eight-force force of the compatibilizer and the polymer reduces the interfacial tension to promote the non-phase. The knife is compatible with the common polylactic acid on the market. The agent has the same knives combined with the malay-branched polypropylene (abbreviated as pp-suppressed), the grafted acrylonitrile-butadiene-styrene terpolymer (abbreviated as 201231492 for ABS-g) -MAH), maleic anhydride grafted polyethylene (abbreviated as pE_g ΜΑΗ), maleic anhydride grafted polypropylene (abbreviated as pp_g_MA) H), etc. Although the above polylactic acid compatibilizer is added to the poorly compatible polymer composite material's ability to adjust the properties of the polymer composite material, it still cannot meet the requirements for properties when applied to various fields. Epoxy resins have also been used as compatibilizers for polylactic acid-based composites. For example, in 2004, Tj0ng et al., 39, ρ·1791-ρ.1801, was developed on nylon 6/polycarbonate (PA6). /PC) blending system, adding bisphenol A epoxy resin as a polylactic acid compatibilizer, thereby improving the tensile modulus and elongation at break (ei〇ngati(10) at break). However, in their system Among them, the epoxy resin is easily bonded to the guanamine group on PA6, and there is not such a large number of functional groups on the opposite pLA to react, so the above polylactic acid compatibilizer cannot effectively produce a compatible effect. There is still a need to develop a polylactic acid compatibilizer having a good compatibility effect. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a polylactic acid compatibilizer having a good compatibility effect. Thus, the polylactic acid phase of the present invention Capacity System having the following chemical formula G):

R|一c—0—c—C

CH, OH O II I II -c—c—o—c—r2 ch3 ? ί? 0 H pu Λ I II II I / |H3 0-C—CAC—C-oi-c—c—0-ch3 〇h (I) ; nl and n2 where Ri and R2 represent a C2~Ci〇 alkyl group 201231492, respectively, 55 to an integer employed; and A represents a "divalent group derived from an epoxy compound" And the epoxy compound contains a di-terminal epoxy group and at least one unsubstituted or substituted stabilizing group on the main chain, and the epoxy compound has an epoxy equivalent of between 180 and 5,000. The invention has the advantages that the compatibilizing agent with special structure can make the polylactic acid segment and the benzene ring have good intermolecular force with PLA Xiaopc respectively, thereby increasing the compatibility between PLA and PC, : A composite material having good properties is obtained, so that the object of the present invention can be achieved. [Embodiment] The polylactic acid compatibilizer of the present invention has the following chemical formula (I), m3

Rl-[〇+¥〇11A j—U ? ? 〇-ν Α Λ - (ΐ) , I. Center and r2 respectively represent a C2~C|〇 烧 · d and η2 分 m to 208 a number 'and Α represents a one-bei group derived from an epoxy compound' and the epoxy compound contains a terminal polyoxy group, and two to: an unsubstituted or substituted phenyl group on the primary bond And the epoxy equivalent of the epoxy compound is between 180 and 5,000. Preferably, 'n^n2 represents an integer of 7 〇 to 15 (an integer, respectively. Preferably, the epoxy equivalent of the epoxy compound is between 1 and 5 _ preferably, the polylactic acid compatibilizer of the present invention (4)S(4)S «Compacted with the epoxide: 物 仃 仃 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 C~0-d. ch3 where n represents an integer from 55 to 2〇8.

CH2^〇{X^°-CH2-C-CH2y〇-Y-〇-CH2-C--CH2 OH /m V H I

Broad and r4 respectively represent a Ci~c7 alkyl group, and a c2~c7 aroma is preferred. &quot;Hybrid% oxygen compound has the following chemical formula (ΙΠ) (III) or 虱: R5 to R12 respectively represent a Ci~ An alkyl group, a halogen or a hydrogen of C3; and m represents an integer of from 1 to 250.车乂佳地's feet 3 and r4 respectively represent a burning base or gas of Ci~c?. Preferably, the scales 5 to Ri2 represent halogen or hydrogen, respectively. Preferably, the epoxy compound is selected from the group consisting of bisphenol A type epoxy resin, double age F type epoxy resin, desertified epoxy resin, or the like. The polylactic acid compatibilizer of the present invention is prepared by first preparing a lactic acid oligomer and then uniformly mixing the lactic acid oligomer with an oxime compound, and adding a tetrabutyl bromide domain (abbreviated as TBAB) to make the same The reactant is subjected to a polymerization reaction to obtain a polylactic acid compatibilizer of the present invention. The lactic acid oligomers suitable for use in the present invention may be commercially available or lactic acid oligomers prepared according to the prior art. Preferably, the ratio (weight ratio) of the lactic acid oligomer to the epoxy compound is preferably 0.1 to 4 Å, and the amount ratio is 〇 5 to 2. 201231492 In a specific embodiment of the present invention, the lactic acid oligomer of the present invention is produced by self-polymerization of lactide under the catalysis of stannous octoate. Preferably, the propylene and stannic acid octanoate are firstly subjected to a purification treatment, and the lactic acid oligomer obtained after the polymerization is also purified to remove residual methanol and di-methane, thereby obtaining Purified lactic acid oligomers for subsequent processing. The present invention will be further illustrated by the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting. &lt;Chemical Source&gt; 1. Lactide: purchased from Xingji Biotech Co., Ltd.; molecular weight is 144. 2. Bisphenol A type epoxy resin: purchased from Shell; model: epikote 1010: epoxy equivalent: 3030~4762 g/equivalent of epoxide. 3. Stannous octoate · purchased from Alfa Aesar, 98%. 4. Tetrahydrofuran (THF): purchased from TEDIA; HPLC grade. 5. Dioxane: purchased from ECHO; HPLC grade. 6. Dimethylformamide (DMF): purchased from TEDIA; ANHYDROSOLV. 7. Tetrabutylammonium bromide (TBAB): purchased from TCI-Ace; reagent grade. <Instrument and Equipment> 1. High Magnetic Field Resonance (Nuclear Magnetic Resonance; 201231492 NMR): purchased from the label: Varian; model is Unity-300MHz. 2. Fourier Transform Infrared Spectrometer (FT-IR): purchased from Perkin Elmer; Model Spectrum RX. 3. Thermogravimetric Analyzer (TGA): purchased from ΤΑ Instruments; model number Q50 〇 4. Differential Scanning Calorimeter (DSC): Eyes from ΤΑ Instruments; model DSC Q10. 5. Scanning Electron Microscope (SEM) (Thermal Type Field Emission Scanning Electron Microscope; TFSEM for short): purchased from JEOL; model is JSM7000F. 6. Polarized optical Miscroscope (POM): purchased from Nikon; model number is 100LV. &lt;Synthesis of lactic acid oligomers&gt; [Preparation Example 1] The preparation steps of the preparation examples are as follows: (1) Purification of vinegar: Dissolve propylene in acetone at 60 ° C, and recrystallize using an ice bath. The obtained crystals were separated by placing them in a vacuum oven at 40 ° C for 24 hours to remove residual acetone, thereby obtaining purified lactide. (2) Purification of stannous octoate: Stannous octoate was subjected to vacuum distillation treatment at 180 ° C to obtain purified stannous octoate. (3) The purified lactide of the step (1) having a molar ratio of 10:1 and the purified stannous octoate of the step (2) are added to a three-neck reaction flask, and two vacuum nitrogen substitutions are performed. Thereafter, three 201231492 reaction bottles were placed in an oil bath, and the propylene glycol was subjected to polymerization for 24 hours under the catalysis of stannous octoate to obtain a lactic acid oligomer. (4)

The lactic acid oligomer of the step (7) is dissolved in a gas chamber, and the insoluble matter is separated by purification, and then the product is precipitated by adding ice methanol, and the above purification operation is repeated twice. Finally, the obtained product was placed in a 4 (vacuum oven of TC to be dried to remove the residual methanol and the gas of the second gas) to obtain a purified lactic acid oligomer, and the number was averaged. The molecular weight [preparation example ^) was paid; the molecular weight distribution (PDI) was 18. Acidic oligo 2 cases 2 i 7 The chyle was prepared in the same preparation procedure as in Preparation Example 1, except that the amount of purified clofibrate and hydrazine purified stannous octoate in the step (3) was used. The ratio, the oil bath temperature at the time of the reaction, and the time. Further, in Preparations 2 and 4, the unpurified xin === is used, that is, the preparation examples are not subjected to the step (7)), and the above-mentioned respective systems are:::: two\ 'And these lactic acid oligomers... 201231492

Dosage ratio (Morby) oil bath temperature rc) reaction time (hours) PDI

The ratio is intended to be the same as that of octanoic acid & sulphate &lt;structural identification of lactic acid oligomers&gt; ruthenium NMR and FT_IR for structural identification of lactic acid oligomers of the preparation examples' confirms that the products of these preparations are indeed It is a lactic acid oligomer. Taking the preparation example 7 as an example, the NMR identification result is 丨h_nmr (ΑΜχ 300 S(CD2C12): the absorption peak of CH3 visible on the hydrogen diagram (the absorption peak of 1 59 卯, _ CH ( 5"5 ppm), solvent (3) The absorption peak of the heart 2 "howling and the integral value at 1.59 ppm is 76 99, and the integral value at 5 15 ppm is 23.01, so the ratio of the -CH3 integral value to the _ch integral value It is 3.34, because the absorption position of water is 158 ppm, which overlaps with the absorption peak of 丨59卯 of _CH3; as for the carbon spectrum, there are absorption peaks of -67% with 16.87 ppm and 20.68 PPm. 67. 〇4 ppm and 69 38 ppm have an absorption peak of ch〇, and 169.86 ppm has an absorption peak of CO. In addition, the FT_IR identification result is: 1715~1760 cm·1 with C=〇 stretching absorption peak, 1〇 35~124〇cm I has C-0 stretching oscillation absorption peak, 284〇~3〇〇〇em-i has C_H stretching absorption peak, and 1462cm·1 has C_H bending Swing absorption peak, 1375 £ 10 201231492 * There is a CH3 stretching oscillation absorption peak nearby, and no cyclic bimolecular absorption peak is found near 920 cm·1, indicating that there should be no monomer lactide residue. The above results show that Preparation Example 7 The product obtained is indeed a lactic acid oligomer. &lt;Synthesis of the polylactic acid compatibilizer of the present invention&gt; [Example 1] The preparation steps of this example are as follows:

(1) The lactic acid oligomer of Preparation Example 7 and the bisphenol A type epoxy resin (epikote 1010) in a weight ratio of 2:1 were respectively dissolved in DMF to obtain a lactic acid oligomer solution and a bisphenol. A type epoxy resin solution. (2) Pour the above two solutions into a three-neck reaction flask while homogenizing with a stirrer, and add yttrium by weight (based on the total weight of the lactic acid oligomer and the bisphenol hydrazine type % oxygen resin) The TBAB' and the reactants were allowed to enter the polymerization reaction in a 12 〇〇c oil bath for 2 hours, and anhydrous nitrogen was passed through the three-way reaction flask. (7) & After completion, the solvent was removed and the product was dried to obtain the polylactic acid compatibilizer of the present invention, and it was found to be 10400 by measurement; pdi was 2.01. [Examples 2 to 18] The inventive polydiphenyl phthalocyanine 18 was prepared in the same preparation procedure as in Example 1 except that the lactic acid body and the bismuth in the step (1) were different. The ratio of the amount of the epoxy resin, and the time of the reaction 201231492 in the step (7), and the steps n to (a) of the examples 4-6 and 10-12) further precipitate the product by adding decyl alcohol, and then The product is baked: #,# to obtain the polylactic acid compatibilizer of the present invention, and the different operations of the above embodiments are as shown in Table 2 of Table 2.

Note 1] [Note 2] "Using - Λ means that it is milk acid, f condensing &lt; Thermal stability test &gt; [TGA analysis] The inventors used TGA to heat the polylactic acid phase obtained in some of the examples. Stable analysis 'A outside' will also be mixed in different proportions but not into the 201231492 reaction of lactic acid oligomers and double 19A epoxy resin composition, as ... and placed in TGA for thermal stability analysis, of which, comparative examples [The weight ratio of lactic acid oligomer to bisphenol A epoxy resin in 4 is 2:1, 1:2, 4:7 and 5:4, respectively. The operating conditions of TGA are under nitrogen atmosphere. It is heated from 3 〇 〇〇 ' and its heating rate is IGt / min, and the low temperature cracking temperature (Tdi) measured by TGA, the weight loss percentage (wi) of low temperature cracking, pyrolysis temperature

(Td2), the weight loss percentage (W2) of pyrolysis, and the weight ratio of the amount of loss of the lactic acid polymerizer to the amount of loss of the bisphenol A type epoxy resin are described in Table 3 below.

table 3

Note that the ratio of the total loss of loss weight refers to the change in the total loss id of the ratio emulsion and the value of the bisphenol A-type epoxy resin from Table 3 'from the thermal cracking of the comparative example and the example, It can be confirmed that there is a reaction between the lactic acid oligomer and the bisphenol A type epoxy resin. 13 201231492 [DSC analysis] The inventors used DSC to measure the thermal properties of pure lactic acid oligomers, pure bisphenol A type % oxygen tree, and the polylactic acid compatibilizers of the respective examples. The operating conditions of Ds匚 are as follows: After 1 (rc is held for a few minutes, the temperature rises from 1〇°c to 18〇t at the heating rate of the order/min: the first temperature rises, and at 18 (rc holding temperature) 1 minute' then cool down to 1Gt (1st to undercooling) at 2G °C/rnin, and hold the temperature at i〇°c for 1 minute' and then heat up to 18 (TC' for the second time from the temperature increase rate of 1Gt/min. The temperature rise. The intermediate process of the first temperature rise and the first temperature drop, that is, holding the temperature at 180 ° C for 1 minute is to eliminate the thermal history of the material. 1. DSC analysis result of pure lactic acid oligomer The inventors took the lactic acid of Preparation Example 7. The oligomer is representative, and the first-time temperature rise, temperature drop and second temperature rise are observed by DSC. From the DS-th graph of the first temperature rise, we can see that (the TC starts to have a broad crystallization heat curve extending to 125.) The heat of crystallization is 10.8 J/g' and then immediately adjacent to the heat curve of _, the melting peak (ie, fineness) is at 156.rc, the heat of fusion is 412 j/g, and the crystallinity is about 45.27%. The lactic acid oligomer is close to the upper limit of its crystallinity. In addition, the lactic acid oligomer does not undergo crystallization behavior in the DSC chart of the first cooling. There is no heat of crystallization, only a glass transition temperature at the price. Furthermore, from the second temperature rise DSC chart, 5〇c is the glass transition temperature 'has obvious recrystallization heat and heat of fusion, and the recrystallization heat is 29·8 J/g,® 4 士a丨, e rfc &amp; g recrystallization peak temperature is 118.7 ° C, heat of fusion is 28.5 J / g, melting temperature is 145. 乞 and i54 3 it.

In the process of reducing the fire and drying, the solvent acts as a lubricant and can increase the molecular alignment ability. Therefore, it is easier to arrange the crystals. Since the second heating process of DSC 201231492 has only crystallization time of 3 to 5 minutes, the first The secondary heat of fusion heat is lower than the first heat of the heat of fusion, and the crystallization is incomplete due to the short crystallization time. In addition, in the DSC chart of the first temperature rise, the melting peak has some micro-double melting peak, the high temperature peak is more obvious, and the low temperature peak is less obvious, but in the second heating DSC chart, the high and low temperature peak of the melting peak It is obvious that the low-temperature melting peak area is larger than the high-temperature melting peak area. The inventors reasoned that the phenomenon of multiple melting peaks may be due to the fact that the lactic acid oligomers have a wide molecular weight distribution, some of them are easier to crystallize, and the other part is less likely to crystallize, resulting in crystal forms of different particle sizes, and thus high and low temperature melting peaks. The phenomenon arises. 2. DSC analysis results of bisphenol A epoxy resin No crystallization and melting behavior were observed in the DSC chart of the first heating, cooling and the second heating of the bisphenol A epoxy resin. It is known that the glass transition temperature at the first temperature rise is 83.3 ° C, and the glass transition temperature at the first temperature drop is 82.4 ° C. 3. Results of DSC analysis of Examples 1 to 12 From the DSC chart of the first temperature rise of Examples 1 to 12, the recrystallization temperature (Tc) and recrystallization heat of the polylactic acid compatibilizers of Examples 1 to 12 were known ( The values of △ He), low temperature melting temperature (Tml), high temperature melting temperature (Tm2), heat of fusion (ΔHm), and material heat of fusion He can be used to indicate the properties of the material after drying, as shown in Table 4 below. 15 201231492 Table 4

Tc(°C) △ He (J/g) Tml (°C) Tm2 α) Δ Hm (J/g) △ Hmm (J/g) Pure lactic acid oligomer 101.75 ±0.55 10.85 ±0.15 — 156.2 ±0.4 41.55 ±5.25 30.7 ±5.40 Example 1 68.65 ±4.35 8.4 ±1.0 140.8±1·6 153.8 ±1.5 29.95 ±5.55 21.05 ±7.04 Example 2 85.35 ±0.65 9.45 ±1.75 144·8±0.3 (139.15±0.3) 153.05 ±0.45 34.4 ±1.0 25.0 ±2.73 Example 3 81.27 ±7.3 11.55 ±0.45 145.8±〇.〇(140.25±0.05) 153.75 ±0.65 35.5 ±0.45 23.9? ±0.86 Example 4 78.5 ±1.5 9.5 ±1.0 141.45 ±0.55 154.3 ±2.5 41.1 ±4.5 31.65 ±5.49 Example 5 78.2 ±2.3 8.5 ±1·7 141.44±1.05 155.89 ±0.25 41.24 ±0.2 28.24 ±1.47 Example 6 79.9 ±0.4 8.7 ±3.0 146.35 ±0.65 154.55 ±1.25 45.0 ±5.6 36.29 ±0.86 Example 7 79.45 ±0.95 7.85 ±0.35 140·25±0.45 151.4 ±0.3 12.95 ±2.65 30.52 ±2.84 Example 8 96.3 ±12.5 7.38 ±1.05 138.4±0.5 148.7 A±0.8 29.25 1 ±7.45 17.19 ±1.29 Example 9 89.1 ±7.0 4.0 ±2.0 135.3±2.0 148.3 ±1.9 36.65 ±2.95 13.03 ±3.93 Example 10 84.0 1.4 1.6 ±0.9 152·7±1.8 — 32.65 ±2.45 5.07 ±2.25 Example 11 88.4 ±1.8 6.75 ±0.35 144.97±0.95 — 23.95 ±1.65 26.73 ±12.32 Example 12 86.3 ± 0.4 Γ i 1.6 ± 0.5 145·45 ± 0.95 14.73 ±2.83 29.01 ±7.3

1. Since the pure lactic acid hand polymer has only one melting temperature and the temperature is closer to Tm2 of the embodiment, the melting temperature is regarded as Tm2. In the case of Example 1 〇 -12, no Tm2 was observed. 2· Real, ΐ J, three melting peaks appear on the DSC chart, that is, there are three melting temperatures, so there are two Tml. &amp; In Table 4, 'the pure lactic acid oligomer recrystallization temperature is about ι〇1 7χ:, and the copolymer after polymerization with the biguanide A type epoxy resin (ie, the polylactic acid of Examples 1 to I: The recrystallization temperature of the agent is between 68. (: ~96 ° C, both lower than pure milk £ 16 201231492 acid oligomer 101.7 ° C, recrystallization heat between 丨 j / g ~ 1 〇 J / g, melting temperature from the original pure lactic acid oligomer The melting temperature (丨5 6 2) becomes a plurality of melting temperatures, or a wide range and lower than the melting temperature of the pure lactic acid oligomer. The inventors speculate that after the polymerization, since the copolymer is derived from lactic acid The portion of the polymerizer is not easily aligned, and contains an epoxy resin unit, so that the crystal structure is loose and the crystal form is not uniform, thereby causing a phenomenon of multiple melting peaks and a decrease in melting temperature.

Further, from the DSC chart of the first cooling of Examples 1 to 12, it is understood that the glass transition temperatures of the polylactic acid compatibilizers of Examples 1 to 12 are not larger than those of the pure lactic acid oligomers as shown in Table 5 below. The temperature is switched, and most of the polylactic acid compatibilizers of the examples exhibit two glass transition temperatures (represented by the nickname and Tg2 in the table), wherein the first glass transition temperature is derived from the lactic acid oligomer portion. The second glass transition temperature is derived from the epoxy portion.

Example 6 Example 47.65±0.35 50.3±0.55~56.9±0.9 79.25±〇.25~1^65ITJ5_Example Example 10 Example 11 Example 12 48_25 soil 0.75 62.35 ± 2.35 46.45 Soil 1.15 ~ T7.8 ±1.3- 48.45±0.25 70.465±〇_72 Note•” represents only one glass transition temperature of 76.85±〇.75 76.7±〇73^ Further, the DSC diagram of the second temperature rise from Examples 1 to 12. 17 201231492 Glass transition temperatures (τ§丨, Tg2), recrystallization temperature (Tc), recrystallization heat (△ He), low temperature melting temperature (Tml), high temperature of the polylactic acid compatibilizers of Examples 1 to 12. The smelting temperature (Tm2) and the heat of fusion are shown in Table 6 below, and from the difference between the second glass transition temperature and the pure epoxy resin, it is also proved that there is indeed a difference between the lactic acid oligomer and the epoxy resin. The reaction takes place. Table 6

Tgl(°C) Tg2(°C) Tc(°C) Δ He (J/g) Tml re) Tm2 CC) △ Hm (J/g) Real p 1 53.35 ±0.85 83.65 103.5 ±1.3 20.75 ±4.35 147.75 ± 1.35 152.5 ±0.1 22.9 ±5.6 Real ' 2 51.65 ±0.25 80.2 ±0.0 106.3 ±1.0 23.9 ±0.2 145.95 ±0.45 151.85 ±0.25 24.25 ±0.25 Implementation 3 52.15 ±0.35 — 102.5 ±2.1 24.07 ±1.45 146.3 ±0.9 — 25.5 ±2.9 Implementation 』4 53.5 ±0.9 — 103.1 ±1.7 29.55 ±3.95 150.05 ±1.35 — 30.7 ±4.1 Implementation Interest 5 Implementation 6 50.85 ±0.25 — 106.5 ±2.4 17.15 ±0.75 148.8 ±2.4 — 17.25 ±2.4 53.35 ±0·65 — 110.1 ± 5.9 30.85 ±6.25 149.75 ±1.35 — 31.85 ±6.75 Implementation 54.1 ±0.7 72.1 ±0.4 115.35 ±6.55 1.7 ±1.3 147.55 ±0.95 a 1.8 ±0.2 Implementation 51.95 ±0.45 71.15 ±1.95 116.25 ±0.25 8.5 ±1.1 146.8 ±1.4 — 7.1 ± 0. 5 Implementation 50.0 ± 0.28 67.6 ± 2.8 110.35 ± 1.35 2.2 Soil 1 · 0 143.35 Soil 0.65 — 2.3 ± 1.8 Application 51.65 ± 0.65 77.75 ± 0.6 96.5 ± 0.2 10.9 ± 0.4 148.8 ± 0.4 153.9 ± 0.8 12.65 ± 0.65 Implementation ^ Jll 51.05 ±1.95 78.3 ±0.2 108.8 ±0.0 12.49 ±0.9 143.85 0.85 - 11.95 Shi Shi 175 poor persons _ ^ M2_ 51.45 0.85 76.85 ± 0.45 105.15 ± 1.55 9.7 ± 0.2 147.6 ± 1.3 - 10.9 0.8 L soil NB stands for "_" is not observed. ---

4_DSC analysis results of Examples 13 to 18

S From the DSC chart of the first temperature rise of Examples 13 to 18, the glass transition temperatures (Tgl, Tg2), low temperature melting temperature (Tml), and heat of fusion (AHm) of the polylactic acid compatibilizers of Examples 13 to 18 are known. As shown in Table 7 below, the DSC results for 18 201231492, as in Example 3 and Comparative Example 4, are also listed in Table 7 below. Table 7 Tgl (°C) Tg2 (°C) Tml (°C) △ Hm (J/g) Comparative Example 3 45.95±3.35 I 124.0±0.39 14.4±2.14 Example 13 48.9 ±〇114.54±1.97 7_8 ±1.2 Example 14 47.05±0.5 a 117.85±2.15 6·8±0·5 Example 15 38.1 ±1.3 — 112.09±2.0 4.7 ±0.6 Comparative Example 4 39.6 ±3.7 55.0 118.3±0.3 17.25 ±2.35 Example 16 46.25± 0.75 74.95 ± 0.55 126.35 ± 0.25 10.65 ± 0.55 Example 17 43.0 73, 5 122.7 10.2 _ Example 18 [Note 1 Γ -, 〆 41.45 ± 0.15 ¥矣去Μ目,:丨ni 64·75±0·05 121.85 ±0.05 10.6 Soil 0.5 In Table 7, the heat of fusion of the polylactic acid compatibilizer of Example 丨6_丨8 is higher than that of the polylactic acid compatibilizer of Examples 13-15. More specifically, lactic acid oligomerization When the weight ratio of the body to the bisphenol A type ethoxylate resin is 5:4, the heat of fusion of the copolymer obtained from 6 hours to 1 hour is about 10 J/g, but The heat of fusion of the copolymer prepared at a weight ratio of 4:7 decreases as the polymerization time increases, and decreases from 6 hours to 8 hours, and decreases from 8 hours to 10 hours. 〇, in the system with a large amount of bisphenol a-type epoxy resin, as the polymerization time increases, the more the copolymer is synthesized, the more compatible the lactic acid oligomer is with the bisphenol A epoxy resin. Reducing the crystallization behavior of the acid oligomers, and further reducing the heat of melting, while in the system of lactic acid oligo and body k, the continuous phase is lactic acid oligomer, and the double-type A epoxy tree is increased with the reaction time. It is more compatible with lactic acid rallies, but has a limited effect on the degree of crystallization of the overall phytic acid oligomer, and the heat of fusion of the copolymer obtained by the polymerization for 6 hours to j 10 hours is almost the same. Further, 'Table 8 below is the glass transition temperature (Tgl, Tg2) as described in the DSC chart of the first drop of the examples n to a, respectively, and 19 201231492 from the second of the embodiments. The glass transition temperature (Tgl, Tg2') known in the DSC chart of the secondary temperature rise. Table 8

<Crystal Form Observation - SEM> The inventors prepared the copolymers of Examples 6, 12, 15 and 18 and the compounds of Comparative Examples i to 4, respectively, in an appropriate amount of methylene chloride and at a temperature of 40 C. A plurality of test samples were obtained by vacuum drying "days", and each test sample was observed by SEM to analyze changes in phase behavior before and after the polymerization. 1 to 4 are SEM images of the test samples of the comparative examples (i.e., before the lactic acid oligo and the bismuth A type epoxy resin were subjected to the reaction), and the magnification thereof was 3,000 AiL y ΙΞΙ 1 . The microstructures shown in Figures 1 to 4 are attached to a plurality of surfaces; the dimorphic structure of the particles, that is, the phase separation; and the testing of Examples 6, 12, 15 and 18 in Figure 5 The sample (ie, lactic acid oligomer 1 : SEM type epoxy resin was polymerized after 1 G of polymerization, and the obtained copolymer had two: Γ magnification of 3000 times'. The micro-1 structure shown in FIG. 5 to FIG. 8 was almost seen. The phase separation of the block copolymer obtained from the particle or the relatively rare self-identified oligomer and the (4) type A epoxy resin for polymerization reaction 201231492 is not obvious. <PLA/PC composite material> [Application Example 1] This application The preparation steps of the examples are as follows: (1) PLA (weighted from NatureWorks; split number 2002D) and PC (purchased from Chi Mei Industrial; model pc U〇u) in a weight ratio of 1:1 are dissolved in CH2C1 solution, respectively. And then uniformly mixing the two to obtain a first solution. (2) Adding 20 parts by weight to the first solution in the step (1) (total weight of the total weight of PLA and PC) The polylactic acid compatibilizer of Example 6 was obtained to obtain a second solution. (3) Approximately 0.5 ml of the step (2) was obtained. The second solution was dropped on a glass slide, and the solvent in which it was allowed to stand was completely evaporated to obtain a PLA/PC composite material. [Application Example 2] Application Example 2 was prepared in the same manner as in Application Example 1. The pla/pc composite material 'is different only in that the polylactic acid compatibilizer of Example 6 in this step is substituted with the polylactic acid compatibilizer of Example 12. [Comparative Application Example 1] Comparative Application Example 1 is direct The first solution obtained by the step of Application Example 1 of about 〇5 ml was dropped on a glass slide, and the solvent was allowed to stand until the solvent was completely evaporated to prepare a PLA/PC composite material. 21 201231492 &lt;; observation of the crystal form of the polarizing microscope&gt; _. The inventors will compare the pLA/pc composite material obtained in Application Example 1 and Application Examples 1 and 2 into a test sample conforming to the sample specification of a polarizing microscope, and observe with a polarizing microscope. The maternal group measures the 纟 θ type of the sample under different conditions, and the POM map of the pLA/Pc composite material of the application example 1 and the application examples 1 and 2 can be deduced from the POM map at room temperature. Compare the particle size appearing in the PLA/PC composites The PC particle size of the non-continuous phase of 5 〇em is the same as that of the PC particles of Examples 1 and 2, respectively, about 4 〇 "m φ and 20 /zm 〜 35 μ m. The other inventor will also test the sample at Hold the temperature at 23 〇t for 5 minutes, make it into a molten state, and observe its crystal form by polarized light microscope. After that, the test samples are cooled to 120 ° C and held at 12 ° t for 1 hour. The crystal form was observed by a polarizing microscope. Comparing the different crystal forms, it was found that the PLA/PC composite of Comparative Application Example 1 obtained by adding the polylactic acid compatibilizer of the present invention, after melting, would be in PLA. PC particles with a particle size of about 50 #m~100 &quot; m appear in the continuous phase because the molecules have good fluidity in the molten state, making PC molecules more likely to get together, resulting in larger particles. In the PLA/PC composite material of Application Example 1, after thawing and cooling crystallization, the PC particles in the discontinuous phase were significantly reduced, and the boundary between the PC particles and the continuous phase was also less obvious. As for the PLA/PC composite material of Application Example 2, after heating and melting, the compatibility of the pla/pc composite material is improved, and the pc particles are less and uniformly dispersed in the PLA continuous phase, so the crystal form is observed by a polarizing microscope. No crystalline particles were observed in the state, indicating that the crystalline particles may be very

S 22 201231492 Small or no crystallization behavior occurs. In summary, the present invention can be prepared by first preparing a lactic acid oligomer, and then mixing the lactic acid oligomer with an epoxy compound to make the reactants undergo a poly-σ reaction. a special structure (that is, a copolymer containing both a polylactic acid segment and a benzene ring structure), and the copolymer has been experimentally confirmed to contribute to the compatibility between PLA and PC, and is a good compatibilizer, so it can indeed The object of the invention is achieved. However, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention, All remain within the scope of the invention patent. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an SEM image showing the crystal form of the test sample of Comparative Example 1 (ie, before the lactic acid polymerizer and the double-presence A type epoxy resin are not reacted), and the magnification is 3000 times; 2 is an SEM image showing the crystal form of the test sample of Comparative Example 2 (ie, before the lactic acid polymerizer and the bisphenol A type epoxy resin are not reacted), the magnification of which is 3000 times; FIG. 3 is an SEM image. The crystal form of the test sample of Comparative Example 3 (ie, before the lactic acid polymermer and the bisphenol A type epoxy resin were not reacted) was shown to have a magnification of 3000 times; FIG. 4 is an SEM image showing the comparative example 4 The crystalline honey state of the test sample (ie, before the lactic acid oligomer and the bisphenol A type epoxy resin are not reacted) has a magnification of 3000 times; 23 201231492 FIG. 5 is an SEM image showing the test sample of Example 6 (ie, The crystal form of the copolymer obtained by polymerizing the lactic acid oligomer with the bisphenol A type epoxy resin for 10 hours has a magnification of 3000 times; FIG. 6 is an SEM image showing the test sample of Example 12 ( That is, the lactic acid oligomer and the bisphenol A epoxy resin are polymerized 10 times. The crystal form of the copolymer obtained afterwards has a magnification of 3000 times; FIG. 7 is an SEM image showing the test sample of Example 15 (ie, polymerization of lactic acid oligomer and bisphenol A type epoxy resin). The crystal form of the obtained copolymer after 10 hours has a magnification of 3000 times; and FIG. 8 is an SEM image showing the test sample of Example 18 (ie, lactic acid oligomer and bisphenol A type epoxy resin). The crystal form of the copolymer obtained after the polymerization reaction for 10 hours had a magnification of 3,000. [Main component symbol description] M. *»*, £ 24

Claims (1)

201231492 VII. Patent application scope: 1. ^ Seed gas-gas acid compatibilizer, which has the following chemical formula (1): (I) wherein 'K and r2 represent an alkyl group of c2 to c10, respectively; n1 and n2 each represent an integer of 55 to 208; and A represents a divalent group derived from a ruthenium oxide, and the epoxy The compound contains a terminal epoxy group and at least one unsubstituted or substituted phenyl group on the main chain, and the epoxy compound has an epoxy equivalent of from 18 Å to 5 Å. The polylactic acid compatibilizer according to claim 1, wherein the epoxy compound has an epoxy equivalent of between 1,000 and 5,000. 3. The polylactic acid compatibilizer according to claim 1, wherein the lactic acid polymer having the following chemical formula (11) is subjected to ring-opening condensation polymerization of the epoxy compound. : 5^lactic acid compatibilizer as described in the article, Fuzhong Wherein 'η represents an integer from 55 to 208. 4. Condensation according to item 1 of the patent application scope | The epoxy compound has the following chemical formula (III): Η 25 201231492 R5 r9 Wherein, X and Y respectively represent R8 R7 Rl2 R11, and R3 and R4 respectively represent a CrC? alkyl group, a c2~c7 aromatic group or argon, and R_5 to Rl2 respectively represent a CfCs alkyl group, halogen or hydrogen; And m represents an integer from 1 to 250. 5. The polylactic acid compatibilizer according to claim 4, wherein the epoxy compound is selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and desertified epoxy resin. Or a combination of these. £ 26