JPH05295069A - Production of aliphatic polyester having high molecular weight - Google Patents

Abstract

PURPOSE:To obtain the subject polymer useful for various uses such as film, molded material and fiber by adding a polyvalent isocyanate in a molten state to a polyester obtained by the polycondensation of three specific components and having a molecular weight increased as far as possible. CONSTITUTION:The objective polymer having a number-average molecular weight of >=20,000 can be produced by compounding (A) 100 pts.wt. of a polyester having a melting point of >=60 deg.C and a number-average molecular weight of >=10,000 and produced by the polycondensation of (i) an aliphatic dicarboxylic acid (anhydride) component containing succinic acid (anhydride) as essential component, (ii) a (cyclo)aliphatic glycol component (e.g. 1,4-butanediol) and (iii) an epoxy resin or an epoxy compound component containing >=2 epoxy groups (e.g. bisphenol A glycidyl ether) with (B) 0.3-5 pts.wt. of a polyvalent isocyanate (e.g. 2,4-tolylene diisocyanate) in a molten state at a temperature above the melting point of the component A, preferably at 150-250 deg.C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a high molecular weight aliphatic polyester. More specifically, the present invention relates to a high molecular weight aliphatic polyester useful for various uses such as films, molded articles and fibers. The present invention relates to a manufacturing method of.

[0002]

2. Description of the Related Art Conventionally, aliphatic polyester is polyethylene terephthalate (hereinafter abbreviated as PET).
Unlike polyesters with aromatic structures such as, PE with a molecular weight (number average, the same below) of 15,000
It did not show the excellent physical properties that T had.
Further, even if the molecular weight of the aliphatic polyester is increased, the thermal stability of the aliphatic polyester is poor, so that the decomposition reaction has priority over the growth reaction, which is very difficult. Furthermore, most of the aliphatic polyester,
It is only an exaggeration to say that it showed only a melting point of 100 ° C. or lower and was not practical in the molecular weight range reached by polycondensation. Conventionally, polyester as a raw material found in the polyurethane industry has a molecular weight of 1,00 whether it is a molded product, paint, adhesive, hard-soft foam, or rubber.
0 to 3,000 and a vinyldroxyl number of 50 to 150, which is, so to speak, oligomeric (hereinafter referred to as prepolymer), and is a large amount of diisocyanate (or other compound) such as 7 to 30 parts by weight per 100 parts by weight of polyester. It is not possible to obtain practical physical properties unless an adduct of bisphenol and diisocyanate is used. However, when such a large amount of diisocyanate is used in combination, in other words, when the concentration of the isocyanate group is high, gelation is always caused at a high temperature of 100 ° C. or higher regardless of the composition. , The desired product is not obtained. For example, in the case of foams or molded products by resin injection method,
When a liquid polyol component, an isocyanate component (including prepolymerized type), and a catalyst for accelerating the reaction are mixed into the mold immediately before discharge, gelation and curing process within a short time immediately after injection into the mold. And does not form a stable intermediate, and the cured resin is crosslinked.

In products produced in the polyurethane industry, isocyanates are used as follows. For example, in the case of paints and adhesives, the heat curing type uses masked isocyanate, and the isocyanate is regenerated and cured by heating. In the case of moisture-curing type, the end group of the prepolymer is made into an isocyanate, and it is considered that the isocyanate group is urea-bonded by the action of water and the isocyanate group reacts with this to cure. ing. In the case of polyurethane rubber, when isocyanate is directly reacted with polyester prepolymer, it partially gelates, and the deterioration of physical properties as rubber is unavoidable.Therefore, isocyanate is not used directly but the end of prepolymer is used. Is converted into an isocyanate, and the type of the diol or diamine component is selected and added to this according to the physical properties of the rubber. The fiber is similar to the above, but it is not a simple polyester or polyether but a so-called segmented type. There are thermosetting types and thermoplastic types, but in any case, it is still the case that a prepolymer and a correspondingly large amount of isocyanate are used. That is, the final structure of polyurethane contains a large amount of urethane bonds. For example, molecular weight 2,
If 000 prepolymers are used, from the calculation, polyurethane having a molecular weight of 10,000 has 8 to 10 urethane bonds, and a molecular weight of 30,000 has about 30 urethane bonds. The present inventors mainly from the standpoint of obtaining a film using biodegradable plastics,
Through repeated research into increasing the molecular weight of aliphatic polyesters, I have found that conventional polyurethane resins, which have a high concentration of urethane bonds in the molecule, are not necessarily suitable for films. For example, in the case of a crystalline polyester synthesized from 1,4-butanediol and succinic anhydride, if the concentration of urethane bonds in the molecule is high, it becomes stiff and poor in elongation and is not suitable for a film. is there. An object of the present invention is to solve the conventional problems as described above and to provide a method for producing a high molecular weight aliphatic polyester useful for various applications such as films, molded articles and fibers.

[0004]

As a result of intensive studies, the present inventors were able to solve the above-mentioned conventional problems. That is, the present invention provides [I] (1) an aliphatic dicarboxylic acid (or an acid anhydride thereof) component containing succinic acid (or succinic anhydride) as an essential component, (2) an aliphatic or cycloaliphatic glycol. Component, (3) an epoxy resin (or a compound thereof) component containing at least two epoxy groups in one molecule, obtained by polycondensing three components,
To 100 parts by weight of a polyester (a) having a melting point of 60 ° C. or more and a number average molecular weight of 10,000 or more, [II] is added 0.3 to 5 parts by weight of a polyvalent isocyanate in a molten state at a melting point of the polyester (a) or more. Then
Provided is a method for producing a high molecular weight aliphatic polyester, which has a number average molecular weight of 20,000 or more.

The present invention will be described in more detail below. Unlike the conventional polyurethane resin, the present inventors have made the molecular weight of the polyester as high as possible, preferably 10,000 or more, and in the state where the end groups are reduced, a small amount of polyvalent isocyanate corresponding to the end groups is melt-mixed. By doing so, it was found that a high molecular weight aliphatic polyester that achieves the above-mentioned object can be obtained, and the present invention was completed. That is, the feature of the present invention is that the number of urethane bonds in the polyester molecule is remarkably small, and it is considered that one urethane bond per 10,000 molecular weight is calculated. As described above, it is difficult to obtain good film physical properties unless the concentration of urethane bonds is low.

In the present invention, succinic acid or succinic anhydride is used as an essential component. The reasons are listed below. (i) The melting point should be 60 ° C or higher, preferably 100 ° C or higher. For example, the melting point of a polyester obtained from 1,4-butanediol and succinic acid is 115 ° C, and the melting point of a polyester obtained from ethylene glycol and succinic acid is about 105 ° C. These have the same melting point as that of polyethylene, and if the melt viscosity is high, it can be molded using a processing machine for polyethylene. (ii) Large room for practical modification. As an example, when adipic acid is used in combination with 1,4-butanediol and succinic acid, the melting point becomes about 90 ° C. when 20 mol (%) is used, and the physical properties are similar to those of soft polyethylene. In addition, by using a small amount of sebacic acid and dotecanedioic acid (10 mol (%) or less with respect to 100 mol (%) of the entire dicarboxylic acid), biodegradability can be accelerated without impairing physical properties. It will be possible. (iii) Highly safe for the human body. Succinic acid is a food additive and its safety has been confirmed. When the polyester decomposes, it becomes succinic acid instead of succinic anhydride.
It should be noted that succinic acid and succinic anhydride should not show a significant difference in the polyester produced using either, when using succinic anhydride, the reason is unknown, especially the weight average molecular weight increases A tendency is recognized and it is preferable. In addition, during the polycondensation reaction, the esterification reaction of succinic acid occurs first, but in the case of succinic anhydride, it is an initial ring-opening addition reaction, and there is a difference in the reaction process depending on the presence or absence of heat generation at the beginning of the reaction. That is, succinic anhydride is an exothermic reaction initially, and succinic acid is an endothermic reaction because water is released. Other,
If the water of reaction is succinic anhydride, it will be half that of succinic acid, so if available at the same price, succinic anhydride is useful for cost reduction.

If desired, an aliphatic dicarboxylic acid (or its acid anhydride) component other than succinic acid or succinic anhydride can be used in combination. Examples thereof include adipic acid, suberic acid, sebacic acid, and dodecanedioic acid, because the melting point is not lowered as much as possible. The usage rate is
If the melting point of the polyester (a) can be 60 ° C. or higher, it is 40 mol (%) or less with respect to 100 mol (%) of the entire aliphatic dicarboxylic acid (or its acid anhydride) component.

The glycol component used in the present invention is 1,4-butanediol, ethylene glycol, 1,
4-Cyclohexanedimethanol is mentioned as a kind which can raise a melting point. The usage ratio is substantially equimolar to the above aliphatic dicarboxylic acid (or its acid anhydride) component, but may be used in excess unless it exceeds 10 mol (%). These glycol components are also suitable for the present invention from the viewpoint of imparting crystallinity to the produced polyester and improving the physical properties of films, molded products and fibers. The presence or absence of crystallinity can be easily judged from the appearance of polyester. Needless to say, the above-mentioned glycol components may be used in combination or other glycols may be added as long as the melting point and the physical properties are not impaired.

An advantage of the present invention is that, in addition to the above-mentioned aliphatic dicarboxylic acid (or acid anhydride) component and glycol component, an epoxy resin (or compound thereof) component containing at least two epoxy groups in one molecule. To 100 parts by weight of the total of the aliphatic dicarboxylic acid (or acid anhydride thereof) component and the aliphatic or cycloaliphatic glycol component,
Polycondensation is carried out by adding 0.1 to 5 parts by weight. The reasons why the epoxy resin (or compound thereof) component is used in combination are listed below. (A) To increase the molecular weight of polyester as much as possible. Since the epoxy resin (hereinafter, also including the compound) acts as a polyhydric alcohol, the two epoxy groups end up having the same action as the four hydroxyl groups. That is, in ordinary polycondensation, it is not easy to set the number average molecular weight to 15,000 or more due to the poor thermal stability of the aliphatic polyester. However, when the epoxy resin is used together, the number average molecular weight can be easily increased to 20,000 or more. In this case, the addition amount of the epoxy resin capable of performing the reaction without danger of gelation is the above-mentioned ratio. (B) The molecular weight ratio becomes large. That is, in forming a film, it is preferable that the ratio M _W / M _N of the weight average molecular weight (M _W ) and the number average molecular weight (M _N ) is large, but this is also feasible. .. The epoxy resin can be added from the beginning of the polycondensation, but may be added during the esterification or deglycolization reaction if necessary. The epoxy resin used in the present invention needs to have at least two epoxy groups in one molecule, but it is not particularly limited in its structure, and commercially available products can be used as they are. It is possible. For example,
Bisphenol A glycidyl ether, bisphenol F glycidyl ether, homologues thereof, novolac glycidyl ethers, polyhydric alcohol glycidyl ethers such as 1,4-butanediol diglycidyl ether, trimethylolpropane triglycidyl ether, glycidyl Examples thereof include esters such as adipic acid diglycidyl ester, succinic acid diglycidyl ester and the like, glycidyl isocyanurate and the like.

Polyester synthesis is generally carried out by esterification and deglycolization of the above components.
The conditions include, for example, an esterification reaction at a temperature of 18
It can be performed at 0 to 230 ° C. for 5 to 16 hours. In this case, the acid value is preferably 30 or less. The deglycol reaction is performed at a temperature of 180 to 230 ° C. for 2 to 16 hours and a pressure of 1 Torr.
The following deglycolization reaction is carried out by using an organic compound of titanium (eg, a tetraalkoxytitanium compound, titanium oxyacetylacetonate, etc.), zinc,
It is preferable to use organic acid salts of metals such as lead and zirconium, chelate compounds and antimony oxide. The deglycolization catalyst is preferably used in an amount of 0.001 to 0.1 part by weight based on 100 parts by weight of the produced polyester.

Number average molecular weight 1 obtained as described above
A polyvalent isocyanate is added to the polyester (a) having a molecular weight of 000 or more in order to further increase the molecular weight. The polyvalent isocyanate that can be used may be any commercially available one and is not particularly limited. For example, 2,4-tolylene diisocyanate, 2,4-tolylene diisocyanate and 2,
Mixture with 6-tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate,
Examples include hexamethylene diisocyanate, adducts of these isocyanates with polyhydric alcohols or trimers, and triphenylmethane triisocyanate. The addition amount of the polyvalent isocyanate is sufficient in the range of 0.3 to 3 parts by weight in the case of diisocyanate, but 0.5 to 5 parts by weight in the case of an adduct of trimethylolpropane and isocyanate. A range of parts is required. Taking these into consideration, the addition amount of the polyvalent isocyanate is required to be 0.3 to 5 parts by weight based on 100 parts by weight of the desired polyester. If it is less than 0.3 parts by weight, the effect of the addition is poor, and if it exceeds 5 parts by weight, not only the physical properties are rather adverse but the risk of gelation is significantly increased. The addition of the polyvalent isocyanate depends on the melting state of the polyester (a) or higher, that is, depending on the melting point of the polyester,
It is good to carry out between 150-250 degreeC.

The apparatus used for producing the high molecular weight aliphatic polyester of the present invention is not particularly limited as long as it is capable of high-viscosity stirring. The aliphatic high molecular weight polyester containing a small amount of urethane bond according to the present invention can be used in combination with a reinforcing material, a filler, a colorant, various stabilizers, a lubricant wax, a saturated or unsaturated polymer in practical use. Of course.

[0013]

EXAMPLES Examples will be shown below to facilitate understanding of the present invention. Example 1 300 g of succinic anhydride was placed in a 1 liter separable flask equipped with a stirrer, a fractionating condenser, a thermometer, and a gas introduction tube.
300 g of 1,4-butanediol, 9 g of bisphenol A glycidyl ether (Epicoat 827, manufactured by Yuka Shell Co., Ltd.) as an epoxy resin, and 0.6 g of tetraisopropyl titanate were charged, and the mixture was put into a nitrogen gas stream at 205 to 21.
After esterification at 0 ° C to give an acid value of 7.7, the product was finally deglycolized at 215 to 220 ° C for 4 hours under a reduced pressure of 0.6 torr. It was a slightly yellowish white wax. Having a melting point of about 115 ° C., a weight average molecular weight (M _W ) of 82,000 and a number average molecular weight (M _N ) of 24,1.
It was obtained at 00 (M _W / M _N ≈3.4). 300 g of polyester (a) was melted at 200 ° C., and 5 g of hexamethylene diisocyanate was added. The viscosity increased rapidly but did not gel. The obtained high molecular weight aliphatic polyester (A) of the present invention containing a small amount of urethane bond is a pale yellow wax and has a melting point of 117 to 118 ° C. and a weight average molecular weight.
The number average molecular weight was 337,000, the number average molecular weight was 49,600, and M _W / M _N ≈6.8. This is judged to be advantageous in film formation.
In the melt flow measurement of polyester (A) by JIS-K-7210A method, when the temperature is 190 ° C. and the load is 2.16 kg,
It showed 0.3 to 0.5 g / 10 minutes and was suitable for a film. The polyester (A) was press-molded and uniaxially stretched 4 times, and the tensile strength of the film having a thickness of about 40 μ was 11.3 to 14.4 kg / mm ² and was extremely strong. The molecular weight was measured by GPC. Model used Shodex GPC SYSTEM-11 (manufactured by Showa Denko KK) Eluent 5 mM CF ₃ COONa / HFIP column Sample column HFIP-800P HFIP-80M x 2 Reference column HPIP-800R x 2 Column temperature 40 ° C Flow rate 1.0 ml / Min Detector Shodex RI Standard PMMA (Shodex STANDARD M-75)

Example 2 A 1-liter separable flask equipped with a stirrer, a fractionating condenser, a thermometer, and a gas introduction tube was charged with 305 g of 1,4-cyclohexanedimethanol, 180 g of succinic anhydride, 80 g of sebacic acid, and a novolak type flask. Epoxy resin (Dow-Chemical company make, DEN-431) 5g, tetraisopropyl titanate 0.6g were charged, and nitrogen gas stream 205-2 was used.
After esterification at 10 ° C to an acid value of 8.3, 210-
Finally, deglycolization reaction was carried out at 215 ° C. under a reduced pressure of 0.5 torr for 10 hours to give a pale ivory white crystalline polyester (b) having a melting point of 115 to 117 ° C., a number average molecular weight (M _N ) of 20,900, and a weight. Obtained with an average molecular weight (M _W ) of 71,300 (M _W / M _N ≈3.4). Polyester (b) 30
0 g was melted at 205 ° C., and 5 g isophorone diisocyanate was added. The viscosity increased rapidly but did not gel. The obtained high molecular weight aliphatic polyester (B) of the present invention containing a small amount of urethane bond has a melting point of about 120 ° C., is in the form of a light tan wax, and has a weight average molecular weight (M _W ) of 350,000 and a number average molecular weight (M _N ) of 44,700. Then, M _W / M _N ≈7.8.
The above molecular weights were measured in the same manner as in Example 1. According to the JIS-K-7210A method and the melt flow measurement at a load of 2.16 Kg at 190 ° C., the outflow amount was only 0.2 to 0.5 g / 10 minutes, which was suitable for film formation. Polyester (B) was press-molded and uniaxially stretched 4 times to obtain a film having a thickness of about 40μ and a tensile strength of 1
It was extremely strong at 1.4 to 13.9 kg / mm ² . Further, the film embedded 10 cm below the black soil had many pores after 3 months, and biodegradability was confirmed.

Example 3 A 1 l separable flask equipped with a stirrer, a fractionating condenser, a thermometer, and a gas introduction tube was charged with ethylene glycol 205.
g, 300 g of succinic anhydride, and 0.5 g of titanium oxyacetylacetonate were charged, and 195 to 20 in a nitrogen gas stream was introduced.
After esterification at 0 ° C to an acid value of 51.4, 4 g of ethylene glycol diglycidyl ether was added to give an acid value of 30.
After esterification to 1, the mixture was reacted under reduced pressure of 10 Torr for 1 hour to give an acid value of 6.4. Then 210-215 ° C
In a reduced pressure of finally 0.4 torr, for 8 hours to remove the glycol reaction, a white waxy polyester (c ') is, melting point 103 ° C., a weight average molecular weight (M _W) 88,600, number average molecular weight (M _N) It was obtained at 24,700 (M _W / M _N ≈3.6). 300 g of polyester (c ′) was melted at 200 ° C., and 4.5 g of diphenylmethane diisocyanate was added. The viscosity increased rapidly but did not gel. The obtained high molecular weight aliphatic polyester (C) of the present invention containing a small amount of urethane bond has a melting point of 105 to 107 ° C., is a light tan wax, and has a number average molecular weight (M _N ) 49,100 and a weight average molecular weight (M _W ). At 339,000, M _W / M _N ≈7. The above molecular weights were measured in the same manner as in Example 1. Polyester (C) was press-molded and uniaxially stretched 4 times to obtain a film with a thickness of about 40μ with a tensile strength of 11.2
It was extremely strong at about 14.1 kg / mm ² .

[0016]

INDUSTRIAL APPLICABILITY The present invention provides a method for producing a high molecular weight aliphatic polyester useful for various uses such as films, molded articles and fibers.

Claims (2)

[Claims] 1. [I] (1) An aliphatic dicarboxylic acid (or its acid anhydride) component containing succinic acid (or succinic anhydride) as an essential component, (2) an aliphatic or cycloaliphatic glycol. Component, (3) Epoxy resin (or compound thereof) component containing at least two epoxy groups in one molecule, which is obtained by polycondensation, and has a melting point of 60 ° C. or higher and a number average molecular weight of 10,0.
[II] 0.3 to 5 parts by weight of a polyvalent isocyanate is added to 100 parts by weight of a polyester (a) of 00 or more in a molten state at or above the melting point of the polyester (a),
A method for producing a high molecular weight aliphatic polyester, which has a number average molecular weight of 20,000 or more. 2. An epoxy resin (or compound thereof) component containing at least two epoxy groups in one molecule,
(1) Aliphatic dicarboxylic acid (or its acid anhydride) containing succinic acid (or succinic anhydride) as an essential component
The method according to claim 1, wherein the component and (2) the aliphatic or cycloaliphatic glycol component are used in a proportion of 0.1 to 5 parts by weight based on 100 parts by weight in total.