WO1992021708A1

WO1992021708A1 - Biodegradable polymer, production thereof, and use thereof

Info

Publication number: WO1992021708A1
Application number: PCT/JP1992/000732
Authority: WO
Inventors: Ichihiko Yamamoto; Makoto Kurihara; Taku Sato
Original assignee: Kirin Beer Kabushiki Kaisha
Priority date: 1991-06-07
Filing date: 1992-06-05
Publication date: 1992-12-10

Abstract

A novel biodegradable copolyester composed of the structural units represented by general formulae (I) and (II) and having a number-average molecular weight of at least 50,000; a novel pseudomonas which can produce the copolyester; and a process for producing the copolyester by culturing the pseudomonas in formulae (I) and (II) wherein X and Y represent each an integer of 0 to 16.

Description

Meiyanagi Biodegradable polymer compound, its manufacturing method and its application technology

The present invention relates to a biodegradable copolyester, and more particularly to a biodegradable copolyester and a novel microorganism. The method of manufacture and its use.

Hi

冃 Technology

In recent years, as people's interest in environmental issues has been increasing, synthetic plastics have become a serious problem from the viewpoint of environmental pollution and resource recycling. Ri ¾ P «J τάί As a result, biodegradable plastics are being noted. Ο One of the typical biodegradable plastics known in the past is po.

• J-3-Head σ Kishibuchi rate (Ρ Η Β) Powerful. The second substance is a substance that is stored in the cells of many microorganisms as an energy storage substance, while it is a thermoplastic high-grade substance that has excellent biodegradability. It is a numerator. Therefore, this Η Η Η is a petroleum independent polymer that is not dependent on petroleum and is a “clean plastic” that conserves the environment. In addition, the tremendous attention that has been paid to the various physical properties, including biodegradability, required of the current plastics, has been noted. It is impossible to achieve power only with a copolymer containing Ρ Η Η 、、、 It is said that B alone has the problem that it is brittle, and new plastics that have biodegradability regardless of whether they are synthetic or non-synthetic Is required.

With the aim of searching for a new polymer that answers such a demand, the present inventors have separated a large number of microorganisms from soil and separated and searched for the macromolecule produced by them. As a result, they have found that certain microorganisms produce novel and useful copolyesters, and completed the present invention.

Therefore, an object of the present invention is to provide a novel biodegradable copolyester.

Another object of the present invention is to provide a novel microorganism having an ability to produce this novel biodegradable copolyester.

Further, the present invention aims to provide a novel method for producing a biodegradable copolyester using the microorganism.o

Further, the present invention aims to provide a polymer blend having improved flexibility compared to PHB.

Other objects of the present invention will become clear from the following writing power.

Disclosure of the invention

The polyester according to the present invention comprises a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II) And have a number average molecular weight of more than 50,000

CcI.

H H

Two

) C

H X

2 C

H C (I)

o 3

(H = CH, CH C) y CH

OCH-CH and CO (II) In the formula, X and Y each represent an integer of 0 to 16. In addition, the novel microorganism according to the present invention is a novel strain belonging to Pseudonas ♦ funorelesence.

Further, the method for producing the above-mentioned copolyester according to the present invention belongs to the genus Nudus monas and has an ability to produce the above-mentioned copolyester. It is characterized by culturing bacteria and collecting the above-mentioned copolyester tenor from a culture medium.

In addition, the polymer blend according to the present invention is one that includes the above-mentioned copolyester and PHB.

Brief explanation of drawings

The figure shows the infrared absorption spectrum (cast-finolme method) of the polymer of Example: I.

FIG. 2 shows a proton nuclear magnetic resonance spectrum of the polymer of Example 1 (500 MHz, in a heavy-mouthed cavity).

FIG. 3 shows the carbon nuclear magnetic resonance spectrum of the polymer of Example 1. (125 MHz, in heavy chloroform).

FIG. 4 shows the proton nuclear magnetic resonance spectrum (500 MHz) of the monomer A2 in Table 4 obtained from the polymer of Example 1. , During heavy chloro hologram).

FIG. 5 shows the proton nuclear magnetic resonance spectrum (500 MHz) of Monomer B 2 in Table 4 obtained from the polymer of Example 1. (During heavy black hologram).

FIG. 6 shows the proton nuclear magnetic resonance spectrum of the monomer A3 in Table 4 (500 MHz) obtained from the polymer of Example 1. (Heavy black mouth in the home).

FIG. 7 shows the infrared absorption spectrum of the polymer of Example 15 (by the cast film method).

FIG. S shows the proton nuclear magnetic resonance spectrum of the polymer of Example 15 (in t SOO OMH s s heavy chlorophenol).

FIG. 9 shows the carbon nuclear magnetic resonance spectrum of the heavy product of Example 15 (125 MHz, in a double-mouthed cavity).

BEST MODE FOR CARRYING OUT THE INVENTION

CO POLIES Tenoré H Y — 1:

The polyester according to the present invention comprises the structural units (I) and (お) represented by the general formulas I) and (（) described above. (Note that in the present specification, the polyester according to the present invention may be simply referred to as “HY-1”).

Array of structural units (I) and (!!) in HY-1 Can be block or random. The composition of the structural units (I) and (II) can be determined as appropriate in consideration of the physical properties of the plastic material, biodegradability, and the like. The composition of I) is preferably in the range of 0.1 to 99.9, more preferably in the range of 70 to 98 in mol%, and more preferably in the structural unit (H). The composition power is in the range of 99.9 to 0.1, more preferably 30 to 2.

In the general formulas (I) and (11), X and Y can be appropriately determined as long as various physical properties desired for use as a polymer can be realized. , Respectively, from 0 to 16, preferably from 〇 to 12, and more preferably from 2 to 9. Further, as long as the structural unit is included in the range of the above general formula (I) or (II), X and γ are different in each structural unit in the molecule. You may be.

In addition, the structural unit as the third component may be located in the molecule or at the end of the molecule, as long as it does not affect the physical properties, particularly biodegradability, of HY-1. It can exist, for example, through an ester bond.

The molecular weight of HY-1 is appropriately determined in consideration of the physical properties and biodegradability of the plastic material, but the molecular weight obtained by gel filtration is preferred. Is 10, 0 ◦ 0 〜

5, 0 0, 0 0 0, more preferably 10, 0 0 0 to 2, 0 0 U, U 0 0, and the number average molecular weight is

5 0, [] 0 0 or more. HY-1 is generally obtained as a viscous viscous substance at normal temperature by methanol precipitation according to the production method using microorganisms described below, but the solvent is removed under reduced pressure. Some are obtained as solids (films) when completely removed. This Υ-1 is soluble in black mouth porphyry, poorly soluble in acetone, insoluble in methanol, ethanol, and water.

The Υ--1 according to the present invention is a copolyester produced by a microorganism, which is originally stored in the cells of the microorganism and is an energy source of vital activity. It is presumed that the substance is functioning as That is, the above-mentioned Η—1 is a substance that can be incorporated into the natural carbon cycle, and is considered to be a polymer compound that can be decomposed by microorganisms. .

Also, since Η Υ-1 has two double bonds in its molecule, it is possible to use this double bond to modify Η Υ-1 molecule. . For example, by using this double bond to introduce Manka ^ into Υ Υ-1, it is possible to improve various physical properties as a plastic ^. It is possible.

In addition, Η Υ-1 is a generally more flexible substance than the biodegradable highly-integrated / degraded 見出 found in the past, for example, Ρ Η Β. However, it can be used as a polymer blend in addition to this. Also, by adding Η--1 to other biodegradable polymer compounds, it is possible to improve various properties of the polymer, for example, flexibility. . In other words, HY-1 is a property improving agent for other polymer compounds. It has all uses.

When HY-1 is used as a flexibility-imparting agent for a biodegradable polymer, the blend ratio is generally such that HY-1 is 30 to 2.5% by weight, The other biodegradable polymer compound is preferably 70 to 97.5% by weight, and the more preferred blend ratio is HY-1 to 25 to 2.5% by weight. %, The power of other biodegradable polymer compounds is 75 to 97.5% by weight. PH B is preferred as another biodegradable polymer compound. In particular, a PHB force having a number average molecular weight of 100 ° and 100 ° is preferred.

The polymer blend of HY-1 and PHB has improved flexibility as compared with PHB, and the possibility of its use as a molding material is wide. No.

The method for producing the polymer-prend is not particularly limited, but, for example, a solvent that dissolves PHB and HY-1 well together.

(E.g., chlorophoronem, dichloromethane, etc.), dissolve and mix well, evaporate the solvent, and heat and crystallize. After melting and mixing by heating, there is a method of crystallizing by heating.

When using the polymer blend, additives such as stabilizers, release agents, lubricants, plasticizers, and fillers such as pigments, dyes, and glass fibers are used. It is also preferable to add such as.

In the case where HY-1 was obtained as a film by the production method using a microorganism described below, the results of the test in Example 21 described later were shown. As evident from the mechanical properties, HY-1 can be molded directly into, for example, food packaging films, shopping bags, agricultural films, etc., as well as water-resistant coating agents for paper backs, It is expected to be used for materials such as outdoor sports materials, DDS materials, and surgical sutures such as roof _tees.0

New pseudomonas bacteria:

Microbial deposit

The microorganism according to the present invention is a new strain (two types) isolated and collected from soil in Gunma Prefecture. Based on the mycological properties described below, these strains are referred to Bergey's Manual of Deter- nerative B cteriol o 8th edition, and are referred to as pseudomonas. Pseudomonas) is a bacterium belonging to the genus fluorescens (ore uorescens) 力, and each of them is a bacterium belonging to the genus Pseudomonas フ uorescens ·. 0-0 strains and pseudomonas ♦ Phoreolethsens · It was named G1221 strain. These strains were obtained under the accession numbers "Micro-Kenjo No.335" and No.3785 (FERMBP-3351 and BP-3875). Deposited on the Microorganisms Industrial Research Institute of the Ministry of International Trade and Industry on April 10, 1991 and May 27, 1992, respectively.o

Mycological properties

(A3 Pseudomonas fluorescens ^ 0, which is a typical example of a bacterium belonging to the genus Pseudomonas according to the present invention. The following is a list of the bacteriological properties of the 30 strains.

I. Morphological properties (observed at 1-2 days at 30 ° C)

1. Cell shape and size: Bacillus

2. Presence / absence of cell polyplasia: not particularly recognized

3. Motility (flagellated state): Yes (monopolar hair)

4. Spore presence: not formed

5. Gram staining: negative

6. Acid-fast: negative

I I. Growth conditions in each medium (1 ~ at 30 ° C: L observation for 4 days)

It is shown in the following table.

Table 1

The surface is sliding force, with circular uplift

Gravy agar plate medium

The color is light brown

Grows thinly

Gravy

The color is light brown

Grows turbid and precipitates

Broth liquid medium

The broth gelatin puncture medium grows well on the surface,

Liquefaction is observed

Peptone

Litmus milk III. Physiological properties (observed for 1-2 days at 30 ° C) 1. Nitrate reduction: negative

2. Denitrification reaction: negative

3. MR test: negative

4. VP test: negative

5. Indole generation: negative

6. Production of hydrogen sulfide: negative

7. Oxidation of dalonic acid: negative

Degradation of S. esculin: positive

9. Decomposition of horse urea: positive

10. Arginine dihydrolase: positive

11. Lysine decarboxylation: negative

12. Ornithin decarboxylation: negative

1S. Phenylalanine deaminino reaction: negative

14. Alasium Midase: Negative

15. Tween 80 Decomposition: Positive

Hydrolysis of 1 β. Starch: negative

17. Use of citric acid: positive

15. Use of inorganic nitrogen sources

Potassium nitrate: positive

Ammonium sulfate: positive

〗 9. Dye formation: Water-soluble fluorescent dye diffuses into the medium

20. ゥ Laser: positive

21, キキ: Positive Power: positive

Growth range

Grow at pH 5-8, optimal pH 6-7

Growing at a temperature of 10 to 30 ° C, optimal temperature is 250 ° C Attitude to oxygen: aerobic

0 — F test: oxidative

Whether acid and gas are produced from sugar

(Vepton water)

L-arabitose 1

D — Xylose +

D — Guru course +

D — Mannose +

D — Fractose +

D — galactose

Maltose

Sucrose +

Lactose

Tre / Loose +

D — Sonore bit

D—Mannit +

Ino Sit Sat

Glycerin +

Starch + Two

CB j Another typical example of a bacterium belonging to the genus Pseudomonas according to the present invention, s. The list is as follows.

I. Morphological properties (observed at 1-2 days at 30 ° C)

I. Cell shape and size: Bacillus

Presence or absence of cell polyplasia: Not particularly observed

Motility (flag flag formation): Yes (polar flagella) Spores: no formation t,

Gram stainability: negative

I: Growth condition in each medium (30 to 1-: L for 4 days)

IX 'as shown in the table.

Table 2 Juice agar plate medium The surface is slippery, and it protrudes circularly

Light brown color spreads thinly and grows

Gravy agar slant medium

The color is a light brown juice liquid medium.It grows turbid and precipitates.

Meat Pet gelatin spiking medium Grows well on the surface,

Litmus with liquefaction [II. Physiological properties (observed for 1-2 days at 30 ° C) 1. MR test: negative

2. VP test: negative

3. Generate indole: negative

4. Production of hydrogen sulfide: negative

5. Arginine hydrolase: positive

6. Lysine decarboxylation: negative

7. Ornithin decarboxylation: negative

8. Use of citric acid: positive

9. Dye formation: Diffusion of water-soluble fluorescent dye into the medium] 0. ゥ Raise: Positive

11. Oxidase: positive

12. Catalase: positive

13.Range of growth

Growing at pH 5 ~ 10, optimal pH ~ 7

14.0 — F test: oxidative

15.Presence of acid formation from sugar

Medium composition: ammonium dihydrogen phosphate 0, 1%

Potassium chloride 0.02% Magnesium sulfate 0.02%

Ten%

Lara Bittorose

D—Xylose +

D-glucose + D—Mannose +

D—Fructose +

D—Galactooth +

Maltose

Sucrose soil (growth is allowed) lactose

Tore-, ヽ π

D—Sorbit

D—Mannit

Innocent

(Growth is observed even without acid generation) Glycerin +

Starch one

Strain identification

Next, the grounds for identifying the strain according to the present invention as a novel strain belonging to pseudomonas ♦ funoreresence are shown below.

As indicated by the mycological properties described above, this strain is "a gram-negative bacillus that does not form spores, is absolutely aerobic, and is positive for catalase and oxidase". Such a bacterium, such as a bacterium, is suitable for belonging to the genus Shudomonas according to the Bergey's Manual mentioned earlier. Then, when this strain was compared with the 27 species that rot to the genus Pseudomonas described in Bergey's Manual, the strain was found to be stubble. The mycological properties are almost the same as the pseudomonas fluorescens described in Bergey's Manual, except for the point that the positive result is obtained by using a black stain. Based on the above results, the strain according to the present invention was determined to be a new strain of pseudomoss ♦ fluoresence, and the strain according to the present invention was screened. Domonas Fluoresceins ♦ 0—30 strains and G1221 strains. Cultivation conditions

The cultivation of the novel Pseudomonas spp. Bacterium according to the present invention may be any purpose, including the type of culture medium and the culture conditions. In addition, it is possible to obtain a desired amount of bacterial cells by growing the cells by culturing.

As a carbon source of the medium, any power that the bacteria according to the present invention can utilize can be used (specifically, methanol, ethanol, etc.). Synthetic carbon sources such as oil and acetic acid; inorganic carbon sources such as carbon dioxide; natural products such as yeast ex., Molasses, peptone, meat ex., Fructoses, Sugars such as glucose, sucrose, etc., sonorebito, mannitol, inoitols, soybean oil, olive oil, etc. Oils, organic acids such as citric acid, succinic acid, and dalconic acid. In particular, sugars such as Practice, Glucose, and Xylose are preferred.

Similarly, nitrogen sources include inorganic nitrogen compounds such as ammonia, ammonium salts, and nitrates, urea, and cones. , Peptone, yeast ex, meat ex Various synthetic or natural products that can be used by the bacterium, such as organic nitrogen-containing substances such as sulfur, can be used. In particular, in the case of the strain G1221, addition of yeast extract is preferable for growth, in which case 1 to 8? . Is very effective.

In addition, according to the usual method of culturing microorganisms, inorganic salts such as calcium salt, sodium salt, and phosphate, manganese, zinc, copper, and molybdenum Micronutrients such as sodium, potassium, nickel, chromium, etc., salts of gold m, boron compounds, iodine compounds, vitamins, and amino acids. Can be added in the same way.

The cultivation temperature is about 20 to 40 ° C, preferably about 25 to 35 ° C. The pH at the start of the cultivation is about 6-1 °, preferably about 6.5-9.5. Under the above conditions: Incubate with aerobically stirring or shaking for ~ 3 days. The culture method can be either batch culture or continuous gun culture.

When the culture is performed under the above conditions, the growth of the microorganisms is relatively poor, but it does not prevent the culture from being performed under these conditions.

Production of H Y-1:

The bacterium belonging to the genus Pseudomonas according to the present invention has a property of producing the HY-1 and the HY-1 is added to the microorganism while the growth is being continued. Thus, it is synthesized and stored mainly in the cells. Therefore, the bacterium according to the present invention is cultured, and the HY-1 is collected from the culture. -1 1-HY-1 can be manufactured.

Preferred culture conditions for the production of HY-1 include temperature and temperature, preferably from 20 to 40 ° C, preferably from 25 to 35 ° C, and pH.

6 to: L 0, preferably 6.5 to 9.5. The microorganism according to the present invention continues to produce HY-1 while the growth is continued. Therefore, HY-1 can be produced while culturing the cells by culturing in the above-mentioned ordinary medium. On the other hand, the microorganism of the genus Pseudomonas according to the present invention grows on the condition that the amount of the assimilable carbon compound present in the substrate is sufficient. Higher levels can be achieved by culturing in a medium with at least one essential component, preferably nitrogen and / or phosphorus, restricted. Until then, the polymer synthesizes and accumulates (for the preferred medium composition for such HY-1 production, refer to the experimental examples described later). Among the novel m strains according to the present invention, it is preferable to use saccharides as an assimilating carbon source, and the strain according to the present invention uses saccharides as a carbon source. Producing a copolyester having a double bond in its molecule is likely to be unique.

In the method for producing HY-1 according to the present invention, the cells grown in a normal culture medium are separated by a conventional solid-liquid separation means such as filtration or centrifugation. Preferably, a two-stage culture of collecting the cells and further culturing the cells in a medium for HY-1 production is preferred. Note that the temperature and pH at the time of this subsequent cultivation may be the same as those of the previous cultivation. 8 Next, HY-1 is collected from the culture containing the bacterial cells cultured as described above. Since HY-1 is mainly accumulated in the cells, it is preferable to isolate the cells from the culture and to isolate HY-1 from the cells. . Isolation of H'Y-1 from the cells isolated from the culture is performed by washing the cells, freeze-drying, and then removing HY-1 by the black hole holm. It is preferable that the extraction and the precipitation and recovery using a solvent (eg, water, alcohol) be performed by the 'O method. Shine Monas Funoreolecce 0-30 shares

A 5 L triangular flask with a wart was inoculated in 1 L of medium having the following composition (1 L of distilled water or r ') *, and pH 7.5,

The cells were aerobically shake cultured and grown in U for 24 hours. Earth Exhaust: 10 g

1! ^ Photon: 10 g

ぺ 2-Γ "■: 5 g

: 5 g

The cells were collected by centrifugation (600 rpm, 20 min) and the following composition in a triangular flask with a 5-L wart (1 L / distilled water) And inoculated in the same manner as above at pH 7.5, 30 ° C for 24 hours with aerobic shaking, and 20 g of gel course.

^ HP 0 _A g 9

N a HP ₄ • 2 H 0 1 g

N a C 1 1

M g S 0 H 0: 0.5. 5

4 · ⁷ g

Trace vat element solution: 10 ml

The trace element solution has the following composition (INHC1

Per liter).

M n S 0

4 ♦ ⁴ H 0: 1.98 g

Z n S 0 H 0: 0. 2

4 * ⁷ 9 g

C u C 1 2-2 H 0: 0. 17 g

C a C 1 2 ♦ 2 H 0: 1.47 g

C o S 0 H ₉ 0: 2.8

4 - ⁷ 1 g

F e S 0 H ^ 0: 2.7 g

4 ♦ ⁷

The cells were collected by centrifugation (6000 rpni, 2 Omin), purified with an acetate, freeze-dried, and then ticked at 12:00 with a sock slide extractor. A home extraction was carried out, and a 20-fold amount of medium was added to the extract, and colorless, transparent and viscous HY-1 was recovered by precipitation. The results showed that the cells contained 4.6% (heavy / heavy) polymer. Also, polymer

The ratio of the structural units of (I) and (II) was determined according to the NMR measurement. The result is as shown in Table 3

Furthermore, the composition of the heavy form is determined by converting methyl 13-hydroxy acids produced by methanolysis into high-performance liquid chromatography (HPLC). And the content of the ingredients Regarding the structure, methylenol — 3-hydroxyacids produced by methanolysis are separated and purified by HPLC, and then analyzed by NMR and GC analysis. The results determined by the spectrum analysis are as shown in Table 4.

Further, the molecular weight of the base was determined by a gel filtration method using HPLC under the following conditions. Polystyrene was used as a reference material.

Equipment: T O S O H L C-800 A

Detector: RI

Solvent system: Chlorophorne 100? . , 1 m 1 / min

Column: The following four cables were connected in series.

T S K gel G 2 0 0 0 H

T S K gel G 3 0 0 0 H

T S K gel G M H X L

The obtained molecule S was in the range of 15,400,170,000, and the number average molecular weight was 1,200,000. Projection Example 2-S

Under the same conditions as in Example 1 above, cell culturing and production of a superstructure were performed as in Examples 2 to 8.

Example 9: L 2

Cell culture and production of heavy bodies were performed in the same manner as in Examples 9 to 12 in the same manner as in Example 1 except that a triangular flask without warts was used during the culture. I went. Examples 13 and 14

Cultivation of cells and production of a haploid were carried out in the same manner as in Example 1 except that sucrose and mannose were used instead of glucose. Examples 13 and 14 were used. Example 15

SHUDMONAS ♦ Fluorescence Strain 'G1221 strain has the following composition (per 1 L of distilled water) in a triangular flask with a 5 L divo. Inoculated medium (1 L), pH 7.5,

The cells were grown aerobically with shaking at 30 ° C for 24 hours.

Exhaust: 50 g

Polypeptone: 5 g

Meat kiss: 3 g

Glucose: 5 g

Next, the cells are collected by centrifugation (6000 rpm, 2 Ora in), and have the following composition (per 1 L of distilled water) in a triangular flask with a 5 L divo. Inoculate 1 liter of medium and proceed as above.

The cells were cultured aerobically with shaking at 70 ° C. for 72 hours at 30 ° C.

Glucose: 75 g

K ^ HP0: 2.1 g

Four

N a H P 0 2 H 0: 1

4 9

N a C 1: 1 g

M g S 0,! ♦ 7 H ₉ 0: 0.5 g

Trace original purple solution: 10 in 1 While-Trace element solution NHC 1

Per 1 L)

M n S 0 4 H 0 9 8 g

4 ♦

Z n S 0 7 H 1 0 0 2 9 g

Four ·

C u C 1 2 * 2 H ₂ 0 0 17 g

C a c 1 2 2 H 1 0 4 7 g

C os 0 7 H 0 2 8 1 g

4 ♦

F e s 0 7 H 0 7 8 g

Four ·

The cells were collected by centrifugation (6000 rpiii, 20 lines), washed with acetone, lyophilized, and then closed for 12 hours with a sock tray extractor. The extract was extracted with water, and 20 times the volume of methanol was added to the extract to precipitate a colorless and transparent viscous substance. The solvent was then removed under reduced pressure to obtain a solid HY-1 was recovered. As a result, is the cell 18.5? . Including (heavy m) heavy forms:: and are shown. The ratio of the structural units of (I) and (H) was determined by subjecting the superstructure to proton NMR measurement. The conclusions are as shown in Table 3.

In addition, the composition of the polymer is determined by converting methyl 3-hydroxy acids produced by methanolysis to high-performance liquid chromatography (HPLC). The structure of the components was determined by HPLC, and the methyl 3-hydroxy acids produced by methanolysis were analyzed by HPLC. After preparative purification by NMR, determination by NMR and GC mass spectral analysis was performed. The results are as shown in Table 4.

Further, the molecular weight of the polymer was determined by a gel filtration method using HPLC under the following conditions. Polystyrene was used as a standard substance.

Equipment: T O S O H L C-8 0 2 0

Detector: RI

Solvent-based black hole home 1 0 0% 1 πι 1 / min

The following two columns were connected in series.

T S K gel G M H X L

The obtained molecule m was in the range of 10,600,677,000, and the number average molecular weight was 80,60 °.

Example] 6 1 9

The cells were cultured and the polymer was produced under the same conditions as in Example 15 as in Examples 16 to 19.

HY-1 was isolated from the bacterial cells obtained in the above-mentioned Examples 2 14 and 16 19 in the same manner as in Examples 1 and 15 and its content was determined. And composition. The results are as shown in Table 3 below. Table 3

Body weight content 9. Ratio of structural units Structure (I)

1 4, 6 SO. 1 19.9

· 2 79. 7 U.-?

3 丄 u, 丄 SO. 6 丄,

4 1 丄. 1 81.5 O 丄 C>,-> r 16, 0 79.6 20. 4

J し j »η リ 79. 9 n U ♦ 丄 1

14, 1 79. 8 20. 2

1 7 75. 9 4 · 丄 η and J. U 93.3 D · / n n 91.7 «

: 0.01 97. 2 2. 8

3.6 79.0 21.0

2. S 78. 0 22. 0

IS. 5 94.5.5.5 U, 1.092.47.6 i 15.1 94.15.9, '12 .4 94.5.5.5C 13.6 92.8 7. Two Further analysis of the II coalescence obtained according to Examples 2, 13, 14, 15 and 18 shows that the compositions of these polymers are shown in the following table. Was shown to be as described in

Table 4

Mol% of monomer in polymer

Example

A B 1 A2 B 2 A3 B 3 A4

1 4. 7 6. 1 39. 3 9. 7 36. 1 4.1-1 14. 1 10. 6 47. 0 7. S 20.4

13 3.3 57.3 14.4 21.

14 9.8 8.7 51.5 13.3 16.7

15 28. 3 52. 2 5.5 10, 0 4.0

18 19.5 69.4 5.5.5.6

In the table, A 1 to A 4 represent the following structures

A 1: (Shi II) _{4 S} α · ^

1

0CH-CH C0

B 1 CH CH = CH (CH) 3 CH ₃ OCH-CH CO-

A2 (CH) ^ CH ^ OCH— CH CO B 2 CH ₉ CH = CH (CH) ₅ CH

0CH-CH C0-

(A3 and xi) gCH

OCH-CH ₉ CO

B 3 CH CH = CH (CH) ₇ CH

OCH— CH and CO—

A 4: (CH) 丄 Q CH

One OCH—CH and CO— Example 2

P-8150 (manufactured by Sigma, Cat. O. P-8150) and HY-1 obtained in the above Example 1 were used as shown in Table 5 below. After it was dissolved in a film and mixed well, the solvent was evaporated to give a film-like molded product. 70 for this film. It was heated and crystallized for 2 B with C.

For the finolem-shaped polymer blend obtained in this way, the elongation, the cutting strength and the jangling rate were measured in accordance with JISK7113. The results are relevant as shown in Table 5. Table 5

Mixing ratio of p H B · H V-1 (weight ratio)

P fiber 50: 1 40: 1 20: 1 10: 1 6 1 4: 1 3: 1 2: 1 Elongation

4.6 4.4 6.8 10.0 14.8 64.0 133.6

(%)

Cutting strength 1.1 1.1 1.0 1.0 0.8 0.4 0.3 0.3 0.2 (kg)

Young's rate

114 114 95 51 39 34 31 25 14 (kg / mm ² ) Example 2 1

The HY-1 obtained in the above Example 15 was dissolved in a black mouth film, and the solvent was evaporated to obtain a film-like molded product. This phenol was left under vacuum for 18 hours to completely remove the solvent, and the polymer in the form of ί ': ί was removed from the solution. ♦ As a sample manufactured by the cast method, the degree of mediation and cutting strength were measured according to JISK7113.

In addition, HY-1 obtained in Example 15 above was dissolved in chloroform and the solvent was evaporated to obtain a film-like molded product, which was left under vacuum for 18 hours. Leave the solvent and completely remove the solvent, and use a heat press to add 200. Press for 5 seconds without heating with C. Immediately in liquid nitrogen, leave at room temperature for 18 hours, and remove the fin The polymer is defined as a sample made by the melt-quenching method. The elongation and the breaking strength were measured according to the above.

These results are as shown in Table 6.

Table 6

Physical properties of H Y-1

Elongation (¾) Cut body (kgZ eyebrow :)

H Y-1 (Solution ♦ Cast) 4 1 2— 5 Q _ 0.2

H Y-1 (Melt ♦ quench) ― 64 0 0.6 Industrial applicability

The present invention provides a novel biodegradable copolyester, and more particularly, a copolyester having both biodegradability and flexibility. It can be used as a plastic material that can be used as a plastic material that has various physical properties, such as being a material, and a copolyester of the present invention. By blending with other biodegradable polymerized products, it is possible to improve the characteristics of the polymerized platform, and in addition to molding village materials in various fields. Therefore, it can be said that the field has a large mechanical strength that can be used as well as the field of the U river.

Claims

Range of request

1. It has a number average molecular weight of 50,000 or more consisting of a structural unit represented by the following general formula (I) and a structural unit represented by the general formula (1). , Copolyester.

(CH)-^-C H 2

OCH—CH CO (I)

CH CH = CH (CH) _Y CH

OCH CH CO (II)

(In the formula, X and Y each represent 0 to an integer of I 6.)

2. Pseudomonas * fluorescens · 0-30 strains with positive stub black staining.

3. Pseudomonas and fluorosence G1221 strains with positive stern black staining.

4. Culturing a bacterium belonging to the genus Pseudomonas and having the ability to produce the copolyester according to claim 1.

5. The method for producing a copolyester according to claim 1, characterized in that the copolyester described in claim 1 is collected from an animal.

5 ¾ Bacterial power 《Seed Monas Funoreolessensu ♦

The method according to claim 4, wherein the method is 0 to 30 strains.

6. Bacterial power “Side Monas' Funoreolessensu ・

The production method according to claim 4, wherein the production method is G1221 strain.

A polymer blend comprising the copolyester according to claim 1 and-another biodegradable polymerized product.

S. The polymer blend according to claim 7, wherein the other biodegradable polymer compound is a poly (3-hydroxybutyrate) (PΗB). .

9. An agent for imparting flexibility to a neutral molecule, comprising the polyester according to claim 1.