JPS63225653A - Beta-memthyl-delta-valerolactone polymer composition having improved thermal stability - Google Patents

Abstract

PURPOSE:To provide the title compsn. having excellent thermal stability, by blending a beta-methyl-delta-valerolactone polymer with an org. carbodiimide compd. CONSTITUTION:beta-Methyl-delta-valerolactone (i) and optionally, not more than 50mol.% of a copolymerizable monomer (ii) are subjected to a ring opening polymn. reaction in the presence of a catalyst (e.g., n-butyllithium) and a polymn. initiator which is an org. compd. having active hydrogen, pref. amino group and/or hydroxyl group (e.g., ethylene glycol) to obtain a beta-methyl-delta-valerolactone polymer (a). The component (a) is blended with 0.01-5wt.%, pref. 0.05-1.0wt.% [based on the amount of the component (a)] org. carbodiimide (b) of formula I (wherein R1 and R2 are each a 1-18C hydrocarbon group; A and B are each a group of formula II or III; R3 and R4 are each H or R1; R5 is R1; n is 1 or greater, pref. 1-10) (e.g., dicyclohexylcarbodiimide) and optionally, additives (c) such as an ultraviolet absorber, an antioxidant, etc.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a β-methyl-δ-valerolactone polymer composition (hereinafter referred to as β-methyl-δ-valerolactone polyester) with improved thermal stability. (Sometimes called polyol.) Polymers containing β-methyl-δ-valerolactone are liquid polyesters and are not only easy to handle, but also useful for imparting amorphous properties to crystalline polymers. In general, polyester diols obtained by using β-methyl-δ-valerolactone with diamines or diols as initiators are useful as soft segments for polyurethanes, and in this case, they have higher durability than conventionally known polyester polyurethanes. It has excellent properties such as hydrolyzability and high mold resistance.

[Conventional technology]

The lactone ring-opening polymer is converted from the terminal to the original seven polymers by heating.
It is known that it decomposes into

This decomposition temperature strongly depends on the type of lactone; for example, ξ-caprolactone polymer shows a decomposition temperature as high as 250°C or higher, and for this reason, in the case of boy + g-caprolactone, the heat resistance is critical in practical use. This is not a serious problem. -cn2cucn2c obtained by ring-opening polymerization of β-methyl-δ-valerolactone using glycol as an initiator.
It is known that the thermal stability of polymers having n2on groups is extremely low (Japanese Unexamined Patent Publication No. 60-248727), but the thermal stability of such β-methyl-δ-valerolactone-based polyester polyols is Previously, attempts to improve this were completely unknown.

[Problem that the invention seeks to solve]

As described in JP-A-60-248727, β-methyl-δ-valerolactone polyester polyol is heated to liberate β-methyl-δ-valerolactone from its terminal ends.

Therefore, when used in plasticizers such as vinyl chloride, monomer bleed and odor become a problem, and even if melt polymerization is attempted with incyanate compounds when producing polyurethane, the 7-mer is liberated. Changes in molecular weight cause serious problems such as the inability to increase viscosity. β−
In order to fully utilize the features of the methyl-δ-valerolactone polyester polyol, such as high hydrolysis resistance, its use must be improved unless the thermal stability of the diol is increased and the dissociation of the monomer due to heating is suppressed. The current situation is that it has no choice but to become extremely limited.

Generally, various compounds have been developed as heat resistance improvers for polyester, and organic phosphorus compounds, epoxy compounds, amine compounds, and phenolic compounds are usually added.

However, these compounds either have no effect at all on improving the thermal stability of β-methyl-δ-valerolactone-based polyester polyols, or on the contrary, they have problems such as drastically lowering the thermal stability, and the above-mentioned problems cannot be solved. Can not do it.

The object of the present invention is to provide β-methyl-δ-
An object of the present invention is to provide a valerolactone-based polymer composition.

[Means for solving problems]

The present inventors have conducted extensive studies on β-methyl-δ-valerolactone polymer compositions that have increased thermal stability and suppressed monomer dissociation due to heat. As a result, only systems to which an organic carbodiimide compound was added showed remarkable thermal stability. The present inventors have discovered that it is possible to obtain a β-methyl-δ-valerolactone polymer with improved properties and suppressed dissociation of monomers due to heat, and have completed the present invention.

That is, in the present invention, the organic carbodiimide compound is added to the β-methyl-δ-valerolactone polymer in an amount of 0.01 to 5
% by weight of a stabilized β-methyl-δ-valerolactone polymer composition.

The β-methyl-δ-valerolactone polymer used in the present invention can be produced by a conventionally known method for producing a lactone polymer. It can be obtained by ring-opening polymerization of -methyl-δ-valerolactone in the presence of a catalyst.

As catalysts, known lithium, sodium, n-butyllithium, sulfuric acid, phosphoric acid, BFa-(Oozes
) □ etc. are used in an amount of 0.01 to 10 mol % based on the initiator.

As the initiator, an organic compound having one or more active hydrogens in an amino group or a hydroxyl group is preferably used. These may be low molecular weight compounds or high molecular weight compounds. Specific examples include monoalcohols having 1 to 18 carbon atoms such as methanol, ethanol, butanol, 2-ethyl alcohol, 2,7-octanediol, lauryl alcohol, cyclohexanol, benzyl alcohol, ethylene glycol, 1,2 -propanediol,
2-methyl-1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-
1,8-octanediol, 1,9-nonanediol,
1. Polymers having 2 to 22 carbon atoms, such as 10-decanediol, 3-methyl-1°5-bentanediol, neopentyl glycol, naphthalene diol, diethylene glycol, tetraethylene glycol, glycerin, trimethylolpropane, and triethanolamine. polyoxyalkylene glycols whose fullkylene group is alkylene with 2 to 12 carbon atoms or cycloalkylene with 4 to 10 carbon atoms, such as polyoxyethylene glycol or polyoxypropylene glycol with an average molecular weight of 200 to 2000; , butylamine, 2-ethylhexylamine, laurylamine, diethylamine, dibutylamine, morpholine and other monoamines of carbon LHI ~ 18, ethylenediamine, 1,4-butanediamine, 1.
Examples include polyamines having 2 to 12 carbon atoms, such as 6-hexanediamine, P-phenylenediamine, and piperazine.

Even if the polymer applicable to the present invention is polymerized with β-methyl-δ-vareplactone alone using an initiator, it can be copolymerized with about 50 mol% or less of other copolymerizable lactones. It may also be something that has been done.

Specific examples of the copolymerizable monomer include δ-valerolactone, ε-caprolactone, formaldehyde, and ethylene oxide.

There is no particular restriction on the average molecular weight of the polymer, but it is preferably in the range of 300 to 20,000.

The polymerization reaction is carried out in the presence of a catalyst, but depending on the type and amount of catalyst, the hydrolysis resistance and storage stability of the polymer may be deteriorated, so the catalyst is usually removed as much as possible by known methods such as washing with water. (It is desirable.

Since the ring-opening polymer of β-methyl-δ-valerolactone has low thermal stability, it is desirable to remove the solvent and unreacted additives by shortening the heating time.

In the present invention, it is essential to add an organic carbodiimide compound in an amount of 0.01 to 5 weight percent to the β-methyl-δ-valerolactone polymer obtained by the above method. When the amount of organic carbodiimide added is 0.01% by weight, almost no improvement in thermal stability is observed. On the other hand, if more than 5% by weight is used, it not only does not have a great effect compared to when it is less than 5% by weight, but also has a negative effect on the resin obtained using β-methyl-δ-valerolactone polymer. On the other hand, it is not preferable because it causes a plasticizing effect and changes the physical properties.The most preferable addition amount is 0.05 to 1.0 weight liter<-cent.

The organic carbodiimide compound used in the present invention has the general formula A -Rt +N-0=N-31129B (wherein B1 and B2 are the same or different hydrocarbon groups having 1 to 18 carbon atoms, and M and B are respectively H and NHCONRs
14, -NHCOOBs. B3, B
4 is fl or a hydrocarbon group having 1 to 18 carbon atoms, and B
5 represents a hydrocarbon group having 1 to 18 carbon atoms. Also, n is 1
or more, preferably an integer of 1 or more and 10 or less]. These organic carbodiimide compounds can be easily synthesized by reacting an incyanate compound with a phosphoryl compound as a catalyst by a known method (T, W, Oampbell).

et, al,, J, mer, Ohem, 8oc,
, 84, 3673 (1962)).

Specific examples of the organic carbodiimide compounds used in the present invention include dicyclohexylcarbodiimide, diphenylcarbodiimide, di-p-tolylcarbodiimide, di-p-nitodiphenylcarbodiimide, di-2-methyl-4-nitrophenylcarbodiimide, bis -2,6-
Carbodiimide polymers containing the structure of diimbrobyl-4-hydroxyphenylcarbodiimide, bis-2,6-diitubrobylcyclohexylcarposi, etc.
Ru. Among them, dicyclohexylcarbodiimide is suitable for improving the thermal stability of β-methyl-δ-valerolactone polymers.

In the present invention, it is particularly preferable to add the organic carbodiimide compound to the β-methyl-δ-valerolactone polymer after the hexamer is removed, or after the polymerization reaction.
If water is used to remove the catalyst, it may be used immediately after the water has been completely distilled off, or even before or during the distillation of unreacted β-methyl-δ-valerolactone. An important person.

The polymer obtained by adding an organic carbodiimide compound to a β-methyl-δ-valerolactone polymer is preferably stirred sufficiently so that it is uniformly mixed.

In addition to the organic carbodiimide compound of the present invention, conventionally known additives such as ultraviolet absorbers and antioxidants may be appropriately added to the β-methyl-δ-valerolactone polymer of the present invention.

The β-δ-valerolactone polymer composition of the present invention has improved thermal stability and can be used as a plasticizer such as vinyl chloride or as a raw material for polyurethane produced by melt polymerization.
It is possible to apply it to a wide range of uses by taking advantage of its excellent properties such as high hydrolysis resistance.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

〔Example〕

Synthesis Example 1 15 fl of anhydrous ethylene glycol and 571 g of anhydrous β-methyl-a-valerolactone were charged into a 1 g three-neck flask equipped with a thermometer, a dropping funnel, and a stirring device, and the mixture was stirred under a nitrogen atmosphere. n-BuLi
Hexane solution (concentration 1.5 molez4) 1.0
mj was added dropwise. The reaction was carried out for 2 hours at a reaction temperature of 60°C. The obtained polymerization liquid was dissolved in toluene 600-
Wash twice with 300 ynJ of water each time. Toluene was distilled off from the toluene layer using a rotary evaporator.

The polymerization solution containing unreacted 7-mer was treated under a reduced pressure of 140 DEG C. and 3 Torr using a wiper-equipped thin film evaporator to distill off 7-mer.

The physical properties of the obtained β-methyl-δ-valerolactone polyester diol were as follows. Average molecular weight 20
40, acid value o, 15, β-methyl-δ-valerolactone monomer 0.2w1%, moisture 0.02wt%, viscosity measured by E-type viscometer 20.6 Bois (40″C).

Comparative Example 1 30 g of the β-methyl-δ-valerolactone polyester diol obtained in Synthesis Example 1 was placed in a pressure-resistant glass container, sealed, and heated at 200° C. for 1 hour. After cooling, the polymer was analyzed by liquid chromatography, and the amount of β-methyl-δ-L/R5 lactone monomer was 54 wt%.
The average molecular weight of the polymer analyzed by gel permeation chromatography was 950. Furthermore, analysis of the terminal group structure of this polymer by nuclear magnetic resonance spectroscopy revealed that all the terminal groups were polyester diols that maintained hydroxyl groups.

Further, the β-methyl-δ-valerolactone polyester diol was heated at 110° C. for 4 hours in a sealed tube.

After cooling, the viscosity at 40° C. was measured using an E-type viscometer to determine the rate of viscosity change. The results are shown in Table 1.

Example 1 0.05 wt % of dicyclohexylcarbodiimide was added to β-methyl-δ-valerolactone polyester diol 509 obtained in Synthesis Example 1 and uniformly dissolved. 30 g of this polymer was heated in the same manner as in Comparative Example 1 at 200° C. for 1 hour. After cooling, the polymer was analyzed by liquid chromatography and the amount of β-methyl-δ-valerolactone monomer was 3.0 yt%, and the average molecular weight of the polymer analyzed by gel permeation coomadography was 2010. Met. Furthermore, as a result of analyzing the terminal group structure of this polymer by nuclear magnetic resonance spectroscopy, all terminal groups remained as hydroxyl groups.

Examples 2 to 4 and Comparative Examples 2 to 9 A predetermined amount of the organic carbodiimide compound shown in Table 1 was added to each 20 g of the β-methyl-δ-varep lactone polyester diol obtained in Synthesis Example 1, and the mixture was heated at 110 g in a sealed tube. Heated at <0>C for 4 hours. After cooling, use an E-type viscometer to 40°C.
The viscosity was measured and the viscosity change rate was determined. The results are shown in Table 1.

Example 5 In the same reactor as in Example 1, 14.75 Q 1 ε-caprolactone and 2 β-methyl-δ-valerolactone were added to the same reactor as in Example 1.
53g was charged, and while stirring under a nitrogen atmosphere,
BuLi hexane solution (concentration 1.5 mole/1
>0.5 ml was added dropwise. 2 at a reaction temperature of 60°C
Allowed time to react. The obtained polymerization liquid was added with 500 mJ of toluene.
and washed twice using 200 rrLl of water each time at room temperature. Toluene was distilled off from the toluene layer using a rotary evaporator. 0.2wt96 of dicyclohexylcarbodiimide was added to the polymerization solution containing unreacted supernatant and undistilled toluene. This polymerization solution was treated at 150° C. under reduced pressure of 5 Torr using a wiper-equipped thin film evaporator to distill off unreacted monomers and undistilled toluene.

The obtained polymer has an average molecular weight of β-methyl-
It was a polyester diol containing δ-valerolactone monomer 〇, 15 wt 5% and an acid value of 0.05.

20 g of this polymer was charged into a sealed tube in the same manner as in Example 1 and heat-treated at 200° C. for 1 hour. The treated polymer was a polyester diol with an average molecular weight of 1990, β-methyl-δ-°valerolactone monomer 2.1% by weight, and an oxidation rate of 0.05.

Comparative Example 10 A copolymer was synthesized in Example 5 without adding dicyclohexylcarbodiimide. The obtained polymer was a polyester diol having an average molecular weight of 1985, a β-methyl-δ-valerolactone monomer content of 0.2 wt%, and an acid value of 0.12.

20 g of this polymer was charged into a sealed tube in the same manner as in Example 1 and heat-treated at 200° C. for 1 hour. The treated polymer was a polyester diol with an average molecular weight of 1,100·, 4.5 wt % of β-methyl-δ-valerolactone monomer, and an acid value of 0.12.

Reference Example β-Methyl- with an average molecular weight of 2040 obtained in Synthesis Example 1
δ-valerolactone polyester diol (1'MV
L), dicyclohexylcarbodiimide 0.4w to this
Polyurethane was synthesized from PFilVL and volicaprolactone (average molecular ff 12300, acid value 0.21), and the hydrolysis resistance was compared. The polyurethane was synthesized by reacting polyester diol/1°4-butanediol/4.4'-diphenylmethane diisocyanate in a molar ratio of 1/2/3 in dimethylformamide at 70°C. The polyurethane concentration in the solution was 25w196. A dry film with a thickness of 100 μm was obtained using this solution. This film was heated to 100℃.
After being left in water for 12 days, the films before and after the test were dissolved in dimethylformamide and changes in viscosity were measured. As a result, the viscosity retention rate (viscosity after test/viscosity before test x100) of polyurethane made from l'MVL obtained in Synthesis Example 1 was 8996, and the
P made by adding dicyclohexylcarbodiimide to VL
The viscosity retention rate of polyurethane made from MVL is 8996
Met. Further, the viscosity retention rate of polyurethane made from polycabulactone was 2,096. Like this P
MVL was found to have inherently higher hydrolytic resistance than conventional polycaprolactone systems (related to the addition of carbodiimide).

〔Effect of the invention〕

Dissociation of the β-methyl-δ-valerolactone monomer from the β-methyl-δ-valerolactone polymer was suppressed, and the thermal stability of the polymer was highly improved.

Claims (7)

[Claims] (1) A stabilized β-methyl-δ-valerolactone polymer composition obtained by adding 0.01 to 5% by weight of an organic carbodiimide compound to a β-methyl-δ-valerolactone polymer. (2) A patent claim in which the β-methyl-δ-valerolactone polymer is obtained by ring-opening polymerization of mainly β-methyl-δ-valerolactone using an organic compound having active hydrogen as an initiator. The composition according to item 1. (3) The composition according to claim 2, wherein the initiator is an organic compound having an amino group and/or a hydroxyl group. (4) The organic carbodiimide compound has the general formula A-R_1
-(N=C=N-R_2)-_nB (wherein R_1
and R_2 are the same or different hydrocarbon groups having 1 to 18 carbon atoms, and A and B are each H, -NHCOR_3R
Represents either _4 or -NHCOOR_5. R
_3 and R_4 are H or a hydrocarbon group having 1 to 18 carbon atoms, and R_5 is a hydrocarbon group having 1 to 18 carbon atoms. n represents an integer of 1 or more. ) The composition according to claims 1 to 3, which is a compound represented by: (5) The composition according to claim 4, wherein n is an integer of 1 or more and 10 or less. (6) The composition according to claim 5, wherein the organic carbodiimide compound is dicyclohexylcarbodiimide. (7) The amount of organic carbodiimide compound added is 0.05~
A composition according to claims 1 to 6, wherein the content is 1.0% by weight.