JP2873478B2 - 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 a method for producing an olefin-terminated polyester by reacting an olefin-terminated diester compound with a lactone.

[Problems to be Solved by Conventional Techniques and Inventions] Aliphatic polyesters derived from lactones are excellent in flexibility and heat resistance. Therefore, components such as thermoplastic elastomers, urethane elastomers, adhesives, and paints, or It is used as a plasticizer and modifier for various polymers.

As a method for producing such an aliphatic polyester,
In general, a method is known in which a lactone is polymerized using a compound containing a hydroxyl group, for example, glycol or the like as an initiator, to obtain a polyester having a hydroxyl group terminal. However, polyesters having hydroxyl groups at their terminals 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.

A conventionally known method for obtaining an olefin-terminated polyester is to produce a hydroxyl-terminated polyester and then modify the hydroxyl group. However, this method has many problems, such as the necessity of severely strict reaction conditions in order to increase the reaction rate.

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,
An object of the present invention is to provide a method for obtaining an olefin-terminated polyester having a high functionalization rate from an olefin-terminated diester compound and a lactone.

[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). Reaction in the presence of an active catalyst to produce an olefin-terminated polyester having a molecular weight of 5,000 to 50,000, the total amount of unreacted lactones present in the reaction system, other than the ester bond in this unreacted lactone It is characterized in that lactone is added sequentially so as not to exceed 10-fold molar equivalent to other ester bonds present in the reaction system.

That is, in the reaction system, if the lactone is present in excess from the olefin terminal diester compound from the beginning, the reaction in which the lactone is inserted into the diester compound by the transesterification reaction and the polymerization reaction of the lactone itself compete with each other,
The functionalization rate of the terminal olefin is reduced. Therefore,
As in the present invention, the total amount of the unreacted lactone present in the reaction system is different from the ester bond present in the unreacted lactone in addition to the other ester bond present in the reaction system (the ester bond of the diester compound and the diester compound). By successively adding lactone to the reaction system so that the molar ratio does not exceed 10 times the molar equivalent to the ester bond of the inserted polyrataton chain, the insertion reaction of lactone into the diester compound is prioritized, and the functionalization An olefin-terminated polyester having a high ratio can be obtained. Preferably, two or more lactones are sequentially added to the reaction system so as not to exceed 5 molar equivalents, more preferably not to exceed 2 molar equivalents. Two or more types of lactones may be mixed in advance or may be added 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 0,000 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;
And a divalent hydrocarbon group is more preferable. Specific examples of such a diester compound include, for example, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl malonate, diallyl succinate, diallyl glutarate, diallyl adipate, diallyl pimerate, divinyl phthalate,
Examples thereof include divinyl isophthalate, divinyl terephthalate, divinyl malonate, divinyl succinate, divinyl glutarate, divinyl adipate, and divinyl pimerate. In particular, diallyl isophthalate, diallyl adipate, and diallyl succinate are preferred from the viewpoint of easy handling and easy handling.

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, ε-methyl-ε
-Caprolactone, β-methyl-ε-caprolactone,
Lactide, dimethyl-ε-caprolactone and the like. In particular, one of the two or more lactones used in the present invention is preferably ε-caprolactone from the viewpoint of ease of reaction, availability, and the like. Also,
When one of the two or more lactones is ε-caprolactone, the remaining lactones may be β-propiolactone, pivalolactone, α-methyl-β-propio from the viewpoint of availability. Lactone, δ-valerolactone, β-methyl-δ-valerolactone, and γ-methyl-δ-valerolactone are preferred. Furthermore, considering the reactivity, δ-valerolactone, β-methyl-δ-
Valerolactone and γ-methyl-δ-valerolactone are more preferred.

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, etc. Is mentioned. In particular, titanium-n-butoxide and titanium isopropoxide are preferable from the viewpoint of easy availability and easy handling. The amount of the catalyst used is 0.
A range from 0001 to 1.0 molar equivalent is preferred. 0.1 mole equivalent or less is preferable from the viewpoint of the functionalization rate of the terminal, and 0.001 mole equivalent or more is preferable from the viewpoint of the reaction rate.

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 and a lactone.

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

Example 1 A glass four-necked flask equipped with a stirrer, 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 to 2.2 ml (10 mmol). 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 dried with molecular sieve 4A1 / 16 while stirring at 170 ° C.
56 ml (500 mmol) of ε-caprolactone and 40 mO (360 mmo
The mixture of 1) with β-methyl-δ-valerolactone is
4.0 ml (36 mmol), 4.0 ml (36 mmol), 8.0 ml (72 mmo
l), 16 ml (144 mmol), 32 ml (288 mmol) and 32 ml (288
(mmol) from the dropping funnel. At the time of each drop, after the end of the previous drop, the reaction mixture is analyzed at regular intervals by proton NMR (nuclear magnetic resonance), and after confirming that the dropped ε-caprolactone is almost consumed, the next drop is performed. Was performed. All the dropwise addition was completed in about 13 hours, and thereafter, the mixture was heated and stirred at 170 ° C. for 5 hours. Next, the pressure is reduced at 120 ° C. and unreacted β remaining in the system is removed.
-Methyl-δ-valerolactone monomer was removed.

When the obtained compound was analyzed by proton NMR, the NMR spectrum shown in FIG. 1 was obtained, and poly (caprolactone)-(β-methyl-δ-valero having an average of 1.85 allyl ester groups in one molecule was obtained. (Lactone) copolymer. Further, the number average molecular weight by VPO (vapor pressure osmometry) analysis was 8,000.

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 a molecular sieve 4A1 / 16 (4.4 ml). 20mmo1) diallyl isophthalate and 0.20m
l (0.60 mmol) of tetrabutyl titanate was added.
After stirring this at 170 ° C for 30 minutes, molecular sheep 4A1
A mixture of 56 ml (500 mmol) of ε-caprolactone and 36 ml (325 mmol) of β-methyl-δ-valerolactone, dried using / 16, was added in one portion. Then at 170 ° C 12
The mixture was heated and stirred for an hour.

When the obtained compound was analyzed by proton NMR, a peak at 4.5 ppm corresponding to Hq _′ in FIG. 1 was hardly observed, and it was confirmed that there was almost no allyl group bonded to the polyester terminal. Was. In addition, methylene protons of the allyl group of diallyl isophthalate 4.
From the ratio of the integrated value of the peak at 8 ppm and the peak at 7.4 to 8.7 ppm due to aromatic protons, the ester bond of diallyl isophthalate shows a transesterification reaction (insertion reaction of ε-caprolactone and β-methyl-δ-valerolactone). Received very little, and the resulting product was a poly (caprolactone)-(β-methyl-δ-valerolactone) copolymer,
The mixture was confirmed to be a mixture of diallyl isophthalate and β-methyl-δ-valerolactone monomer.

[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 (5)

(57) [Claims] (1) 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), and the olefin-terminated diester compound is transesterified with two or more lactones. Reaction in the presence of a catalyst having a molecular weight of 5,
In producing an olefin-terminated polyester having a molecular weight of 000 to 50,000, the total amount of unreacted lactone present in the reaction system is an ester bond of the olefin-terminated diester compound and an ester bond of a polylactone chain already inserted into the olefin-terminated diester compound. A production method characterized by adding lactone sequentially so as not to exceed 10 molar equivalents. 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 one of the two or more lactones is ε-caprolactone. 4. One of the two or more lactones is ε-caprolactone, and the remaining lactones are β-propiolactone, pivalolactone, α-methyl-β-propiolactone, δ-valerolactone. , Β-methyl-δ
Valerolactone, γ-methyl-δ-valerolactone,
Dimethyl-δ-valerolactone, δ-methyl-ε-caprolactone, ε-methyl-ε-caprolactone, β-methyl-ε-caprolactone, lactide, dimethyl-ε-
At least one selected from the group consisting of caprolactone
The method according to claim 1, wherein the method is a seed. 5. The method according to claim 1, wherein the catalyst having transesterification ability is tetrabutyl titanate and / or tetraisopropyl titanate.