JPH06248060A - Production of lactone polymer - Google Patents

Abstract

PURPOSE:To obtain the subject polymer useful for molded article, film, etc., having excellent hue and thermal stability by using a complex catalyst comprising a metal compound and a ligand. CONSTITUTION:A lactone monomer such as epsilon-caprolactone is polymerized in the presence of a complex catalyst comprising a metal compound such as monobutyltin triacetate and a ligand such as hexamethylphosphoric triamide preferably by using a polyhydric alcohol such as ethylene glycol to give the objective polymer as an initiator.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a lactone polymer using a specific composite catalyst. For more details,
The present invention relates to a production method for rapidly obtaining a lactone polymer in a short time by using a composite catalyst composed of an organic metal and a Lewis base.

Lactone polymers are widely used in many industrial fields due to differences in their average molecular weight and functional groups. For example, the molecular weight of glycol is 500
Lactone polymers of up to 5000 are very useful as raw materials for polyurethanes and paints, and lactone polymers having radically polymerizable double bonds are used as acrylic coating materials in fields such as automobiles and home appliances. . Lactone polymers having a molecular weight of more than 10,000 have practical mechanical strength and are used in plastic molded products, films, hot melt adhesives and the like.

[0003]

BACKGROUND OF THE INVENTION A large number of catalysts used to obtain lactone polymers are known, but typical ones are alkali metal compounds (Japanese Patent Publication No. 40-26557, USP).
atent 3,021,314), alkaline earth metal compounds (US P
atent 3,021,310; 3,021,311), aluminum compounds (Japanese Patent Publication No. 43-2473), inorganic acids (Japanese Patent Publication No. 35-497), titanium compounds such as tetrabutyl titanate and tin compounds (Japanese Patent Publication No. 41-19559; Japanese Patent Publication No. Sho 64-19559). 1491) and the like. Among these, alkali metal compounds, alkaline earth metal compounds, aluminum compounds, etc. all have problems in stability and handling safety such as immediate ignition or decomposition when they come into contact with oxygen or moisture. is there. Also, the amount of catalyst used to obtain the lactone polymer is relatively large and often adversely affects the hue and thermal stability.

Inorganic acids have a problem that the lactone polymerization rate is slow and a high-molecular lactone polymer cannot be obtained. On the other hand, titanium compounds such as tetrabutyl titanate and tin compounds such as dibutyl tin laurate, dibutyl tin oxide and stannous octylate and metal compounds such as chromium molybdenum, tungsten, antimony, zirconium and lanthanoids are easy to handle, and lactone It has sufficient solubility in the monomer and toxicity is not a problem.

[0005]

However, when only these metal compounds are used as a catalyst, the lactone polymerization rate is relatively slow, and further the hue and thermal stability of the obtained lactone polymer cannot be sufficiently satisfied. However, it was often found that the molecular weight distribution was too wide to be applied to industrial applications.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have used a composite catalyst composed of a specific metal compound and a ligand when producing a lactone polymer. Then, it was found that a lactone polymer excellent in hue and thermal stability can be stably obtained at a very high polymerization rate, and the present invention has been completed.

That is, the present invention provides a method for producing a lactone polymer characterized by using a composite catalyst comprising a metal compound such as a tin compound and a ligand.

Examples of the metal compound in the present invention include organic metal compounds, metal halides, metal oxides and metal hydroxides.

The metal element is not particularly limited,
Metal elements belonging to IIIA, IVA, VIA, and IV of the periodic table are preferred, among which tin, titanium, molybdenum,
Tungsten and lanthanoids are the most preferable, and tin can be exemplified by a large number of compounds.

The tin compound in the present invention is represented by the formula [1],
[2] and [3] , R is optionally selected from hydrogen, alkyl groups and aryl groups.

Y ¹ to Y ^{4 in the} formulas [1] to [3] may be the same or different, and the formulas [1] to
The tin compound [3] is used alone or as a mixture of two or more kinds. R- in formulas [1] to [3] is hydrogen,
It is arbitrarily selected from an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 30 carbon atoms.

Specifically, hydrogen, methyl group, ethyl group, n
-Propyl group, iso-propyl group, n-butyl group, iso
-Butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-peptyl group, n-octyl group, n-nonyl group, n-denyl group, n-dodenyl group Group, n-undenyl group, cyclopentyl group, cyclohexyl group, benzyl group, cyclohexylmethyl group, methoxymethyl group, methoxyethyl group, ethoxyethyl group, butoxymethyl group, phenyl group, biphenyl group, alkyl group-substituted phenyl group and amber acid,
Examples thereof include an alkenyl group having an ester group or a carboxyl group, an alkylene group, and a phenyl group, which are introduced from a dibasic acid such as maleic acid or phthalic acid.

As the halogen in the formulas [1] to [3],
Included are chlorine, bromine, fluorine and iodine, with chlorine being the most common.

Specific examples of the tin compound belonging to the formula [1] include dibutyltin oxide, dimethyltin oxide, monobutyltin oxide hydroxide, monomethyltin oxide hydroxide, monobutyltin oxide chloride, monobutyltin oxide methoxide, and tin oxide dioctylate. , Monooctyl tin oxide hydroxide, monobutyl monooctyl acid tin oxide, monobutyl monoacetic acid tin oxide, monobutyl monoheptanoic acid tin oxide, and the like.

Specific examples of the tin compound belonging to the formula [2] include dibutyltin dichloride, dimethyltin cyclolide, stannic chloride, dibutyldi (monobutylmaleic acid) tin, dibutyldi (monomethylmaleic acid) tin,
Dimethyl di (monobutyl maleate) tin, dibutyl di (monobutyl succinate) tin, dibutyl tin dioctylate, monobutyl tributyrate, tin monobutyl triacetate, tributyl tin chloride, dibutyl dimethacrylate tin, di (monobutyl maleate) dichloride , Dioctyl tin dichloride, trioctyl chloride, and the like.

Specific examples of the tin compound belonging to the formula [3] include tin dioctylate, tin dilaurate, stannous chloride, stannous bromide, stannous iodide and monobutyltin chloride. In the tin compound of the present invention, the formulas [1] to [3] show the structure of the monomer tin compound, but there is no problem even if a dimer tin compound or a polymer tin compound is contained separately.

Specific examples of the metal compound other than tin in the present invention include tetra-n-butyl titanate and tetra-n-butyl titanate.
Propyl titanate, tetraethanol titanate, diammonium titanium dioxide disoxalate, titanium dipotassium hexafluoride, titanium diammonium hexafluoride, molybdenum diacetate dioxide, molybdenum acetylacetonate, phosphotungstic acid, zirconium diacetate oxide and lanthanum diacetate oxide, etc., There are many.

The ligand in the present invention is a compound that can donate an electron pair (lawn pair) to a metal compound to form a composite catalyst by coordination bond. Although not particularly limited,
Compounds composed of elements belonging to VB and VIB in the periodic table are common.

Specific examples will be given below. As the nitrogen-based ligand, ammonia, ethylenediamine, pyridine, triethylamine, diazabicycloundecene, azobisisobutyronitrile, triethylenediamine, 2,2'-
Bipyridine, N, N, N ′, N′-tetramethylethylenediamine, phosphorus ligands such as trimethylphosphine, tributylphosphine, triphenylphosphine, trimethoxyphosphine, triphenoxyphosphine, triphenylphosphine oxide, trimethylphosphine oxide , Tri (dimethylamino) phosphine, hexamethylphosphoric triamide, BINAP, DIOP, CHIRAPHOS
Examples of asymmetric phosphorus ligands and oxygen-based ligands abbreviated as
Carbon monoxide, acetone, acetylacetone, benzoquinone, crown ether, others, cyclopentadienyl, cyclooctadiene, benzene, pentamethylcyclopentadienyl, triphenylarsenic, triphenylarsenic oxide, tributylarsenic, triphenylantimony, tri Phenyl antimony oxide, diphenyl sulfide, diphenyl sulfoxide, diphenyl selenium,
Diphenyl diselenide etc. are mentioned.

The coordination number of the ligand with respect to the metal compound and the method for producing the composite catalyst by coordinating the ligand with the metal compound are not particularly limited. The molar ratio of the metal compound to the ligand is usually preferably in the range of 1: 0.1 to 1: 8, and it is preferable to set and use the molar ratio with the strongest activity.

In the method for producing the composite catalyst, various production conditions such as temperature, pressure, gas atmosphere, addition method, addition order and the like can be selected depending on the nature of the ligand of the metal compound. For example, when using monobutyltin oxide hydroxide and triphenylphosphine oxide,
The present invention can be achieved only by dissolving each equimolar mixture in the lactone monomer at room temperature.

The composite catalyst comprising a metal compound and a ligand according to the present invention has no problems in stability, solubility in lactone monomer, low toxicity and the like, and may be used alone or in consideration of the activity of the composite catalyst. It can be used as a mixture of two or more kinds.

The lactone polymer in the present invention means a group of compounds produced by the ring-opening addition reaction of one or more molecules of the lactone monomer or 50% by weight of these compounds.
It is a mixture containing the above. Specifically, a viscous liquid obtained by ring-opening addition polymerization of a lactone monomer using a polyhydric alcohol or a polymer having a hydroxyl group in the molecule as an initiator, a waxy solid, an oligomer or polymer such as plastic, and hydroxyethyl. Examples thereof include a monomer having a radical-polymerizable double bond produced by a ring-opening addition reaction of a methacrylate and a lactone monomer.

Examples of the lactone monomer here include δ-valerolactone, ε-caprolactone, enanthlactone (7-hydroxyheptanoic acid lactone), 8-hydroxyoctanoic acid lactone, 12-hydroxydodecanoic acid lactone and 13-hydroxy. Lactic acid tridecanoate, 14
-Hydroxytetradecanoic acid lactone, 15-hydroxypentadecanoic acid lactone and alkyl and alkoxy derivatives of these lactones. 3 more
-Ethyl-2-keto-1,4-dioxane, 1,4-dioxan-2-one, 3-propyl-2-keto-1,4
-Dioxanes such as dioxane also apply. These lactone monomers are used alone or as a mixture of two or more kinds.

Of these lactone monomers, ε-caprolactone, methylated ε-caprolactone, δ-valerolactone, 3-ethyl-2-keto-1,4-dioxane and the like, which have the greatest practical value, are preferably used. To be

The active hydrogen-containing initiator is a compound or polymer having a hydroxyl group, an amino group, a thiol group, a carboxyl group or the like in the molecule, and a polyhydric alcohol such as water, glycol, triol or tetraol, or radical polymerization. Examples thereof include alcohols having a functional group such as a polymerizable double bond, amines, and polymers having a hydroxyl group in the molecule. Specifically, water, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6- Hexamethylene diol, glycerin, pentaerythritol,
Methoxyethanol, monoacetylethylene glycol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-aminoethanol, 6-
Hydroxyhexanoic acid, allyl alcohol, 4-hydroxybutyl vinyl ether, 2-hydroxyethyl vinyl ether, polyethylene oxide, polypropylene oxide, polytetramethylene glycol, epoxy resin containing hydroxyl groups, polybutadiene containing hydroxyl groups and 2-hydroxyethyl. Examples thereof include polymers obtained by copolymerizing or grafting methacrylate.

The method for producing the lactone polymer in the present invention is not particularly limited, but in the presence of an initiator having active hydrogen, it is generally 80 to 230 ° C., preferably 100 to
At a temperature of 180 ° C, 0.1 to 1000 ppm, preferably 1 to 100 ppm of a composite catalyst consisting of a metal compound and a ligand is added,
A method in which a lactone monomer is subjected to ring-opening polymerization (addition) reaction is desirable.

When the reaction temperature is lower than 80 ° C., the reaction rate is slow, and when it is higher than 230 ° C., coloration due to the oxidation reaction or decomposition reaction of the resulting polymer is unfavorable. The reaction rate was slow even when the amount of the composite catalyst was less than 0.1 ppm.
When it exceeds 00 ppm, the hue and thermal stability of the resulting polymer are deteriorated, which is not preferable.

In the method for producing the lactone polymer of the present invention, any polymerization method such as bulk polymerization, solution polymerization and suspension polymerization can be used without any problem. As the organic solvent that can be used in the solution polymerization, aromatic hydrocarbons such as toluene and xylene are preferable because they are inert to the reaction and have a relatively high boiling point. The solvent is preferably substantially anhydrous.

The type of production apparatus in the method for producing the lactone polymer of the present invention is not particularly limited. For example, batch type, semi-continuous type and continuous type ordinary stirring type reactors and kneader type reactors can be used without problems. Also,
The pressure and gas atmosphere in the reaction system are not particularly limited. 0.
The reaction can be arbitrarily performed under the conditions of 01 Torr to 10 atmospheres, an inert gas such as nitrogen, and an atmosphere such as air.

In the method for producing the lactone polymer of the present invention, the method of adding the metal compound, the ligand, the lactone monomer, the initiator, the various stabilizers and the like, the addition order is not particularly limited, and any method can be used. It is possible to carry out the reactions in order.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 Example 1 A 1-liter flask equipped with a stirrer, a nitrogen introduction tube, a thermometer and a condenser was charged with ε-caprolactone (water content).
0.005%) 500 g, tin monobutyltriacetate 0.02 g as a metal compound, hexamethylphosphoric triamide 0.01 g as a ligand, and diethylene glycol 0.5 g as an initiator, while nitrogen is being included 160
Stirred at ° C.

After 4 hours, a white rigid crystalline polyester was obtained. Polystyrene-reduced number average molecular weight by gel permeation chromatography measurement of this product,
Molecular weight distribution (weight average molecular weight / number average molecular weight), time required for polymerization (reaction) rate to exceed 99%, and hue (APHA value of 30% solid content xylene solution: JIS K 155)
7) is summarized in Table 1.

EXAMPLE 2 400 g of ε-caprolactone (water content 0.005%) and δ-valerolactone (water content) were placed in a device similar to the device of Example 1.
0.010%) 100 g, stannous chloride 0.03 as metal compound
g, diazabicycloundecene 0.024 g as a ligand and ethylene glycol 0.3 g as an initiator,
The mixture was stirred at 160 ° C. while sprinkling nitrogen. After 6 hours, a transparent and very viscous polyester was obtained.

Example 3 500 g of ε-caprolactone (water content: 0.005%), 0.03 g of tetrabutyl titanate as a metal compound, 0.023 g of triphenylphosphine as a ligand and ethylene glycol as an initiator were placed in a device similar to that of Example 1. 16
g was charged, and the mixture was stirred at 140 ° C. while sprinkling nitrogen.

After 7 hours, a white waxy polyester was obtained.

Example 4 In a device similar to that of Example 1, 500 g of ε-caprolactone (water content 0.005%), 0.02 g of dibutyltin oxide as a metal compound, 0.022 g of triphenylphosphine oxide as a ligand and diethylene glycol as an initiator were used. Charge 58 g, and while rubbing nitrogen, 140
Stirred at ° C. After 8 hours, a white waxy polyester was obtained. The physical properties of those obtained in Examples 2, 3 and 4 were measured in the same manner as in Example 1, and the results are summarized in Table 1.

Comparative Examples 1 to 4 The same devices as those of Examples 1 to 4 were added to Example 1 respectively.
No addition of the ligand used in Examples 4 to 4 was carried out under the same conditions except that the lactone monomer, the metal compound and the initiator were charged in the same proportions as in Examples 1 to 4 except for the above. did. The time required for the polymerization rate to exceed 99% and the physical properties of the obtained product were measured in the same manner as in Examples 1 to 4, and the results are also shown in Table 1. The relationship between the reaction time and the polymerization rate in Example 1 and Comparative Example 1 is shown in FIG.

In Examples 1 to 4, when the reaction was carried out only with the ligand without using the metal compound, the polymerization hardly proceeded.

Example 5 300 g of ε-caprolactone (water content 0.005%), 342 g of 2-hydroxyethyl methacrylate, 3 g of hydroquinone monomethyl ether as a polymerization inhibitor, and monobutyltin hydroxide oxide as a metal compound were placed in a device similar to that of Example 1. 0.03 g and 0.04 g of triphenylphosphine oxide as a ligand were charged, and the mixture was stirred at 100 ° C while blowing air.

The polymerization rate of ε-caprolactone was measured by gas chromatography.
It exceeded 99%. This lactone-modified 2-hydroxyethyl methacrylate had a good APHA value (JIS K 1557) 10 and a hue, and when another monomer was copolymerized with this, a good acrylic polyol resin was obtained.

Comparative Example 5 ε-caprolactone was added to the same apparatus as in Example 1 without adding the triphenylphosphine oxide used in Example 5 and in the same proportion as in Example 5 except that. 2-Hydroxyethyl methacrylate, hydroquinone monomethyl ether and monobutyltin hydroxide oxide were charged and stirred under exactly the same conditions. This product has a reaction rate of ε-caprolactone of 99%.
It took 15 hours to exceed. APHA value (JI
SK 1557) was slightly colored with 50. The relationship between the reaction time and the reaction rate in Example 5 and Comparative Example 5 is shown in FIG. Incidentally, when the reaction was carried out only with triphenylphosphine oxide without using monobutyltin hydroxide oxide in Comparative Example 5, the reaction hardly proceeded.

[0044]

As shown in Table 1, FIG. 1 and FIG. 2, the rate of polymerization (ring-opening addition) of a lactone monomer by adding a ligand such as triphenylphosphine oxide to a tin compound or the like. It has been clarified that it has the effect of significantly speeding up

By adding a ligand, the hue and other physical properties of the obtained polyester were improved. (Margins below) Table 1 Examples / Comparative Examples / Polymerization time / List of physical properties Metal reaction Polymerization rate Number average molecular weight Hue * Compound temperature 99% hours Molecular weight distribution (APHA) * (° C) Example 1 A 160 4 116000 1.50 10 Example 2 B 160 6 102000 1.68 10 Example 3 C 140 7 2000 1.60 10 Example 4 D 140 8 1000 1.54 10 Comparative Example 1 A 160 8 111000 1.55 30 Comparative Example 2 B 160 10 98000 1.72 30 Comparative Example 3 C 140 13 2000 1.75 50 Comparative Example 4 D 140 25 1000 1.60 50 Note (1) Hue: NV30% xylene dye (2) Abbreviations for the catalysts used are shown below.

(3) The polymerization rate of 99% means the time required for the total rate to exceed 99%.

A: CH ₃ (CH ₂ ) ₃ Sn (OCOCH ₃ ) ₃ B: SnCl ₂ C: Ti [O (CH ₂ ) ₃ CH ₃ ] ₄ (4): In Examples 1 to 4, the ligand having the following structure was used.

Example 1: Example 2: The following chemical formula 1

[Chemical 1] Example 3: PPh ₃ Example 4: O = PPh ₃ (hereinafter referred to as margin)

[Brief description of drawings]

FIG. 1 is a graph showing a change with time of a polymerization rate in Example 1 and Comparative Example 1.

FIG. 2 is a graph showing the change over time in the reaction rate in Example 5 and Comparative Example 5.

[Explanation of symbols]

 None (the margin below)

Claims (5)

[Claims] 1. A method for producing a lactone polymer, which comprises using a composite catalyst comprising a metal compound and a ligand. 2. The metal compound is a tin compound.
A method for producing the lactone polymer described. 3. The method for producing a lactone polymer according to claim 1, wherein a polyhydric alcohol is used as an initiator. 4. The method for producing a lactone polymer according to claim 1, wherein a polymer having a hydroxyl group in the molecule is used as the initiator. 5. The method for producing a lactone polymer according to claim 1, wherein an alcohol having a double bond in the molecule is used as an initiator.