JP2818897B2 - Method for producing olefin-terminated polyester - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing an olefin-terminated polyester, and more particularly, to an olefin obtained by copolymerizing an olefin-terminated diester compound, a lactone, a cyclic acid anhydride and an epoxy compound. The present invention relates to a method for producing a terminal polyester.

[Problems to be Solved by Conventional Techniques and Inventions] Aliphatic polyesters are excellent in flexibility and heat resistance. Therefore, components such as thermoplastic elastomers, urethane elastomers, adhesives and paints, or plasticizers of various polymers are used. And as a denaturant.

Usually, as a method for producing an aliphatic polyester, a method of obtaining a polyester whose terminal is a hydroxyl group or a carboxyl group by polycondensing various diol compounds and a dibasic acid or a derivative thereof, or a compound containing a hydroxyl group, for example, It is well known that lactone is polymerized using glycol or the like as an initiator to obtain a hydroxyl-terminated polyester. However, polyesters whose terminals are hydroxyl groups or carboxyl groups have limited uses, and attempts have been made to modify them into other functional groups. In particular, olefin-terminated polyesters are more important than their reactivity diversity.

Conventionally known methods for obtaining an olefin-terminated polyester include, when polycondensing various diol compounds and dibasic acids or their derivatives, a monohydric alcohol having a terminal olefin, a monocarboxylic acid, or a monocarboxylic acid or a monocarboxylic acid having an olefin at the terminal. After reacting a derivative or producing a hydroxyl-terminated or carboxyl-terminated polyester, the terminal hydroxyl or carboxyl group is modified. However, there have been many problems such as the fact that the reaction conditions must be considerably strict in order to increase the introduction rate of the terminal olefin.

Also, as seen in JP-A-61-37813,
By reacting an ester compound having a functional group with ε-caprolactone, polyesters having various functional groups at their terminals can be synthesized. However, it is also possible to obtain an olefin-terminated polyester using this method. . However, in this method, the insertion reaction of the lactone chain into the ester compound and the homopolymerization reaction of ε-caprolactone itself compete with each other, and the functionalization ratio of the olefin does not increase (olefin-terminated polyester having a large number of ester bond units, That is, an olefin-terminated polyester formed by inserting many lactone chains cannot be obtained.)

Therefore, an object of the present invention is to solve the above problems,
It is an object of the present invention to provide a method for obtaining an olefin-terminated polyester having a high functionalization rate from an olefin-terminated diester compound, a lactone, a cyclic acid anhydride and an epoxy compound.

[Means and Actions for Solving the Problems] The method for producing an olefin-terminated polyester of the present invention comprises:
General formula (Wherein, R represents a divalent organic group having 1 to 20 carbon atoms, n represents an integer of 0 or 1 to 5). An olefin-terminated diester compound, lactone, cyclic acid anhydride and epoxy compound represented by the following formula: The reaction is carried out in the presence of an exchangeable catalyst, and the molecular weight is 5,000 to 5
In producing an olefin-terminated polyester having a molecular weight of 0,000, the amount of each of the lactone, cyclic acid anhydride and epoxy compound present unreacted in the reaction system is not limited to an ester bond in the unreacted lactone. It is characterized in that lactone, cyclic acid anhydride and epoxy compound are added successively so as not to exceed 10 molar equivalents relative to other ester bonds present.

That is, if the lactone, cyclic acid anhydride and epoxy compound are present in excess in the reaction system from the beginning, the lactone, cyclic acid anhydride and epoxy compound are inserted into the diester by transesterification. And the homopolymerization reaction of the lactone itself and / or the reaction of copolymerizing only the cyclic acid anhydride and the epoxy compound, and the functionalization rate of the terminal olefin decreases. Therefore, as in the present invention,
The amount of each of the lactone, the cyclic acid anhydride and the epoxy compound which are present unreacted in the reaction system is different from the ester bond present in the unreacted lactone in the other ester bond present in the reaction system (the ester bond of the diester compound and Lactone, cyclic acid anhydride and ester bond formed by epoxy compound already inserted into diester compound)
By adding lactone, cyclic acid anhydride and epoxy compound to the reaction system so as not to exceed 10 molar equivalents, the insertion reaction of lactone, cyclic acid anhydride and epoxy compound into the diester compound becomes possible. It is possible to obtain an olefin-terminated polyester with high priority and a high functionalization rate. The lactone, cyclic acid anhydride and epoxy compound are sequentially added to the reaction system so as not to exceed preferably 5 times molar equivalent, more preferably not to exceed 2 times molar equivalent. These three components may be added in a pre-mixed state or separately.

In particular, when a polyester having a molecular weight of 5,000 to 50,000 is obtained, an olefin-terminated polyester having a high functionalization rate can be obtained by this method. Molecular weight
In the case of obtaining a polyester smaller than 5,000, a polyester having a high degree of functionalization can be obtained without using this method. On the other hand, when the molecular weight exceeds 50,000, the effect of the terminal olefin becomes difficult to develop. Preferably, the molecular weight is 2
In this case, an olefin-terminated polyester having a molecular weight of not more than 10,000 is obtained.

R in the olefin-terminated diester compound represented by the general formula (1) has 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms;
The divalent organic group is more preferably a divalent organic group. Specific examples of such a diester compound include, for example, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl malonate, diallyl succinate, diallyl glutarate, diallyl dipate, diallyl pimerate, divinyl phthalate,
Examples include divinyl isophthalate, divinyl terephthalate, divinyl malonate, divinyl succinate, divinyl glutarate, divinyl adipate, and divinyl acid pimerate. In particular, diallyl isophthalate, diallyl adipate,
Diallyl succinate is preferred.

As the lactone used in the present invention, for example, β-
Propiolactone, pivalolactone, α-methyl-β-
Propiolactone, δ-valerolactone, β-methyl-
δ-valerolactone, γ-methyl-δ-valerolactone, dimethyl-δ-valerolactone, ε-caprolactone, δ-methyl-ε-caprolactone, dimethyl-ε-
And caprolactone. These lactones are 1
The species may be used alone or in combination of two or more. Among them, ε-caprolactone is preferred from the viewpoint of easy reaction and availability. When two or more are used in combination, one of them is preferably ε-caprolactone. As the lactone used in combination with ε-caprolactone, β-propiolactone, pivalolactone, α-methyl-β-propiolactone, δ-valerolactone, β-
Methyl-δ-valerolactone and γ-methyl-δ-valerolactone are preferred. Further, in consideration of reactivity, δ-valerolactone, β-methyl-δ-valerolactone, and γ-methyl-δ-valerolactone are more preferable.

The innumerable cyclic acids used in the present invention may be any, but from the viewpoint of availability, ease of handling, etc., phthalic anhydride, succinic anhydride, maleic anhydride and acid anhydrides derived therefrom (for example, , Methylendmethylenetetrahydrophthalic anhydride, endmethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, etc.).

The epoxy compound used in the present invention has the general formula (In the formula, R ′ and R ″ are each hydrogen or carbon atom 1
Represents a monovalent organic group of -20. ) Is preferred. Further, among them, phenyl glycidyl ether, n-butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dibromocresyl glycidyl ether, styrene oxide and derivatives derived therefrom from the viewpoint of easy availability and easy handling. One or more epoxy compounds to be used are more preferred.

Further, in the present invention, an epoxy compound is necessary for the cyclic acid anhydride to be polymerized, and a cyclic acid anhydride is required for the epoxy compound to be polymerized.
In order to increase the reaction rate, the total molar ratio of the cyclic acid anhydride and the epoxy compound (cyclic acid countless number / epoxy compound) is set to 0.
It is preferably from 8 to 1.2.

As the transesterification catalyst used in the present invention, generally known catalysts can be used in a wide range, and in particular, metal alkoxides are preferable. Examples of such metal alkoxides include magnesium ethoxide, aluminum isopropoxide, potassium t-butoxide, zirconium-n-propoxide, titanium-n-butoxide (n-butyl titanate),
Titanium isopropoxide (isopropyl titanate), titanium allyloxide (allyl titanate),
Butyltin trimethoxide, dibutyltin dimethoxide, tributyltin methoxide, zinc di-n-butoxide and the like. In particular, titanium-n-butoxide and titanium isopropoxide are preferred from the viewpoint of easy availability and easy handling. The amount of the catalyst used is 0.0001 to olefin terminal diester compound used.
A range of 1.0 molar equivalent is preferred. 0.1 mol equivalent or less is preferable from the viewpoint of the functionalization rate of the terminal, and 0.0 mol equivalent or less is preferable from the viewpoint of the reaction rate.
It is preferably at least 01 molar equivalent.

The reaction temperature is preferably from 80 to 230 ° C, more preferably from 100 to 200 ° C, from the viewpoint of catalytic activity.

The olefin-terminated polyester obtained by the present invention can be used as a copolymer component as it is,
It can also be used as a plasticizer or modifier for various polymers. Further, the terminal olefin can be used after being modified to another functional group. For example, a room temperature curable resin can be obtained by adding a hydrosilane having a hydrolyzable group by a hydrosilylation reaction.

[Effects of the Invention] According to the present invention, an olefin-terminated polyester having a high functionalization rate can be obtained from an olefin-terminated diester compound, a lactone, a cyclic acid anhydride and an epoxy compound.

[Examples] In order to further clarify the present invention, examples will be given below.

Example 1 After replacing a 100 ml glass four-necked flask equipped with a stirring rod, a thermometer, a dropping funnel, a nitrogen blowing tube and a cooling tube with nitrogen gas, the mixture was dried using molecular sieve 4A1 / 16 and dried 2.2 ml (10 mmol). ) Of diallyl isophthalate and 0.1
0 ml (0.30 mmol) of tetrabutyl titanate was added. After stirring this at 170 ° C for 30 minutes,
While stirring with, 4.0 ml (36 mmol) of ε-caprolactone dried using a molecular sieve 4A1 / 16 was added dropwise. Three
After 0 minutes, the reaction mixture was analyzed by proton NMR (nuclear magnetic resonance), and it was confirmed that the dropped ε-caprolactone was almost consumed. Next, 0.7 g (7.0 mmol) of succinic anhydride
And 0.95 ml (7.0 mmol) of phenylglycidyl ether were simultaneously added. 30 minutes after the addition, the reaction mixture is protonated
Analysis by NMR confirmed that the added succinic anhydride and phenylglycidyl ether were almost consumed. Thereafter, similarly, dropping of ε-caprolactone, and addition of succinic anhydride and phenylglycidyl ether, respectively,
10 times, a total of 40 ml (36 mmol) of ε-caprolactone,
7.0 g (70 mmol) of succinic anhydride and 9.5 ml (70 mmol) of phenylglycidyl ether were added in about 10 hours. Thereafter, the mixture was heated and stirred at 170 ° C. for 5 hours.

When the obtained compound was analyzed by proton NMR, the NMR spectrum shown in FIG. 1 was obtained, and poly (caprolactone-succinic anhydride-phenylglycidyl ether) 3 having an average of 1.75 allyl ester groups in one molecule was obtained.
It was confirmed that the copolymer was an original copolymer. Further, the number average molecular weight by VPO (vapor pressure osmometry) analysis was 6,300.

Example 2 A glass four-necked flask equipped with a stirring rod, a thermometer, a dropping funnel, a nitrogen blowing tube, and a cooling tube was replaced with nitrogen gas, and then dried using molecular sieve 4A1 / 16 (6.6 ml, 30 mmol). 0.30m with diallyl isophthalate)
l (0.90 mmol) of tetrabutyl titanate was added.
After stirring at 170 ° C for 30 minutes, 10.0 ml (90 mmol) of ε-caprolactone dried using molecular sieve 4A1 / 16 was added dropwise while stirring at 170 ° C. After 30 minutes, the reaction mixture was analyzed by GPC (gel permeation chromatography), and it was confirmed that the dropped ε-caprolactone was almost consumed. Next, succinic anhydride 4.
5 g (45 mmol) and phenyl glycidyl ether 6.1 ml (45 m
mol) were added sequentially. 30 minutes after the addition, the reaction mixture is G
Analysis by PC confirmed that the added succinic anhydride and phenylglycidyl ether were almost consumed. Thereafter, in the same manner, dropping of ε-caprolactone and addition of succinic anhydride and phenylglycidyl ether were performed 8 times, respectively, to obtain a total of 80 ml (720 mmol) of ε-caprolactone, 36.0 g (360 mmol) of succinic anhydride and 48.8 g of succinic anhydride. ml (360m
mol) of phenylglycidyl ether was added in about 8 hours. Thereafter, the mixture was heated and stirred at 170 ° C. for 5 hours.

When the obtained compound was analyzed by proton NMR, an NMR spectrum similar to that of FIG. 1 was obtained, and poly (caprolactone-succinic anhydride-phenylglycidyl ether) having an average of 1.81 allyl ester groups in one molecule was obtained.
It was confirmed to be a terpolymer. Further, the number average molecular weight by VPO analysis was 6,600.

Example 3 After replacing a stainless steel reaction vessel equipped with a stirring rod, a thermometer, a dropping funnel, a nitrogen blowing pipe, and a cooling pipe with nitrogen gas, 60.0 ml (0.27 mol) dried using molecular sieve 4A1 / 16. And diallyl isophthalate and 2.7 ml
(8.1 mmol) of tetrabutyl titanate was added. This was stirred at 170 ° C. for 30 minutes, and then dried using molecular sieve 4A1 / 16 while stirring at 170 ° C.
133 ml (1.20 mol) of caprolactone were added dropwise. After 30 minutes, the reaction mixture was analyzed by GPC, and it was confirmed that the dropped ε-caprolactone was almost consumed. Next, a mixture of 60 g (0.60 mol) of succinic anhydride and 86 ml (0.60 mol) of n-butyl glycidyl ether was added. 30 minutes after the addition, the reaction mixture was analyzed by GPC, and it was confirmed that the added succinic anhydride and n-butyl glycidyl ether were almost consumed. Thereafter, in the same manner, dropping of ε-caprolactone and addition of a mixture of succinic anhydride and n-butyl glycidyl ether were performed 8 times, respectively, for a total of 1,064 ml.
(9.60 mol) of ε-caprolactone, 480 g (4.80 mol) of succinic anhydride and 688 ml (4.80 mol) of n-butyl glycidyl ether were added in about 8 hours. Thereafter, the mixture was heated and stirred at 170 ° C. for 5 hours.

The obtained compound was analyzed by proton NMR.
It was confirmed that the copolymer was a poly (caprolactone-succinic anhydride-n-butyl glycidyl ether) terpolymer having an average of 1.85 allyl ester groups in the molecule.
Further, the number average molecular weight by VPO analysis was 8,400.

Example 4 After replacing a 100 ml glass four-necked flask equipped with a stirring rod, a thermometer, a dropping funnel, a nitrogen blowing tube and a cooling tube with nitrogen gas, the mixture was dried using molecular sieve 4A1 / 16 and dried 2.2 ml (10 mmol). ) Of diallyl isophthalate and 0.1
0 ml (0.30 mmol) of tetrabutyl titanate was added. After stirring this at 170 ° C for 30 minutes,
While stirring with, 4.0 ml (36 mmol) of ε-caprolactone dried using molecular sieve 4A1 / 16 was added dropwise. Three
After 0 minute, the reaction mixture was analyzed by proton NMR, and it was confirmed that the dropped ε-caprolactone was almost consumed. Next, 1.0 g (7.0 mmol) of phthalic anhydride and 0.95 ml (7.0 mmol) of phenylglycidyl ether were sequentially added.
Thirty minutes after the addition, the reaction mixture was analyzed by proton NMR, and it was confirmed that the added phthalic anhydride and phenylglycidyl ether were almost consumed. Thereafter, in the same manner, the dropping of ε-caprolactone, and the addition of phthalic anhydride and phenylglycidyl ether were each performed 10 times,
Total of 40 ml (360 mmol) of ε-caprolactone, 10.0 g (70 mm
ol) of phthalic anhydride and 9.5 ml (70 mmol) of phenylglycidyl ether were added in about 10 hours. Then 170 ° C
For 5 hours.

The obtained compound was analyzed by proton NMR.
It was confirmed that the polymer was a poly (caprolactone-phthalic anhydride-phenylglycidyl ether) terpolymer having an average of 1.75 allyl ester groups in the molecule. Further, the number average molecular weight by VPO analysis was 6,300.

Comparative Example 1 A glass four-necked flask equipped with a stirring rod, a thermometer, a dropping funnel, a nitrogen blowing tube, and a cooling tube was replaced with nitrogen gas, and then dried using molecular sieve 4A1 / 16 (2.2 ml, 10 ml). 0.10m with diallyl isophthalate)
l (0.30 mmol) of tetrabutyl titanate was added.
This was stirred at 170 ° C. for 30 minutes, and subsequently, while stirring at 170 ° C., 40 ml (360 mmol) of ε-caprolactone dried using molecular sieve 4A1 / 16, 7.0 of succinic anhydride,
g (70 mmol) and 9.5 ml of phenylglycidyl ether (70
mmol) was added in one portion. Thereafter, the mixture was heated and stirred at 170 ° C. for 10 hours.

When the obtained compound was analyzed by proton NMR, almost no 4.5 ppm peak corresponding to H _k in FIG. 1 was observed, and it was confirmed that almost no allyl group bonded to the polyester terminal was present. . 4.8 ppm due to methylene protons of the allyl group of diallyl isophthalate
The ester bond of diallyl isophthalate is found to be a transesterification reaction (insertion reaction of ε-caprolactone, succinic anhydride and phenylglycidyl ether) from the ratio of the integrated value of the peak of the above and the peak of 7.4 to 8.7 ppm by the aromatic proton.
And the obtained product was confirmed to be a mixture of a poly (caprolactone-succinic anhydride-phenylglycidyl ether) terpolymer and diallyl isophthalate.

[Brief description of the drawings]

FIG. 1 is an NMR spectrum of a compound obtained in one example of the present invention.

Continuation of front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08G 63/00-63/91

Claims (8)

(57) [Claims] (1) General formula Wherein R is a divalent organic group having 1 to 20 carbon atoms, n is an integer of 0 or 1 to 5, and an olefin-terminated diester compound, lactone, cyclic acid anhydride and epoxy compound Reaction in the presence of a catalyst having exchange capacity
When producing an olefin-terminated polyester having a molecular weight of up to 50,000, the amount of each of the lactone, cyclic acid anhydride and epoxy compound present unreacted in the reaction system is not limited to the ester bond in the unreacted lactone. So that it does not exceed 10-fold molar equivalent relative to other ester bonds present in
A production method characterized by sequentially adding a lactone, a cyclic acid anhydride, and an epoxy compound. 2. The method according to claim 1, wherein the olefin-terminated diester compound is
2. The method according to claim 1, wherein the method is at least one of diallyl isophthalate, diallyl adipate and diallyl succinate. 3. The method according to claim 1, wherein the lactone is ε-caprolactone. 4. The method according to claim 1, wherein said cyclic acid anhydride is at least one of phthalic anhydride, succinic anhydride, maleic anhydride and an acid anhydride derived therefrom. . 5. The epoxy compound according to claim 1, wherein (In the formula, R ′ and R ″ are each hydrogen or carbon atom 1
Represents a monovalent organic group of -20. The method according to claim 1, wherein the epoxy compound is represented by the following formula: 6. The method according to claim 1, wherein said epoxy compound is at least one of phenyl glycidyl ether, n-butyl glycidyl ether, t-butyl glycidyl ether and an epoxy compound derived therefrom. Method. 7. The method according to claim 1, wherein the total molar ratio of the cyclic acid anhydride and the epoxy compound is 0.8 to 1.2. 8. The method according to claim 1, wherein the catalyst having transesterification ability is tetrabutyl titanate and / or tetraisopropyl titanate.