JPH06157704A - Production of block polyester - Google Patents

Abstract

PURPOSE:To produce a block polyester as a product adaptable to a general molding machine, capable of melt molding and excellent in flexibility by reacting a polyvalent isocyanate with a specified mixed polyester. CONSTITUTION:0.1 to 5 pts.wt. Polyvalent isocyanate is added to 100 pts.wt. mixture of polyesters prepared by melt blending 99 to 20wt.% aliphatic polyester (including an alicyclic compound) exhibiting >=100 deg.C melting point and >=5000 number-average molecular weight and treated with an organic or inorganic phosphorus compound for deactivation of the remaining catalyst used in the deglycolation reaction and 1 to 80wt.% aliphatic polyester (including an alicyclic compound) exhibiting <100 deg.C melting point and >=5000 number-average molecular weight and treated with an organic or inorganic phosphorus compound for deactivation of the remaining catalyst used in the deglycolation reaction, and reacted. In addition, a polyester having >=10000 number-average molecular weight and >=50000 weight-average molecular weight is produced by using the above two kinds of polyesters respectively having >=30000 weight-average molecular weight.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a block polyester which is useful for various applications such as films, various molded articles and fibers and is also biodegradable.

[0002]

2. Description of the Related Art Synthetic polymers having biodegradability are very limited, and it is no exaggeration to say that they are essentially only aliphatic polyesters. However, the aliphatic polyester generally has a low melting point and also has poor thermal stability during polyester production, and thus far, no type having a high molecular weight that can be practically used has been introduced. The present inventors have found that in an aliphatic polyester having a number average molecular weight of 5,000 or more and a terminal group being substantially a hydroxyl group, 1/10 to 2 equivalents of an isocyanate group per 1 equivalent of the hydroxyl group of the polyester are used. It was found that a practical high molecular weight aliphatic polyester can be obtained by adding and reacting a diisocyanate having the above formula, and it was previously proposed (JP-A-4-189822). In addition, the present inventors
For example, a polyester synthesized from butanediol-1,4 and succinic acid is reacted with an appropriate amount of polyvalent isocyanate to increase the molecular weight to obtain a high molecular weight aliphatic polyester. Knowing that it can be used for various purposes such as products and fibers, it has already been proposed in Japanese Patent Application No. 4-116239, Japanese Patent Application No. 4-148310 and Japanese Patent Application No. 4-117655. The above-mentioned high molecular weight aliphatic polyester can be applied as it is to most applications, but it has been clarified at the practical stage that it is somewhat hard depending on the application, for example, packaging film, blow molded containers, etc. It was also found that there was a case where flexibility was required or an aliphatic polyester having better moldability was required depending on the application.

As a method of imparting flexibility, it is effective to replace a part of succinic acid with a longer chain fatty acid such as adipic acid or sebacic acid to obtain a cocondensed polyester.
It is also practical. However, this method lowers the melting point (softening point) of the polyester, so if it is acceptable, the melting point of the polyester from rabbit corn, butanediol-1,4 and succinic acid (about 115 ° C ) Is not applicable when you want to maintain.

[0004]

The present invention has a melting point of 10
Aliphatics that can be directly melt-molded at 0 ℃ or higher in a general-purpose plastic molding machine such as polyethylene or polypropylene as polyethylene and polypropylene
It is an object of the present invention to provide an aliphatic (including cycloaliphatic) polyester which is a polyester (including cycloaliphatic) and which is capable of molding a product having high flexibility.

[0005]

As a result of various studies to improve the drawbacks of the above-mentioned conventional aliphatic (including cycloaliphatic) polyesters, the present inventors have found that the moldability of films, various molded products, etc. The weight average molecular weight is more than the number average molecular weight, and the polyester having a different structure from the single composition polyester is blocked, that is, a specific high melting point aliphatic (including cycloaliphatic) polyester And a specific low-melting point aliphatic (including cycloaliphatic) polyester are melt-mixed, a polyvalent isocyanate is added to this melt-mixed polyester, and a terminal hydroxyl group of both polyesters and an isocyanate group are reacted. The block polyester of high melting point polyester and low melting point polyester obtained by Flexibility is improved, know that it is associated by many fields of application, it was possible to complete the present invention.

That is, the first aspect of the present invention is [I] (1)
Aliphatic (including cycloaliphatic) polyester having a melting point of 100 ° C. or higher, a number average molecular weight of 5,000 or higher, and eliminating the action of the remaining catalyst used in the deglycolization reaction with an inorganic or organic phosphorus compound. 99-20% by weight and (2) melting point less than 100 ° C, number average molecular weight 5,000
1 to 80% by weight of the aliphatic (including cycloaliphatic) polyester in which the action of the residual catalyst used in the deglycolization reaction with the inorganic or organic phosphorus compound has been eliminated
The present invention relates to a method for producing a block polyester, which comprises melt-mixing and and mixing 100 parts by weight of the mixed polyester with [II] 0.1-5 parts by weight of a polyvalent isocyanate and reacting them.

The second aspect of the present invention is that the melting point of [I] (1) is 100.
Aliphatic (including cycloaliphatic) polyesters 99 to 20 having a weight-average molecular weight of 30,000 or more and a weight-average molecular weight of 30,000 or more and having lost the action of the remaining catalyst used in the deglycolization reaction with an inorganic or organic phosphorus compound % By weight and (2) the melting point is less than 100 ° C., the weight average molecular weight is 30,000 or more, and the residual catalyst used in the deglycolization reaction with an inorganic or organic phosphorus compound eliminates the action of an aliphatic (cyclic 1 to 80% by weight of polyester (including aliphatic) is melt-mixed, and 100 parts by weight of this mixed polyester is added and reacted with 0.1 to 5 parts by weight of a polyvalent isocyanate to obtain a weight average molecular weight. It relates to a method for producing a block polyester, which is characterized in that it is 50,000 or more.

A third aspect of the present invention is that the melting point of [I] (1) is 100.
An aliphatic (cyclic group) having a number average molecular weight of 5,000 or more, a weight average molecular weight of 30,000 or more, and an inorganic or organic phosphorus compound used in the deglycolization reaction to eliminate the action of the remaining catalyst. (Including aliphatic) 99 to 20% by weight of polyester and (2) melting point of less than 100 ° C., number average molecular weight of 5,000 or more and weight average molecular weight of 3,0.
1 to 80% by weight of an aliphatic (including cycloaliphatic) polyester in which the action of the remaining catalyst used in the deglycolization reaction with an inorganic or organic phosphorus compound, which is 00 or more, is eliminated, [II] 0.1 to 5 parts by weight of a polyvalent isocyanate is added to 100 parts by weight of the mixed polyester and reacted to give a number average molecular weight of 10,000 or more and a weight average molecular weight of 50,000 or more. And a method for producing a block polyester.

As in the present invention, when a specific high-melting point polyester and a specific low-melting point polyester are converted into block polyesters, even if the low-melting point polyester portion is unexpectedly present, the apparent softening is caused by the high-melting point polyester. Then, the melting point does not decrease. On the other hand, the flexibility is practically sufficiently improved by the presence of the low melting point polyester.
Further, even if polyesters having different melting points but similar structures are blocked with a polyvalent isocyanate, it is found that the blocked polyester has a higher melting point, which is advantageous in terms of moldability. This is one of the points of the invention. For example, as in stretch blow molding, when injection molding is performed in advance and then blow molding is performed in accordance with a mold, the toughness of the polymer itself, that is, the strength, is required as well as the elongation. In such a case, it is advantageous to block polymers having different physical properties from each other than a single polymer.

The present invention will be described in more detail below. The melting point used in the present invention is 100 ° C. or higher, the number average molecular weight is 5,000 or higher, and the weight average molecular weight is 30,000 or higher.
And aliphatic (including cycloaliphatic) polyesters having a number average molecular weight of 5,000 or more and a weight average molecular weight of 30,000 or more (hereinafter sometimes referred to as high melting point polyester) are aliphatic or cyclic fats. Group glycol,
Aliphatic or cycloaliphatic dicarboxylic acid or acid anhydride thereof, or aliphatic or cycloaliphatic glycol, aliphatic or cycloaliphatic dicarboxylic acid or acid anhydride thereof, and trivalent or higher functional polyhydric alcohol, polycarboxylic acid In the presence of a necessary deglycolization catalyst, which is generally used esterification (dehydration condensation), with at least one polyfunctional compound selected from the group consisting of an acid or its acid anhydride and an oxycarboxylic acid. It is synthesized by the deglycol reaction.

Examples of the aliphatic or cycloaliphatic glycols include ethylene glycol, 1,4-butanediol and 1,4-cyclohexanedimethanol. You may use these together.

Aliphatic or cycloaliphatic dicarboxylic acids or acid anhydrides thereof include succinic acid, succinic anhydride, adipic acid, adipic anhydride, suberic acid, sebacic acid, dodecanedioic acid and 1,4-cyclohexanedicarboxylic acid. Etc. are available. Of course, these can be used together. When synthesizing a high melting point polyester having a melting point of 100 ° C. or higher, succinic acid is preferably used, and the melting point is 100 ° C.
Other aliphatic or cycloaliphatic dicarboxylic acids are also utilized when synthesizing polyesters of less than.

Preferred combinations of aliphatic or cycloaliphatic glycols with aliphatic or cycloaliphatic dicarboxylic acids or their acid anhydrides for the synthesis of high-melting polyesters are 1,4-butanediol and succinic anhydride. , 4-
This is the case where butanediol and succinic acid, 1,4-cyclohexanedimethanol and succinic acid, ethylene glycol and succinic acid, and trimethylolpropane are used together.

The ratio of the aliphatic or cycloaliphatic glycol to the aliphatic or cycloaliphatic dicarboxylic acid or its anhydride used is 1 mol of the aliphatic or cycloaliphatic dicarboxylic acid or its anhydride. A cycloaliphatic glycol of about 1.05 to 1.2 is suitable.

In the present invention, for example, a branched product is introduced into the aliphatic polyester to increase the weight average molecular weight, and the molecular weight distribution is broadened to obtain a molded article (for example, a film and a sheet) having excellent physical properties. In addition, at least one polyfunctional compound selected from the group consisting of trihydric or higher polyhydric alcohols, polyhydric carboxylic acids or their anhydrides, and oxycarboxylic acids may be used in combination within a range that does not impair the purpose. it can.

Examples of the trifunctional or higher polyhydric alcohol include glycerin, trimethylolpropane, pentaerythritol, triallyl isocyanurate ethylene oxide adduct and the like. It is also possible to use the dehydrated form of the monoepoxy compound glycidol. This 3
The amount of the polyhydric alcohol having a functionality or higher is such that the total amount of the aliphatic or cycloaliphatic dicarboxylic acid or its acid anhydride component is 10
It is 0.1 to 5 mol% with respect to 0 mol%, and it is good to add it from the beginning of esterification.

As the trifunctional or higher polyvalent oxycarboxylic acid or its acid anhydride, commercially available products can be used, but malic acid, tartaric acid and citric acid are preferable from the viewpoint of low cost. Is. The amount of the trifunctional or higher polyvalent oxycarboxylic acid or its acid anhydride used is 0.1 to 5 mol% based on 100 mol% of the entire aliphatic or cycloaliphatic dicarboxylic acid or its acid anhydride component. Yes, it can be added from the beginning of esterification.

Examples of trifunctional or higher polyvalent carboxylic acids or acid anhydrides thereof include trimesic acid, propanetricarboxylic acid, trimellitic anhydride, pyromellitic dianhydride, benzophenonetetracarboxylic anhydride, cyclopentatetracarboxylic acid. Anhydrous etc. are mentioned. Particularly, trimellitic anhydride, pyromellitic dianhydride and the like are preferable. The trifunctional or higher polyvalent carboxylic acid or its acid anhydride is used in an amount of 0.1 to 5 with respect to 100 mol% of the total amount of the aliphatic or cycloaliphatic dicarboxylic acid or its acid anhydride component.
Mol% and can be added from the beginning of esterification.

On the other hand, the melting point used in the present invention is less than 100 ° C., the number average molecular weight is 5,000 or more, the weight average molecular weight is 30,000 or more, and the number average molecular weight is 5,000 or more, and the weight average molecular weight is 30,000 or more aliphatic (including cycloaliphatic) polyesters (hereinafter sometimes referred to as low-melting polyesters) include aliphatic or cycloaliphatic glycols and aliphatic or cycloaliphatic dicarboxylic acids or acid anhydrides thereof. Or an aliphatic or cycloaliphatic glycol, an aliphatic or cycloaliphatic dicarboxylic acid or an acid anhydride thereof, and a trifunctional or higher polyhydric alcohol, a polyvalent carboxylic acid or an acid anhydride thereof, and an oxycarboxylic acid. From the generally used esterification (dehydration condensation) and at least one polyfunctional compound selected from It is synthesized by de-glycol reaction in the presence of a catalyst.

The aliphatic or cycloaliphatic glycol, the aliphatic or cycloaliphatic dicarboxylic acid or its acid anhydride, and the trihydric or higher-functional polyhydric alcohol, polyvalent carboxylic acid or its acid anhydride used are those described above. The same thing as what was used when synthesize | combining a melting point polyester is used. Examples of the aliphatic or cycloaliphatic glycol include propylene glycol, 1,3-butanediol, 2-methylpropanediol-1,3, neopentyl glycol, 3-methylpentanediol-1,5, nonamethylene glycol, diethylene glycol, Other glycols such as dipropylene glycol and polytetramethylene glycol may be used in combination, but the ratio of combination is changed depending on the intended use.

Use ratio of aliphatic or cycloaliphatic glycol and aliphatic or cycloaliphatic dicarboxylic acid or acid anhydride thereof, and trifunctional or higher functional polyhydric alcohol, polyvalent carboxylic acid or acid anhydride thereof, oxycarboxylic acid. The proportion of the acid used is the same as in the synthesis of the high melting point polyester.

A preferred combination of an aliphatic or cycloaliphatic glycol and an aliphatic or cycloaliphatic dicarboxylic acid or an acid anhydride thereof for synthesizing a low melting point polyester is 1,4-butanediol and adipic acid, ethylene. Glycol and adipic acid, 1,4-cyclohexanedimethanol and dodecanedioic acid, 1,4-cyclohexanedimethanol and dodecanedioic acid and a small amount of trimethylolpropane, ethylene glycol and adipic acid and a small amount of malic acid.

The esterification reaction for synthesizing the high-melting point polyester and the low-melting point polyester is carried out by a conventional method in an inert gas stream at 180 to 230 ° C. until a desired acid value is obtained, and then a necessary amount of deglycolization catalyst is used. Is added and the deglycolization reaction is carried out under reduced pressure of 5 Torr or less, preferably 1 Torr or less at the same temperature to give a number average molecular weight of 5,000.
Or more, preferably 10,000 or more, weight average molecular weight of 30,000 or more, preferably 35,000 or more, and number average molecular weight of 5,000 or more and weight average molecular weight of 30,000 or more, preferably number average molecular weight Is 10,
000 or more and a weight average molecular weight of 35,000 or more. The high melting point polyester and the low melting point polyester have a number average molecular weight of 5,000 or more, a weight average molecular weight of 30,000 or more, or a number average molecular weight of 5,000 in order to maintain moldability and physical properties.
As described above, it is necessary that the weight average molecular weight is 30,000 or more.

Number average molecular weight less than 5,000, weight average molecular weight less than 30,000, or number average molecular weight 5,
If the weight average molecular weight is less than 000 and the weight average molecular weight is less than 30,000, the amount of polyvalent isocyanate used for obtaining the required physical properties and moldability is large, which is extremely risky of gelation when the polyester is melt-added. Become. In order to avoid gelation at the time of adding the polyvalent isocyanate, it is preferable that the polyester has a large molecular weight and the amount of the polyvalent isocyanate used is small.

As the catalyst for the deglycolization reaction, the same kind as used for the production of polyethylene terephthalate can be used. For example, titanium, tin, antimony, cerium,
Examples thereof include organic acid salts, alkoxides and oxides of metals such as zinc, cobalt, iron, lead, manganese, aluminum, magnesium and germanium.

The amount of the deglycolization catalyst used is generally 0.1 to 1 part by weight based on 100 parts by weight of the polyester produced. If the amount of the catalyst used is less than 0.1 parts by weight, the deglycolization reaction will be delayed and not practical, and if it is used in excess of 1 part by weight, the decomposition reaction will be intensified.

In the present invention, after the deglycolization reaction, it is necessary to add an inorganic or organic phosphorus compound to the high melting point polyester or the low melting point polyester to eliminate the action of the catalyst remaining in the polyester.

The reason for using the inorganic or organic phosphorus compound is to stop the catalytic action of the metal compound as the deglycolization catalyst used in the polyester production process by the deglycolization reaction. When the activity of the catalyst remains, when polyesters with different melting points are melt-mixed, an ester exchange reaction occurs and the polyester changes to a co-condensation type instead of a homogeneous structure type, greatly lowering the melting point and changing the physical properties. Results in disadvantages such as markedly. In particular, the fluctuation of the melting point and the decrease of the melt viscosity at the time of molding have a bad influence on the moldability. In order to solve this drawback, a block polymer having a stable structure and stable physical properties is obtained by using an inorganic or organic phosphorus compound that stops the action of the deglycolization catalyst in combination, and then reacting a polyvalent isocyanate. be able to.

In order to lose the activity of these deglycolization catalysts, it is known to use necessary amounts of inorganic and organic phosphorus compounds. For example, in the synthesis of polyethylene terephthalate, in the case of using zinc, cobalt and manganese acetate as a catalyst, it was shown that the catalytic action was deactivated when phosphoric acid was used in an equimolar amount with the metal of the deglycolization catalyst. (For example, Kazuo Yuki, Saturated Polyester Handbook, p. 143, published by Nikkan Kogyo Shimbun).

Examples of inorganic or organic phosphorus compounds used are inorganic phosphorus compounds such as phosphoric acid, polyphosphoric acid, phosphorus pentoxide, phosphorous acid, as well as triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecyl. Organic phosphites such as phosphite, tris (mono and / or dinonylphenyl) phosphite, trialkyl phosphates (where the alkyl group is methyl, ethyl, butyl, octyl, butoxyethyl, etc.), triphenyl phosphate, and Alkyl acid phosphates as the acid phosphate (where the alkyl group is methyl, isopropyl, butyl, octyl, etc.
Mono- or di-substituted compounds) or phosphonates such as dibutyl butyl phosphonate. Two or more kinds of these inorganic or organic phosphorus compounds can be used in combination.

The amount of the inorganic or organic phosphorus compound used is
Although it varies depending on the molecular weight of the phosphorus compound (content of phosphorus atom), it is generally 0.001 to 3 parts by weight, preferably 0.01 to 1 part by weight, relative to 100 parts by weight of the high melting point polyester or the low melting point polyester. Is. When the amount of the phosphorus compound used is less than 0.001 part by weight, the effect of addition is not observed, and when it is more than 3 parts by weight, the effect is not increased. The phosphorus compound is preferably added at a temperature of 150 to 250 ° C.

The melting point is 100 ° C. or higher and the number average molecular weight is 5,
000 or more and a high melting point polyester in which the action of the remaining catalyst used in the deglycolization reaction with an inorganic or organic phosphorus compound is eliminated, and a melting point of less than 100 ° C. and a number average molecular weight of 5,000 or more, and The use ratio of the low melting point polyester in which the action of the remaining catalyst used in the deglycolization reaction with the inorganic or organic phosphorus compound is eliminated,
The former is from 99 to 20% by weight and the latter is from 1 to 80% by weight, and the former is preferably from 90 to 30% by weight and the latter is from 10 to 70% by weight, although it varies depending on the use.

When the proportion of the high melting point polyester treated with the phosphorus compound of the former is less than 20% by weight, the generated block polyester is strongly influenced by the polyester having a melting point of less than 100 ° C., and the melting point tends to be 100 ° C. or less. Becomes stronger. On the other hand, when the proportion of the high melting point polyester treated with the former phosphorus compound exceeds 99% by weight, the meaning of blocking becomes weak.

Further, the melting point is 100 ° C. or more and the weight average molecular weight is 30,000 or more, or the melting point is 100 ° C. or more, the number average molecular weight is 5,000 or more and the weight average molecular weight is 30,
000 or more and a high melting point polyester in which the action of the remaining catalyst used in the deglycolization reaction with an inorganic or organic phosphorus compound is eliminated, and a melting point of less than 100 ° C. and a weight average molecular weight of 30,000 or more, or a melting point Is 100 ° C
With a low melting point polyester having a number average molecular weight of 5,000 or more and a weight average molecular weight of 30,000 or more, and eliminating the action of the remaining catalyst used in the deglycolization reaction with an inorganic or organic phosphorus compound. The use ratio is 99 to 20% by weight of the former and 1 to 80% by weight of the latter, preferably 90 to 30% by weight of the former and 10 to 70% by weight of the latter.

When the proportion of the high melting point polyester treated with the former phosphorus compound is less than 20% by weight, the melting point of the produced block polyester is strongly influenced by the low melting point polyester, and the melting point tends to be 100 ° C. or lower. , 9
When it is more than 9% by weight, the meaning of blocking becomes weak.
In the present invention, in particular, the polyester containing sebacic acid or dodecanedioic acid can be shortened by using a small amount of 1 to 5% of polyester containing succinic acid to shorten the biodegradation period by only slightly lowering the melting point. can do.

The high melting point polyester treated with the phosphorus compound and the low melting point polyester treated with the phosphorus compound are mixed in a molten state.

The present invention further relates to 100 parts by weight of a mixed polyester of the high melting point polyester treated with the phosphorus compound and the low melting point polyester treated with the phosphorus compound, which are mixed as described above, based on 100 parts by weight of the polyvalent isocyanate. 0.
1 to 5 parts by weight is added in a molten state above the melting point of the polyester so that the number average molecular weight is 10,000 or more, preferably 15,000 or more, the weight average molecular weight is 50,000 or more, preferably 80,000. Or more, or a block polyester having a number average molecular weight of 10,000 or more and a weight average molecular weight of 50,000 or more, desirably a number average molecular weight of 15,000 or more and a weight average molecular weight of 80,000 or more.

The polyvalent isocyanate used for this purpose does not need to be particularly limited, but when the polyvalent isocyanate is a diisocyanate, the amount used is 0.1 to 100 parts by weight of the mixed polyester. 3 parts by weight is sufficient, and the polyvalent isocyanate is a dimer or trimer having a valence of 3 or more,
Alternatively, in the case of a type having a low isocyanate value such as an adduct of polyhydric alcohol and diisocyanate, mixed polyester 1
1 to 5 parts by weight is required for 00 parts by weight.

The polyvalent isocyanate used in the present invention is, for example, 2,4-tolylene diisocyanate, 2,4.
-A mixture of tolylene diisocyanate and 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate Nato, isophorone diisocyanate, triphenylmethane triisocyanate, trimer of 1,6-hexamethylene diisocyanate, adduct of 1,6-hexamethylene diisocyanate and polyhydric alcohol, especially trimethylpropane. To be Of these polyvalent isocyanates, aliphatic or cycloaliphatic isocyanates are particularly preferred in the present invention.
It is desirable because the reaction product is not colored.

The reaction between the mixed polyester and the polyvalent isocyanate is conveniently carried out in a molten state above the melting point of the polyester. Although a solvent can be used, it has to be removed later, and an increase in cost is unavoidable.

The block polyester according to the present invention, in practical use, is a reinforcing material, inorganic and organic fillers,
Of course, a colorant, a lubricant, a release agent, a stabilizer, and polymers or oligomers can be used in combination as required.

[0042]

EXAMPLES In order to facilitate understanding of the present invention, examples will be shown below. The molecular weight was measured by the following GPC measurement. Model used: Shodex GPC SYSTEM-1
1 STD: PMMA (Shodex STANDAR
D M-75) _{Eluent: CF 3 COONa 5mmol / HFIP (} 1 L) Column: Sample Column HFIP-800P HFIP-80M × 2 This reference column HFIP-800R × 2 present Column temperature: 40 ° C. flow rate: 1.0 ml / min Detector: Shodex RI

Examples 1 to 6 and Comparative Example 1 Synthesis of high melting point polyester [A] 1,4-butanediol was placed in a 2 liter separable flask equipped with a stirrer, a fractionating condenser, a thermometer, and a gas introduction tube. After charging 568 g and 600 g of succinic anhydride and esterifying at 200 to 210 ° C. in a nitrogen gas stream to an acid value of 7.9, the condenser was changed to a direct distillation tube, and tetraisopropyl titanate as a deglycolization catalyst was added.
2g was added, and finally under reduced pressure of 0.5 Torr, 210-
After carrying out the deglycolization reaction at 215 ° C. for 8 hours, 0.6 g of phosphorous acid was added.

White hard wax with a melting point of about 117 ° C.,
Number average molecular weight 16,600, weight average molecular weight 42,
000 high melting point polyesters [A] were obtained. This was saved in a desiccator. The DSC curve of this product is shown in FIG.

Synthesis of low melting point polyester [B] 600 g of 1,4-butanediol and 8 parts of adipic acid were placed in an apparatus similar to that used for synthesizing the high melting point polyester [A].
After charging 76 g and performing esterification in a nitrogen stream at 200 to 210 ° C. to an acid value of 5.4, 0.2 g of tetraisopropyl titanate was added, and finally under reduced pressure of 0.5 Torr for 7 hours, A deglycol reaction was performed at 210 to 215 ° C., and 0.6 g of phosphorous acid was added.

White and soft waxy substance, melting point 69
° C, number average molecular weight 15,500, weight average molecular weight 42,
100 low melting point polyesters [B] were obtained. The DSC curve of this product stored in a desiccator is shown in FIG.

Synthesis of Block Polyester A 500 cc separable flask was charged so that the total amount of polyester [A] and polyester [B] would be 200 g so as to obtain a desired blend ratio, and 190 to 195
After remelting in a nitrogen stream at 0 ° C., 1.5 g of hexamethylene diisocyanate was added in each case. The viscosity increased rapidly but did not gel. The properties of each of the obtained block polyesters are shown in Table 1. Moreover, Examples 1 to 1
DSC curves of Example 6 are shown in FIG. 3 (Example 1), FIG. 4 (Example 2), FIG. 5 (Example 3), FIG. 6 (Example 4), and FIG.
(Example 5), FIG. 8 (Example 6), and FIG. 9 (Comparative Example 1).

[0048]

[Table 1]

From Table 1, it can be seen that from the point of polyester [A] / polyester [B] = 20 to 80 (mixing ratio), the melting point apparently hardly decreased, and the melting point was rapidly lowered to 10/90. Obviously seen. For reference, a block polyester having a mixing ratio of 50/50 was pelletized, and the pellet was left overnight in a thermostat of 90 to 92 ° C. The original shape was maintained, and fusion did not occur at all.

Synthesis of Block Polyester A 1-liter separable flask was charged with 250 g of polyester [A] and 250 g of polyester [B], and the mixture was heated and melted at 190 to 195 ° C. in a nitrogen stream.
7 g of hexamethylene diisocyanate was added. The viscosity increased rapidly but did not gel. The melting point of the obtained block polyester was 116 ° C., which was virtually unchanged, and the weight average molecular weight was 114,600 and the number average molecular weight was 30,400. After press molding this block polyester, it was stretched 4 times at room temperature to give a thickness of 40μ.
The transparent film had a tensile strength of 12.9 kg / mm ² . In addition, a film obtained by cutting this stretched film into 2 cm x 10 cm was buried under 15 to 20 cm in the black soil at the foot of Akagi, and a decomposition test was carried out. After 3 months in summer, it became worn out and the original shape does not stop after 6 months. It had disappeared.

Examples 7 to 12 and Comparative Example 2 Synthesis of High Melting Point Polyester [C] In a 2 liter separable flask equipped with a stirrer, a fractionating condenser, a thermometer, and a gas introduction tube, 1,4-butanediol was placed. 595 g of succinic acid and 708 g of succinic acid were esterified at 200 to 210 ° C. in a nitrogen gas stream to give an acid value of 9.1, then the condenser was changed to a straight distillation tube, and titanium oxyacetylacetonate was used as a deglycolization catalyst. 0.3 g was added, and finally under a reduced pressure of 0.5 Torr, 21
After performing the deglycolization reaction at 0 to 215 ° C. for 9 hours, 7 g of dibutyl hydrogen phosphite (manufactured by Daihachi Chemical Co., Ltd., trade name DBP-1) was added.

A slightly yellowish waxy polyester [C] having a melting point of about 116 ° C., a number average molecular weight of 15,100 and a weight average molecular weight of 39,000 was obtained.

A low-melting polyester [D] synthetic stirrer, a fractionating condenser, a thermometer, and a 2 liter separable flask equipped with a gas introduction tube were charged with 407 g of ethylene glycol and 876 g of adipic acid, and a nitrogen gas flow was conducted. Esterified at 195 to 205 ° C to give an acid value of 9.6
And then 0.3g of titanium oxyacetylacetonate
Finally, under reduced pressure of 0.5 Torr, 210 to 21
After deglycolization at 5 ° C for 8 hours, diisodecyl pentaerythritol diphosphite (Sanko Chemical Co., Ltd.)
6g of brand name HI-MO manufactured by Co., Ltd. was added.

White, soft wax, melting point about 60 ° C.,
Number average molecular weight 16,900, weight average molecular weight 46,90
0 polyester [D] was obtained. The DSC curve of this polyester [D] is shown in FIG.

Synthesis of Block Polyester A 500 cc separable flask was charged so that the total amount of polyester [C] and polyester [D] would be 200 g so as to obtain a desired blend ratio, and 190 to 195
After remelting at ℃ in a nitrogen stream, 4 g of isophorone diisocyanate was added. The viscosity increased rapidly but did not gel. Table 2 shows the physical properties of the obtained block polyester. Further, the DSC curves of Examples 7 to 12 are shown in FIG. 11 (Example 7), FIG. 12 (Example 8), FIG. 13 (Example 9), FIG. 14 (Example 10), and FIG. 15 (Example). 1
1), FIG. 16 (Example 12), and FIG. 17 (Comparative example 2).

[0056]

[Table 2]

Example 13 Synthesis of High Melting Point Polyester [E] In a 2 liter separable flask equipped with a stirrer, a fractionating condenser, a thermometer and a gas introduction tube, 890 g of 1,4-cyclohexanedimethanol and succinic acid were added. After charging 708 g, esterification in a nitrogen stream at 210 to 215 ° C. to an acid value of 11.4, 3 g of zinc acetate and 0.15 g of titanium tetraisopropoxide were added, and finally 0.4
After deglycolization (including decarboxylic acid) was performed at 220 to 230 ° C. for 8 hours under reduced pressure of Torr, 6 g of polyphosphoric acid was added.

The melting point of the obtained polyester [E] is about 1
15 ° C, white, hard waxy, number average molecular weight 12,1
00 and the weight average molecular weight was 36,800.

Synthesis of low-melting point polyester [F] 590 g of 1,4-cyclohexanedimethanol was added to the same apparatus as used for synthesizing high-melting point polyester [E].
920 g of dodecanedioic acid was charged and reacted under the same conditions to give a melting point of about 70 ° C, a slightly ivory waxy form, a number average molecular weight of 13,900, a weight average molecular weight of 43,0.
00 polyester [F] was obtained.

Synthesis of Block Polyester (a) 300 g of polyester [E] and 300 g of polyester [F] were charged in a 1 liter separable flask, melted at 200 ° C. and 12 g of hydrogenated xylylene diisocyanate was added. The viscosity increased rapidly but did not gel. The block polyester (a) thus obtained had a melting point of 115 ° C., a number average molecular weight of 33,900 and a weight average molecular weight of 127,000.

Separately, 300 g of polyester [E] is added to 20
Melt to 0 ℃ and add hydrogenated xylylene diisocyanate 6
g was added to obtain a high molecular weight polyester (b) having a number average molecular weight of 29,100 and a weight average molecular weight of 119000.

1 polyester each (a) and (b)
It was press molded at 50 ° C. and uniaxially stretched about 3 times at room temperature to obtain a transparent film (thickness: about 55 μ). Polyester (a)
The film molded from was transparent and rich in flexibility. The elongation rate of the film molded from the polyester (a) was 350%, and the tensile strength was 10 kg / mm ² . Both films were buried in black soil under 15 cm to perform a decomposition test. The film of polyester (b) was in a situation where the surface began to collapse like an avatar after 6 months,
The film made of the block polyester (a) was almost completely decomposed and was in a tattered state without completely stopping the original shape.

Example 14 Synthesis of High Melting Point Polyester [G] In a 2 liter separable flask equipped with a stirrer, a fractionating condenser, a thermometer, and a gas introduction tube, 890 g of 1,4-cyclohexanedimethanol and succinic acid were added. After charging 708 g and esterifying in a nitrogen stream at 210 to 215 ° C. to an acid value of 11.4, 3 g of zinc acetate and 0.15 g of titanium tetraisopropoxide were added, and the temperature was 220 to 23.
After the reaction was finally performed at 0 ° C. under a reduced pressure of 0.4 Torr for 8 hours, 0.6 g of polyphosphoric acid was added. The obtained polyester [G] has a melting point of about 115 ° C., is a white and hard wax, and has a weight average molecular weight of 36,800 and a number average molecular weight of 1
It was 2,100.

Synthesis of Low Melting Point Polyester [H] 590 g of 1,4-cyclohexanedimethanol was added to the same apparatus as that used for synthesizing high melting point polyester [G].
Dodecanedioic acid (920 g) and trimethylolpropane (15 g) were charged, and the reaction was carried out under the same conditions to give 0.9 g of polyphosphoric acid, a melting point of about 70 ° C., a slightly ivory colored soft wax, and a weight average molecular weight of 100, A polyester [H] having a number average molecular weight of 200 and a number average molecular weight of 14,900 was obtained.

Synthesis of Block Polyester A 1-liter separable flask was charged with 300 g of polyester [G] and 300 g of polyester [H], melted at 200 ° C., and 12 g of hydrogenated xylylene diisocyanate was added. The viscosity increased rapidly but did not gel. The melting point of the obtained block polyester is 1
At 15 ° C., the weight average molecular weight was 309,000 and the number average molecular weight was 30,900. Polyester [G] is press molded into a sheet with a thickness of about 200μ, 2 cm x 10 cm
It was cut out into a test piece for biodegradation. Separately, press molding the block polyester in the same manner, and
After being double-stretched to form a transparent film having a thickness of 50 μ, it was cut into the same size as the above to obtain a test piece. Example 1
When a soil burial test was conducted under the same conditions as in No. 6, the sheet made of polyester [G] still showed its original shape, even after one year, although there were signs of collapse. The film made from block polyester collapsed into pieces and did not stop its original shape. The tensile strength of the stretched film made of block polyester is 11.4.
The value was kg / mm ² , which was a practically sufficient value.

Example 15 Synthesis of high melting point polyester [I] In a 1 liter separable flask equipped with a stirrer, a fractionating condenser, a thermometer, and a gas introduction tube, 205 g of ethylene glycol, 5 g of trimethylolpropane and 3 of succinic acid were added.
After 54 g was charged and esterification was carried out at 200 to 205 ° C. in a nitrogen stream to an acid value of 9.1, 0.06 g of tetraisopropyl titanate was added and finally 210 to 215 ° C. of 0.4 Torr. 8 deglycolization reaction under reduced pressure
I went on time. Then, 1.5 g of trisisodecyl phosphite was added, and the slightly ivory polyester became almost colorless. The obtained polyester [I] is a pure white wax and has a melting point of 10
At 7 ° C, the weight average molecular weight was 49,000 and the number average molecular weight was 17,100.

Synthesis of Low Melting Point Polyester [J] In the same equipment as used for the synthesis of high melting point polyester [I], 205 g of ethylene glycol, 438 g of adipic acid,
After charging 6 g of malic acid and performing esterification in a nitrogen stream at 200 to 205 ° C. to an acid value of 7.7, 0.08 g of tetraisopropyl titanate was added and 210 to 215
After the deglycolization reaction was finally performed under reduced pressure of 0.5 Torr for 6 hours at ℃, tris isodecyl phosphite 1.8
g was added. It is a slightly yellowish white soft wax with a melting point of 50 ° C and a weight average molecular weight of 64,80.
0, polyester having a number average molecular weight of 19,800 [J]
was gotten.

350 g of polyester [I] and 150 g of polyester [J] were charged into a 1 liter separable flask equipped with a stirrer for block polyester , a reflux condenser, a thermometer, and a gas introduction tube, and melted at 190 ° C. Then 5 g of isophorone diisocyanate was added. The viscosity increased rapidly but did not gel. The block polyester obtained was in the form of a pale yellow wax and had a melting point of 105 ° C., which was almost unchanged. The weight average molecular weight of the block polyester is 1
It was 87,000 and the number average molecular weight was 31,000. The tensile strength of a transparent film having a thickness of about 50μ uniaxially stretched at room temperature after press molding of block polyester is 14.7.
It showed kg / mm ² . When a test piece cut from a transparent film into 2 cm × 10 cm was buried in the same soil as in Examples 1 to 6 and tested, it was found that after 6 months, the original shape was destroyed and it was destroyed.

[0069]

Since the method of the present invention is constituted as described above, it can be applied to a general-purpose plastic molding machine such as polyethylene or polypropylene having a melting point of 100 ° C. or more, and can be stretched at room temperature toughness, It is possible to provide a biodegradable block polyester capable of forming a flexible product.

[Brief description of drawings]

FIG. 1 is a diagram showing DSC measurement results of high melting point polyester [A] in Examples 1 to 6 and Comparative Example 1.

FIG. 2 is a diagram showing DSC measurement results of low melting point polyester [B] in Examples 1 to 6 and Comparative Example 1.

FIG. 3 DS of block polyester in Example 1
It is a figure which shows C measurement result.

FIG. 4 DS of block polyester in Example 2
It is a figure which shows C measurement result.

FIG. 5: DS of block polyester in Example 3
It is a figure which shows C measurement result.

FIG. 6 DS of block polyester in Example 4
It is a figure which shows C measurement result.

FIG. 7 DS of block polyester in Example 5
It is a figure which shows C measurement result.

FIG. 8 DS of block polyester in Example 6
It is a figure which shows C measurement result.

9 is a DS of block polyester in Comparative Example 1. FIG.
It is a figure which shows C measurement result.

FIG. 10 is a diagram showing DSC measurement results of low melting point polyester [D] in Examples 7 to 12 and Comparative Example 2.

FIG. 11: D of block polyester in Example 7
It is a figure which shows a SC measurement result.

FIG. 12: D of block polyester in Example 8
It is a figure which shows a SC measurement result.

FIG. 13: D of block polyester in Example 9
It is a figure which shows a SC measurement result.

14 is a diagram showing a DSC measurement result of the block polyester in Example 10. FIG.

FIG. 15 is a view showing a DSC measurement result of block polyester in Example 11.

16 is a diagram showing a DSC measurement result for the block polyester in Example 12. FIG.

FIG. 17: D of block polyester in Comparative Example 2
It is a figure which shows a SC measurement result.

Claims (3)

[Claims] 1. [I] (1) The melting point is 100 ° C. or higher, the number average molecular weight is 5,000 or higher, and the action of the residual catalyst used in the deglycolization reaction with an inorganic or organic phosphorus compound is eliminated. 99% to 20% by weight of aliphatic (including cycloaliphatic) polyester, and (2) melting point of less than 100 ° C, number average molecular weight of 5,000 or more, and inorganic or organic phosphorus compound used for deglycolization reaction. 1 to 80% by weight of the aliphatic (including cycloaliphatic) polyester in which the action of the remaining catalyst was eliminated, and 100 parts by weight of this mixed polyester was mixed with [II] 0.1 to 5 parts by weight. A method for producing a block polyester, which comprises adding and reacting a polyvalent isocyanate. 2. [I] (1) The melting point is 100 ° C. or higher, the weight average molecular weight is 30,000 or higher, and the action of the residual catalyst used in the deglycolization reaction with an inorganic or organic phosphorus compound is eliminated. 99% to 20% by weight of aliphatic (including cycloaliphatic) polyester and (2) melting point of less than 100 ° C., weight average molecular weight of 30,000 or more, and inorganic or organic phosphorus compound used in deglycolization reaction 1 to 80% by weight of the aliphatic (including cycloaliphatic) polyester in which the action of the remaining catalyst was eliminated, and 100 parts by weight of this mixed polyester was mixed with [II] 0.1 to 5 parts by weight. A method for producing a block polyester, which comprises adding and reacting a polyvalent isocyanate to have a weight average molecular weight of 50,000 or more. 3. [I] (1) The melting point is 100 ° C. or higher, the number average molecular weight is 5,000 or higher, and the weight average molecular weight is 30,000.
99 to 20% by weight of an aliphatic (including cycloaliphatic) polyester in which the action of the remaining catalyst used in the deglycolization reaction with an inorganic or organic phosphorus compound is 0 or more, and (2) the melting point is 100. Below ℃, number average molecular weight is 5,
Aliphatic (including cycloaliphatic) polyesters 1 to 80 having a weight average molecular weight of 30,000 or more and a weight average molecular weight of 30,000 or more and eliminating the action of the remaining catalyst used in the deglycolization reaction with an inorganic or organic phosphorus compound (II) 0.1 to 5 parts by weight of a polyvalent isocyanate is added and reacted with 100 parts by weight of the mixed polyester to give a number average molecular weight of 10,000 or more and a weight average. A method for producing a block polyester, which has a molecular weight of 50,000 or more.