JP2873471B2 - 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, and n represents an integer of 0 or 1 to 5). To produce an olefin-terminated polyester having a molecular weight of 5,000 to 50,000, the amount of unreacted lactone present in the reaction system is reduced in the reaction system in addition to the ester bond in the unreacted lactone. It is characterized in that the lactone is added successively so as not to exceed 10 times the molar equivalent relative to the other ester bonds present.

That is, if the lactone is present in excess in the reaction system with respect to the olefin-terminated diester compound from the beginning, the reaction in which the lactone is inserted into the diester compound by the transesterification reaction and the homopolymerization reaction of the lactone itself compete with each other. The olefin functionalization rate is reduced. Therefore, as in the present invention, the amount of unreacted lactone present in the reaction system is determined by the amount of other ester bonds present in the reaction system other than the ester bond in the unreacted lactone (the ester bond of the diester compound and the diester compound). Lactone is successively added to the reaction system so as not to exceed 10 molar equivalents relative to the ester bond of the polylactone chain already inserted into the diester compound, whereby the lactone insertion reaction into the diester compound is prioritized, An olefin-terminated polyester having a high functionalization rate can be obtained. The lactone is added to the reaction system sequentially so as not to exceed preferably 5 molar equivalents, more preferably not to exceed 2 molar equivalents.

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 availability 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, dimethyl-ε-
And caprolactone. In particular, ε-caprolactone is preferred in terms of ease of reaction and the like.

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 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 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 to 4.4 ml (20 mmol). ) 0.20m with diallyl isophthalate
l (0.60 mmol) of tetrabutyl titanate was added.
After stirring this at 170 ° C. for 30 minutes, it was dried using molecular sieve 4A1 / 16 while subsequently stirring at 170 ° C.
150 ml (1.35 mol) of ε-caprolactone was added to 4.4 ml (40 m
mol), 4.4 ml (40 mmol), 9.0 ml (81 mmol), 18.0 ml
(0.16 mol), 36.0 ml (0.32 mol) and 78.0 ml (0.70 mol
The solution was dropped from the dropping funnel in six times in l).
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 additions were completed in about 3 hours, and then the mixture was heated and stirred at 170 ° C. for 3 hours.

When the obtained compound was analyzed by proton NMR, the NMR spectrum shown in FIG. 1 was obtained, and it was confirmed that the obtained polyester was a polyester having an average of 1.85 allyl ester groups in one molecule. Further, the number average molecular weight by VPO (vapor pressure osmometry) analysis was 8,000.

Example 2 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 dried using molecular sieve 4A1 / 16. ) 0.20m with diallyl isophthalate
l (0.60 mmol) of tetrabutyl titanate was added.
After stirring at 170 ° C. for 30 minutes, the mixture was cooled to 100 ° C., and while maintaining this temperature, 100 ml (0.90 mol) of ε-caprolactone dried using molecular sieve 4A1 / 16 was added to 4.4 m
l (40 mmol), 4.6 ml (41 mmol), 9.0 ml (81 mmol), 18.
0ml (0.16mol), 36.0ml (0.32mol) and 28.0ml (0.25m
ol), and the mixture was dropped from the dropping funnel in order of six times.
At the time of each drop, after the end of the previous drop, the reaction mixture is analyzed at regular intervals by GPC (gel permeation chromatography), and after confirming that the dropped ε-caprolactone is almost consumed, the next drop is performed. Was performed. All drippings are completed in about 5 hours and then at 100 ° C for 5 hours.
The mixture was heated and stirred for hours.

When the obtained compound was analyzed by proton NMR, an NMR spectrum similar to that of FIG. 1 was obtained, and it was confirmed that the polyester was a polyester having an average of 1.83 allyl ester groups in one molecule. Further, the number average molecular weight by VPO analysis was 5,500.

Example 3 27.5 ml (125 mmol) of a stainless steel reaction vessel equipped with a stirring rod, a thermometer, a dropping funnel, a nitrogen blowing tube and a cooling tube was replaced with nitrogen gas, and dried using molecular sieve 4A1 / 16. 1.28m with diallyl isophthalate
l (3.75 mmol) of tetrabutyl titanate was added.
The mixture was stirred at 170 ° C. for 5 minutes, and subsequently dried with molecular sieve 4A1 / 16 while stirring at 170 ° C.
943 ml (8.5 mol) of ε-caprolactone was added to 11.0 ml (99 m
mol), 19.0 ml (171 mmol), 29.0 ml (262 mmol), 42.0 m
l (379 mmol), 64.0 ml (578 mmol), 95.0 ml (857 mmo
l), 144.0 ml (1.30 mol), 217.0 ml (1.96 mol) and 32
2.0 ml (2.91 mol) of the solution was divided into nine times, and was sequentially dropped from the dropping funnel. At the time of each dropping, the reaction mixture was analyzed by proton NMR at regular intervals after completion of the previous dropping, and after confirming that the dropped ε-caprolactone was almost consumed, the next dropping was performed. All the dropwise additions were completed in about 5 hours, and then the mixture was heated and stirred at 170 ° C. for 1 hour.

When the obtained compound was analyzed by proton NMR, an NMR spectrum similar to that of FIG. 1 was obtained, and it was confirmed that the polyester was a polyester having an average of 1.86 allyl ester groups in one molecule. Further, the number average molecular weight by VPO analysis was 8,800.

Comparative 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 dried using molecular sieve 4A1 / 16. ) 0.20m with diallyl isophthalate
l (0.60 mmol) of tetrabutyl titanate was added.
This was stirred at 170 ° C. for 30 minutes, then cooled to 100 ° C., and dried using Molecular Sieve 4A1 / 16, 100 ml (0.90 mol)
Of ε-caprolactone was added all at once. Then 170 ° C
For 2 hours.

When the obtained compound was analyzed by proton NMR, an NMR spectrum shown in FIG. 2 was obtained. In this spectrum, a peak of 4.5ppm which corresponds to H ₃ of FIG. 1 is hardly observed, the allyl groups attached to the terminus of the polycaprolactone chains scarcely present was confirmed. Also, from the ratio of the integrated value of the peak of 4.8 ppm due to the methylene proton of the allyl group of the diallyl isophthalate and the peak of 7.4 to 8.7 ppm due to the aromatic proton, the ester bond of the diallyl isophthalate shows that Almost no exchange reaction (insertion reaction of polycaprolactone chain) was performed, and it was confirmed that the obtained product was a mixture of polycaprolactone 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, and FIG. 2 is an NMR spectrum of a compound obtained in a comparative example.

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

Claims (4)

(57) [Claims] (1) General formula (Wherein, R represents a divalent organic group having 1 to 20 carbon atoms, and n represents an integer of 0 or 1 to 5). To produce an olefin-terminated polyester having a molecular weight of 5,000 to 50,000, the amount of unreacted lactone present in the reaction system is reduced by the ester bond of the olefin-terminated diester compound and the olefin-terminated diester compound. A lactone is sequentially added so as not to exceed a molar equivalent of 10 times the ester bond of the polylactone chain already inserted into the lactone. 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 the catalyst having transesterification ability is tetrabutyl titanate and / or tetraisopropyl titanate.