JP3394124B2 - Method for producing aliphatic polyester having a high degree of polymerization - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to a highly polymerized aliphatic poly
Regarding the method for producing the ester, more specifically,
Made of linear, highly polymerized aliphatic polyester with strength
A new way to build. [0002] 2. Description of the Related Art Thermoplastic polymers are generally excellent in molding.
Properties, mechanical properties, fibers, films, plastics
It is widely used for various purposes. But
In recent years, plastics has become one of the global environmental issues.
Polymer decomposed in the natural environment due to toxic waste
There is a need for material development. Especially for microorganisms
Decomposed plastics have excellent environmental compatibility
It is expected to be a great functional material. [0003] Aliphatic polyesters have conventionally been biodegradable.
Is known to have, for example, poly-3-hydro
Xybutyric acid ester (PHB), poly-ε-caprolactone
(PCL), polylactic acid (PLA), polyglycolic acid
(PGA) and the like can be mentioned as typical ones.
You. PHB is a polymer produced by microorganisms,
Low productivity, general purpose from an industrial point of view or cost
There are limits to replacing plastic. PCL is synthetic
A polymer having a high degree of polymerization is obtained, but the melting point is 6
The temperature is as low as about 0 ° C., and its use is significantly restricted. PLA,
PGA and their copolymers are used as bioabsorbable sutures.
Lactide and glycolide are usually used once
It is manufactured by a method of ring-opening polymerization after manufacturing
It is expensive and has problems with productivity. On the other hand, aliphatic dicarboxylic acids and aliphatic
Polyester made from polyester, e.g. polyethylene
Succinate, polybutylene succinate, etc. are manufactured at low cost
And biodegradable in soil
However, these polymers have low thermal stability and ordinary melt polymerization
Method produces a polymer with a high degree of polymerization that can be used
It is difficult. Titanium oxyacetylacetonate and
Method for polymerizing using lucoxy titanium compound as a catalyst
Japanese Patent Application Laid-Open No. 5-70574) has been proposed,
Is only about 15,000. Melting for a long time under high vacuum
Method for obtaining a polymer having a high degree of polymerization by polymerizing
JP-A-5-310898) has been proposed, but the productivity is high.
And the degree of polymerization is insufficient. [0005] Therefore, the molecular weight of these aliphatic polyesters
Hexamethylene diisocyanate, etc.
With a polyfunctional isocyanate compound of
JP-A-4-189822, JP-A-7-33862
Report), a method of treating with a polyfunctional anhydride (JP-A-6-32)
No. 2091, JP-A-7-53691),
(JP-A-7-5369)
No. 6) has been proposed. Polyfunctional isocyanate
The method used is capable of obtaining a polymer with a high degree of polymerization.
But a urethane bond is formed in the resulting polymer
As a result, light resistance and thermal stability are insufficient, and biodegradability
There is a problem in the physical properties of the polymer such as a slight loss. Many
Method of treating with functional acid anhydride, with polyfunctional epoxy compound
Although there is a so-called thickening effect in the treatment method,
Carboxylic acid groups and hydroxyl groups are formed, respectively.
A branched structure is formed, which is not preferable in terms of physical properties. More
A method of treating with nitrocarbonate (JP-A-7-5369)
No. 5) has been proposed, but according to this, heat resistance,
When aliphatic carbonate bonds with low water resistance are formed
Problem. [0006] SUMMARY OF THE INVENTION The object of the present invention is to
It is difficult to obtain a polymer with a high degree of polymerization by the melt polymerization method
A new method for increasing the degree of polymerization of aliphatic polyesters
Is to provide. Another object of the present invention is to provide a branch structure in a shorter time.
Providing high degree of polymerization linear aliphatic polyester that does not contain structure
It is to be. [0008] That is, the present invention provides a method for producing carbon
An aliphatic dicarboxylic acid component having 4 to 10 atoms and a carbon atom
Reduction mainly composed of aliphatic diol components of Formulas 2 to 6
Viscosity (phenol / 1,1,2,2-tetrachloroethane
In a mixed solvent (weight ratio 6/4), the concentration is 1.2 g / dl,
Measured at a temperature of 35 ° C) 0.3 or more and COOH end group
Amount 40 mol / 10⁶g or less of aliphatic polyester (A)
A compound (B) represented by the following formula (1) is
(2) The amount indicated in (2) was added, and the pressure was reduced in the presence of a polycondensation catalyst.
Under the inert gas atmosphere.
Characteristic, high polymerization degree aliphatic poly with reduced viscosity of 1.0 or more
This is a method for producing an ester. [0009] Embedded image(In the formula (1), R is 2 to 8 carbon atoms.
A valent aliphatic residue, n is an integer from 3 to 11; ) [0011] (Equation 2)                 0.25WX ≦ 10^FourY ≦ 1.2WX (2) (In the formula (2), X is an aliphatic polyester before addition of the component (B).
The amount of OH terminal groups of the ter (A) (mol / 10⁶g)
You. Y represents the amount of the component (B) added (% by weight / polymer).
I forgot. W represents the molecular weight of component (B). ) [0012] DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below. The aliphatic polyester (A) used in the present invention
Is an aliphatic dicarboxylic acid component having 4 to 10 carbon atoms,
Mainly from aliphatic diol components having 2 to 6 carbon atoms
Become. Here, an aliphatic dicarboxylic acid having 4 to 10 carbon atoms
As, for example, succinic acid, glutaric acid, adipic acid,
Sebacic acid and the like can be mentioned. These aliphatic zika
The rubonic acid component may be used as it is for polymerization,
An acid anhydride may be used, or its lower alkyl ester may be used.
May be used as an ester-forming derivative such as An aliphatic diol component having 2 to 6 carbon atoms;
Are ethylene glycol and trimethylene glycol
, Propylene glycol, tetramethylene glycol
, Diethylene glycol, neopentylene glycol
And the like. The aliphatic polyester used in the present invention is as described above.
Components, but components other than the above
May be contained. As the component, for example, glyco
Oleic acid, lactic acid, ε-oxycaproic acid, hydroxyeth
Xyacetic acid, β-hydroxybutyric acid, β-hydroxyvaleric acid
And the like. These are all repeat units
More preferably, it is used in a proportion of about 30 mol% or less.
it can. The method of the present invention comprises the above aliphatic dicarboxylic acid component.
Poly composed mainly of fatty acids and aliphatic diol components
The compound represented by the general formula (1) is added to the ester (A).
(B) is reacted.
The reduced viscosity needs to be 0.3 or more. here
Reduced viscosity is phenol / 1,1,2,2-tetrachloro
Concentration 1.2 g / d in ethane mixed solvent (weight ratio 6/4)
1, measured at 35 ° C. 0.3 reduced viscosity
If less than the number of the compound (B) represented by the general formula (1)
The reaction results in an insufficient increase in the degree of polymerization. fat
The reduced viscosity of the aromatic polyester (A) is preferably 0.5 or less.
Above, more preferably 0.6 or more, about 0.9 or less
Is desirable. The above aliphatic polyester (A) is
COOH terminal group content is 40 mol / 10 ⁶g or less
is necessary. COOH terminal group content is 40 mol / 10⁶g
If more, the compound (B) represented by the general formula (1) and
The amount of reactive OH end groups is relatively small, which is preferable.
I don't. The amount of COOH end groups is preferably 30 mol / 10
⁶g or less, more preferably 20 mol / 10⁶g or less
You. The aliphatic polyester (A) is an aliphatic dica.
Rubonic acid, aliphatic dicarboxylic anhydride and aliphatic dica
Fewer compounds selected from alkyl rubonates
Esterification or elimination of a diol with an aliphatic diol
A conventional known method of melt-polycondensing after steal exchange
Can be manufactured more. The above general formula used in the present invention
In the compound (B) represented by (1), R represents a carbon atom
Represents a divalent aliphatic residue of Formulas 2 to 8, specifically,
, Trimethylene, tetramethylene, hexamethylene,
Octamethylene, cyclohexylene, etc. can be mentioned.
Wear. m and n are each an integer of 3 to 11, and l is 0 or
There is one. The compound can be obtained by a conventionally known method.
You. For example, dicarboxylic acid dihalide and 2 mole times
Easily obtained by an acylation reaction with lactam.
It is. As the compound (B) represented by the general formula (1)
Is specifically N, N'-succinylbis-ε-capro
Lactam, N, N'-glutaroylbis- [epsilon] -caprola
Butam, N, N'-Adipoylbis- [epsilon] -caprolacta
, N, N'-sebacoil bis-ε-caprolactam, etc.
Aliphatic dicarboxylic acid biscaprolactam
I can do it. The process of the present invention is characterized in that
The compound (B) represented by the general formula (1) is added to (A)
Add in an amount that satisfies the above formula (2), and inactive under reduced pressure
It is characterized by carrying out a melting reaction in a gas atmosphere. [0021] (Equation 3)                 0.25WX ≦ 10^FourY ≦ 1.2WX (2) In the formula (2), X is an aliphatic polyester before the addition of the component (B).
OH end group amount (mol / 10⁶g) and Y are components (B)
(Wt% / polymer), W is the molecule of component (B)
Indicates the amount. The amount Y of the component (B) falls within the range of the formula (2).
In the case of deviation, the effect of increasing the degree of polymerization is insufficient and it is preferable.
I don't. The added amount of the component (B) satisfies the following formula (3).
It is more preferable that the following formula (4) is satisfied.
Good. [0022] (Equation 4)                 0.30WX ≦ 10^FourY ≦ 1.0WX (3)                 0.35WX ≦ 10^FourY ≦ 0.9WX (4) The melting reaction is carried out under reduced pressure in the presence of a polycondensation catalyst.
Or it is carried out under an inert gas atmosphere. Polycondensation here
As the catalyst, a conventionally known catalyst in the art is used.
Antimony such as antimony oxide
Compounds, tin compounds such as tin acetate and dibutyltin oxide,
Titanium compounds such as traalkoxy titanates, zinc acetate
Calcium compounds such as zinc compounds such as calcium acetate
Substances, manganese compounds such as manganese acetate, sodium carbonate
And alkali metal compounds such as potassium carbonate.
You. The amount of these polycondensation catalysts depends on the dicarboxylic acid used.
About 0.001 to 0.1 mol% is preferable for the component.
More preferably, about 0.005 to 0.05 mol% is more preferable.
No. Polycondensation catalyst is aliphatic dicarboxylic acid and aliphatic diol
Used when producing aliphatic polyester (A) from
It is preferable to use the catalyst as it is, in which case
Is an addition reaction of the compound (B) represented by the general formula (1).
You do not need to add a new one. At the time of this melting reaction, the above-mentioned general formula (1)
The compound (B) represented does not volatilize,
Terminal OH of component (B) and aliphatic polyester (A)
Reacts a cyclic lactam compound formed by the reaction with
It is preferable to distill it off immediately.
In some cases, it is preferable to carry out the melting reaction under
You. When the compound represented by the general formula (1) is an aliphatic poly
When a ring-opening reaction occurs with the terminal OH group of the ester (A)
This is not restrictive, and an inert gas atmosphere may be used. these
Greatly depends on the catalyst used, e.g.
For tin compounds such as tate, the former reaction is
The latter reaction occurs in titanium compounds such as xititanate.
Easy to stiffen. The reaction temperature is not particularly limited, but is generally about 160
About 260 ° C. is preferable, and about 180 ° C. to 250 ° C.
More preferably. The reaction time is not particularly limited.
Aliphatic polyester represented by the general formula (1)
5 minutes depending on the type of compound and reaction temperature
About 60 minutes, preferably about 10 minutes to 30 minutes
It is more preferable to set the degree. According to the production method of the present invention, the polymerization degree is low.
Increased degree of polymerization of aliphatic polyester, reduced viscosity 1.0 or less
The above aliphatic polyester can be easily manufactured
You. When the reduced viscosity is less than 1.0, the mechanical strength of the polymer
The degree of use and toughness become insufficient, and the range of use is greatly limited.
The reduced viscosity of the aliphatic polyester obtained is preferably
It is 1.2 or more, more preferably 1.5 or more. [0028] According to the method of the present invention, ordinary melt polymerization is carried out.
The method uses a polymer with a high degree of polymerization sufficient to exhibit sufficient mechanical properties.
Aliphatic polyesters that were difficult to obtain
Rapidly increase the degree of polymerization and have sufficient mechanical properties and toughness
As a polymer having a high degree of polymerization. Ma
In addition, such polyester is linearly high without branch structure.
It has a high degree of polymerization and good heat resistance. The linear aliphatic polyester having a high degree of polymerization
Utilizing these properties, plastics, fibers,
It can be advantageously used as lum, sheet and the like. In particular
Containers, packaging materials and disposables utilizing biodegradability
It is useful as a material and other various applications, and its industrial significance is
large. [0030] The present invention will be described below with reference to examples.
The invention is not limited to this. In the examples, "parts" means "parts by weight". The reduced viscosity (ηsp / C) is phenol /
1,1,2,2-tetrachloroethane mixed solvent (weight ratio
6/4), measured at a concentration of 1.2 g / dl and a temperature of 35 ° C.
Was. The amount of COOH terminal groups was 100 mg of polymer.
Was dissolved in 10 ml of chloroform at room temperature for 10 minutes, and then benzene was added.
Add 10 ml of alcohol and phenol red
0.1N sodium hydroxide benzyl alcohol as indicator
Of the solution. The amount of OH end groups was determined by adding 14.5 g of polymer to 2
0 ml of a pyridine solution of phthalic anhydride (phthalic anhydride 2
1 g / 300 ml of pyridine).
After reacting for hours, unreacted phthalic anhydride is
0.2N aqueous sodium hydroxide with phthalein as indicator
Determined by back titration with the solution. The melting point (Tm) of the polymer is determined by using DSC.
At a heating rate of 10 ° C./min. Example 1 Dimethyl succinate 29.8
Parts, ethylene glycol 33 parts and dibutyltin diacete
0.02 parts of a reaction vessel having a distillation system through a rectification column
Until the internal temperature of the reaction vessel reaches 205 ° C.
And gradually heated. Where methanol distillation has ended
To stop the transesterification reaction, and connect the stirrer and vacuum distillation system.
Transfer to a reaction vessel equipped with
5 minutes, then 0.2 mmHg true at the same temperature for 20 minutes
Under an empty condition, a melting reaction was further performed for 120 minutes under the same condition.
The obtained polymer has a reduced viscosity of 0.54 and COOH terminal groups.
Amount 2 (mol / 10⁶g), melting point 106.2 ° C. With respect to the polymer obtained by the above method,
N, N'-succinylbis-.epsilon.-capro
Add lactam (0.6 part) in a nitrogen stream at normal pressure at 230 ° C.
Minutes and then at the same temperature for 15 minutes under a vacuum condition of 0.2 mmHg.
The melt reaction was carried out for a while. The polymer obtained after the reaction has a reduced viscosity
1.34, melting point 103 ° C. Example 2 Dimethyl succinate 28.5
Parts, 30.3 parts of ethylene glycol and tetrabutylthio
0.02 parts of tantalate was placed in the same reaction vessel as in Example 1.
Until the internal temperature of the reaction vessel reaches 200 ° C.
Heated. At the end of methanol distillation,
Terminate the exchange reaction and carry out the polymerization reaction as in Example 1.
(0.16 mmHg for 150 minutes). The resulting polymer
Represents a reduced viscosity of 0.80 and a COOH terminal group content of 4 (mol / 1)
0⁶g), melting point 105.2 ° C. With respect to the polymer obtained by the above method,
N, N'-succinylbis-.epsilon.-capro
0.62 parts of lactam was added, and 230 ° C. in a nitrogen stream under normal pressure
For 3 minutes and then at the same temperature under a vacuum condition of 0.2 mmHg for 3 minutes.
The melting reaction was performed for 0 minutes. The polymer obtained after the reaction is reduced
The viscosity was 3.60 and the melting point was 99.8 ° C. Example 3 Dimethyl adipate 35.8
Parts, 30 parts of ethylene glycol and dibutyltin diacete
Prepolymer as in Example 2 using 0.02 parts
(0.2mmHg for 170 minutes)
Has a reduced viscosity of 0.63 and a COOH terminal group content of 5 (mol / mol).
10⁶g), melting point 50.5 ° C. With respect to the polymer obtained by the above method,
N, N'-Adipoyldi- [epsilon] -caprolatum at normal pressure
0.63 parts of octam, at 230 ° C in a nitrogen stream under normal pressure
3 minutes, then 60 at the same temperature under a vacuum condition of 0.2 mmHg.
The mixture was melted for minutes. The polymer obtained after the reaction has a reduced viscosity.
The degree was 1.23 and the melting point was 47.5 ° C.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-51-11892 (JP, A) US Patent 4,857,603 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 63 / 00-63/91

Claims (1)

(57) [Claims] 1. An aliphatic dicarboxylic acid having 4 to 10 carbon atoms.
An acid component and an aliphatic diol component having 2 to 6 carbon atoms
Mainly reduced viscosity (phenol / 1,1,2,2
Concentrated in a tetrachloroethane mixed solvent (weight ratio 6/4)
Degree 1.2g / dl, measured at a temperature of 35 ° C) 0.3 or more,
And COOH terminal group content of 40 mol / 10 ⁶g or less aliphatic
Compound represented by the following formula (1) in polyester (A)
(B) is added in an amount satisfying the following formula (2), and a polycondensation catalyst is added.
Melt under reduced pressure or inert gas atmosphere in the presence of
High gravity with reduced viscosity of 1.0 or more
A method for producing an aliphatic polyester. Embedded image (In the formula (1), R is a divalent aliphatic residue having 2 to 8 carbon atoms.)
The group, n, is an integer of 3 to 11. ) (Equation 1)                 0.25WX ≦ 10^FourY ≦ 1.2WX (2) (In the formula (2), X is an aliphatic polyester before addition of the component (B).
The amount of OH terminal groups of the ter (A) (mol / 10⁶g)
You. Y represents the amount of the component (B) added (% by weight / polymer).
I forgot. W represents the molecular weight of component (B). )