JP2001525432A - Preparation of polyesters and esters from compounds containing secondary hydroxyl groups - Google Patents

Abstract

  (57) [Summary] A method is described for producing polyesters from polyols containing secondary hydroxyl groups with high yields and improved esterification rates. The method comprises converting a polyol compound containing at least one secondary hydroxyl group into at least one C₁~ C_ThreeReacting with a polycarboxyl compound in the presence of an alkyltin compound. C₁~ C_ThreeAlkyl tin is the carboxylic acid C₁~ C_ThreeAlkyl tin salt, C ₁~ C_ThreeAlkylstanonic acid, oxidized C₁~ C_ThreeAlkyl tin, halogenated C₁~ C _ThreeSelected from alkyl tins and mixtures thereof. The invention also relates to the polyesters produced by the process, which can be used in moldings, fibers, coatings and adhesive formulations. The process of the invention can also be used for the production of esters from secondary alcohols. Thus, in another embodiment, the present invention provides a catalytically effective amount of at least one of the above C₁~ C_ThreeA method for producing an ester, comprising reacting a carboxyl compound with a secondary alcohol in the presence of an alkyltin catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to an improved process for the preparation of esters and polyesters from compounds having at least one secondary hydroxyl group. Esters and polyesters are prepared in high yield and improved esterification rate in the presence of at least one C ₁ -C ₃ alkyl tin catalyst.

BACKGROUND esters and polyesters of the invention may be prepared by direct esterification or ester exchange reaction. In direct esterification, a carboxylic acid is converted to an ester by reaction with an alcohol. Similarly, polyesters can be made by direct esterification between a dihydric or polyhydric alcohol and a dicarboxylic or polycarboxylic acid or anhydride. In the transesterification reaction, esters are produced by reacting monocarboxylic esters with monohydric alcohols, and polyesters are produced by reacting dicarboxylic or polycarboxylic esters with dihydric or polyhydric alcohols. Ester and polyester produced by either method are also useful for use in molded articles, fibers, coatings and adhesives.

[0003] Tin compounds have been used as esterification catalysts in both direct and transesterification reactions to produce esters and polyesters. For example, U.S. Pat. Nos. 2,720,507: 3,162,616;
Nos. 288 and 5,166,310 describe the preparation of polyesters in the presence of an organotin catalyst. Further, U.S. Pat. Nos. 3,345,333 and 3,716,523 describe the preparation of polyesters by a two-stage process using a tin catalyst to increase the efficiency of the process.

[0004] The 1,2-esters of esters of monocarboxylic acids for the production of polyol esters
US Pat. No. 5,498,751 describes the use of dialkyltin oxide and dialkyltin dichloride as catalysts for transesterification with 1,3-polyols. Although this patent teaches that the product is obtained in high yield and excellent purity, the process is limited to the transesterification of esters of monocarboxylic acids with 1,2- and 1,3-polyols. ing.

[0005] US Pat. No. 4,554,344 discloses a process for preparing a polyester from an aromatic dicarboxylic acid or a derivative thereof and a diol containing an adjacent hydroxyl group, at least one of which is a secondary hydroxyl group. . This patent teaches that polyesters made from aromatic dicarboxylic acids and diols containing adjacent hydroxyl groups having at least one secondary hydroxyl group typically have a relatively low molecular weight. Low molecular weight severely limits their usefulness in the production of molded articles, fibers, coatings and other shaped articles. According to this patent, the inherent viscosity and molecular weight of polyesters made from aromatic dicarboxylic acids and diols containing adjacent hydroxyl groups are greatly increased by using a tin catalyst. The tin catalyst contains both inorganic and organic tin compounds, with butylstannoic acid being particularly preferred.

[0006] In the production of esters and polyesters from mono-, di- or polyhydric alcohols in which one or more of the hydroxyl groups is a secondary hydroxyl group, the rate of esterification and transesterification is such that the hydroxyl groups of the alcohol are all secondary. It is known that it is much slower than it is a one hydroxyl group. Accordingly, there remains a need for efficiently producing polyesters from alcohols including at least one secondary alcohol. Such a process increases the rate of the reaction and therefore lowers the production costs. The present invention addresses such needs.

[0007] Summary Surprisingly the invention, when carried out in the presence of at least one C ₁ -C ₃ alkyl tin catalyst of the esterification process, high yield from a polyol containing at least one secondary hydroxyl group And that esters and polyesters can be produced with improved esterification rates.

Accordingly, the present invention relates to polyesters from polyols having secondary hydroxyl groups.
And an improved method of manufacturing the same. The method comprises at least one second hydroxy.
At least one polyol containing at least one sil group and at least one polycarboxyl
Compounds with at least one C₁~ C_ThreeThe reaction is performed in the presence of an alkyltin catalyst.
C₁~ C_ThreeAlkyl tin catalysts react with the carboxylic acid C₁~ C_ThreeAlkyl tin salt, C₁~ C _Three Alkylstanonic acid, oxidized C₁~ C_ThreeAlkyl tin, halogenated C₁~ C_ThreeAl
It is selected from kill tin and mixtures thereof.

In another embodiment, the invention relates to the reaction of at least one secondary alcohol with at least one carboxylic compound in the presence of at least one of the aforementioned C ₁ -C ₃ alkyltin catalysts. And a method for producing an ester from a secondary alcohol.

[0010] The method of the present invention can be used to produce linear high molecular weight polyesters useful for molding and fiber use. The polyesters made by the process of the present invention can also be used as precursors in making relatively low molecular weight carboxyl or hydroxyl functional polyesters. The carboxyl and hydroxyl functional polyesters may be linear or, optionally, branched by the addition of trifunctional or polyfunctional hydroxyl or carboxyl compounds. In another embodiment, the polyesters of the present invention are also useful in coatings and adhesives.

[0011] Other objects and advantages of the invention will be apparent from and will be apparent from the practice of the invention as discussed in the following detailed description. Neither the summary nor the detailed description of the present specification are mere examples, and the present invention is not limited thereto.

[0012] DETAILED DESCRIPTION OF THE INVENTION The present invention, C ₁ -C ₃ alkyl tin salt, C ₁ -C ₃ alkyl static non acid of the carboxylic acid, oxide C ₁ -C ₃ alkyl tin, a halogenated C ₁ -C ₃ alkyl tin, and selected mixtures thereof, in the presence of at least one C ₁ -C ₃ alkyl tin catalyst in a catalytically effective amount, and at least one polyol having at least one secondary hydroxyl group, at least The present invention relates to a method for producing a polyester, comprising reacting a polyester with one kind of polycarboxyl compound.

[0013] The polyol compound used in the method of the present invention contains at least one secondary hydroxyl group and preferably has about 2 to about 40, more preferably about 3 to 3 carbon atoms.
It is about 26. Suitable polyols include triols, for example, 1,2,3-
Trihydroxypropane (glycerol); 1,2,4-butanetriol; 1
, 2,6-trihydroxyhexane; and 1,3,5-cyclohexanetriol. Preferred polyols for use in the present invention have from about 3 to about 20 carbon atoms.
And preferably about 3 to about 8 diols. Suitable diols can be aliphatic, cycloaliphatic or aromatic, with or without unsaturation. Examples include 1,2-propanediol, 1,2-butanediol, 1,4-cyclohexanediol, 2,2,4,4-tetramethylcyclobutanediol, 2,2,2
Examples include, but are not limited to, 4-trimethyl-1,3-pentanediol or mixtures thereof. Particularly suitable diols are 2,2,4-trimethyl-1,3-pentadiol, 1,2-propanediol and 2,2,4,4
-Tetramethylcyclobutanediol.

[0014] Polyesters containing both the second polyol and the first polyol can also be produced by the method of the present invention. Polyols containing no secondary hydroxyl groups suitable for use in the present invention may be saturated or unsaturated, but have from about 2 to about 4 carbon atoms.
0 aliphatic, cycloaliphatic or aromatic polyols. Preferably, the polyol is a diol having about 2 to about 20, more preferably about 2 to about 12, and even more preferably about 2 to about 8 carbon atoms per molecule. Such diols include ethylene glycol, 1,4-butanediol, 1,3-butanediol, pentanediol, hexanediol, heptanediol, neopentyl glycol,
Non-limiting examples include, but are not limited to, nonanediol, decanediol, diethylene glycol, dipropylene glycol, cyclohexanedimethanol, 2-methyl-1,3-propanediol, and mixtures thereof. Preferred diols containing both primary hydroxyl groups include netopentyl glycol, ethylene glycol, cyclohexane dimethanol and mixtures thereof.

[0015] The polycarboxy compound can be aliphatic, cycloaliphatic or aromatic, with or without unsaturation. Also suitable are their anhydrides and lower, for example, C ₁ -C ₈ alkyl esters. Suitable aromatic polycarboxyl compounds can be derived from monocyclic, polycyclic and fused ring compounds. These carboxylic acid groups can be substituted directly on the aromatic ring or a part of the alkyl group substituted on the ring. Further, the aromatic ring may have one or more functional groups, for example,
It can be further substituted with halogen, amine, cyano, nitro, and alkyl, alkoxy and alkylthio groups having 1 to 20 carbon atoms. The aromatic polycarboxyl compound preferably has about 7 to about 20, more preferably about 8 to about 12 carbon atoms.
It is.

The aliphatic or cycloaliphatic polycarboxyl compounds can be derived from saturated, monounsaturated and polyunsaturated carboxylic acids. These acids may be straight or branched chain and may be substituted with one or more groups listed above as suitable for aromatic ring substitution. Aliphatic and cycloaliphatic carboxyl compounds preferably have about 2 to about 40 carbon atoms, more preferably about 3 to about 26 carbon atoms.

Examples of suitable polycarboxyl compounds include 1,2,4-benzenetricarboxylic anhydride (trimellitic anhydride); 1,2,4-benzenetricarboxylic acid (trimellitic acid); 3,5-cyclohexanetricarboxylic acid is exemplified. Preferred polycarboxyl compounds are dicarboxyl compounds. Examples of suitable dicarboxyl compounds include terephthalic acid, isophthalic acid, adipic acid, 1,4-cyclohexanedicarboxylic acid, dimethyl terephthalate, phthalic anhydride, maleic anhydride and mixtures thereof. Not limited. Particularly suitable dicarboxyl-containing compounds include terephthalic acid, isophthalic acid and adipic acid.

The molar ratio of polyol to polycarboxyl compound can vary over a wide range. Preferred molar ratios are from about 0.5 to about 1.5, more preferably from about 0.8 to about 1
. 2.

The C ₁ -C ₃ alkyltin catalyst used in the present invention has the formula (R) ₂ Sn (O ₂ C
_{^{R 1) 2, RSn (O}} 2 CR 1) may be a ₃ or _{(R) 2 Sn (O 2} CR 1) C 1 ~C 3 alkyl tin salt of a carboxylic acid represented by Y. The R groups may be the same or different and are alkyl groups having about 1 to about 3, preferably 1, carbon atoms. R ^{1 s} may be the same or different and are alkyl having about 1 to about 20 carbons, may be linear or branched, and may be substituted or unsubstituted. Preferably, R ¹ has about 1 to about 12, more preferably about 1 to about 8 carbon atoms. R ¹ can also be an aryl group such as phenyl or naphthyl, an alkaryl group such as tolyl or phenylethyl or a cycloalkyl group such as cyclohexyl. Preferred aryl, alkaryl and cycloalkyl groups have about 3 to about 14 carbon atoms. Y is halogen, preferably bromine or chlorine. Examples of suitable organotin salts of carboxylic acids include dimethyltin diacetate, diethyltin diacetate, dipropyltin diacetate, dimethyltin dilaurate, methyltin trilaurate, ethyltin trilaurate, propyltin trilaurate and mixtures thereof. However, the present invention is not limited to these.

C of the formula RSn (O) OH₁~ C_ThreeAlkylstannoic acids are also C₁~ C_ThreeAl
Can be used as kill tin catalyst. The R groups are as previously defined. Suitable C₁~ C _Three Examples of alkylstannic acids include methylstannic acid, propylstanonic acid,
Ethylstanonic acid and mixtures thereof, but are not limited thereto.
There is no.

C₁~ C_ThreeThe alkyltin catalyst also has the formula (R)_TwoOxidation of SnO C₁~ C_ThreeArchi
It can also be tin. R may be the same or different and are as defined above.
You. Suitable oxidation C₁~ C_ThreeExamples of alkyl tin include dimethyl tin oxide and die oxide
Chill tin, dipropyl tin oxide, methyl ethyl tin oxide, methyl propyl tin oxide, oxidation
Ethylpropyltin and mixtures thereof, but are not limited thereto.
There is no. Oxidized C preferably used in the process of the invention₁~ C_ThreeAlkyl tin is an acid
Dimethyltin hydride, dimethyltin dilaurate and methylstannoic acid. these
The oxide can be converted to a suitable halogenated C by a base such as ammonium hydroxide.₁~ C _Three Generated in situ by hydrolyzing the alkyl tin
Can be Suitable halogenated C₁~ C_ThreeThe alkyl tin will be described later.

C ₁ -C ₃ alkyltin catalysts useful in the process of the present invention also include those of the formula (R)
) _N Sn (X) _{3-n wherein} R may be the same or different and are as defined above: n is 1 or 2: X is a halide, preferably chloride or fluoride. include halogenated C ₁ -C ₃ alkyl tin. Examples of suitable halogenated C ₁ -C ₃ alkyl tin trifluoride methyl tin, di- dimethyl tin dichloride, diethyl tin chloride dichloride dipropyl tin, di- methylethyl tin chloride, ethylaluminum dichloride propyl tin, Two Examples include methylpropyltin chloride or mixtures thereof. A preferred C ₁ -C ₃ alkyl tin halide is dimethyltin dichloride. However, under some reaction conditions, the use of dichloride can generate hydrochloric acid.

The C ₁ -C ₃ alkyltin catalyst used in the process of the present invention comprises a catalytically effective amount of
Preferably, based on the weight of the reactants (C ₁ -C ₃ based on tin% alkyltin catalyst) from about 0.001 to about 3 wt%, more preferably from about 0.01 to about 1.0 wt%, most Preferably it is present in an amount ranging from about 0.05 to about 0.2% by weight.

The process of the present invention is performed under conditions sufficient to form the desired polyester. The temperature and pressure should be maintained such that the esterification water or transesterification alcohol is removed to provide maximum reaction rate and allow the reaction to proceed to completion.

The process of the present invention can be carried out as a melt of a polyol and a polycarboxyl compound under an inert or non-oxidizing atmosphere using normal polyester forming conditions of temperature, pressure and time. The reaction temperature depends on the desired properties of the reactants and the polyester. Preferably, the temperature is from about 160 to about 280 ° C, more preferably about 18
0 to about 250 ° C. Temperatures below about 150 ° C. are generally not sufficient to provide a sufficient reaction rate.

The pressure at which the reaction is carried out also depends on the nature of the reactants and the desired polyester. Generally, the pressure ranges from about 700 to about 1,500 mmHg. If a relatively high molecular weight polyester is desired, the reaction should be terminated at a relatively low pressure. Depending on the desired molecular weight, the reaction pressure can be from about 100 mmHg to about 10 mm
The range is less than Hg.

The method of the present invention can also be performed in a suitable solvent. Suitable solvents include, but are not limited to, aromatic hydrocarbons, ethers, sulfones, halogenated aromatic hydrocarbons, ketones, sulfolane, sulfoxides, and combinations thereof. Particularly suitable solvents include toluene, xylene, diphenyl ether, dimethyl sulfolane and combinations thereof. The solvent can be a solvent for the reactants, products or both. The solvent is about 4% based on the weight of the reactants.
0 to about 95%, preferably about 45 to about 90%, more preferably about 50 to about 90%
Available in quantity.

To control the molecular weight, monofunctional compounds can be incorporated into the reaction mixture. Suitable monofunctional reactants include benzoic acid, tert-butylbenzoic acid,
Examples include, but are not limited to, phenylbenzoic acid, stearic acid, tert-butylbenzoic acid, phenylbenzoic acid, stearic acid, tert-butylphenol, benzyl alcohol or combinations thereof. If you use
The monofunctional compound is present in an amount of about 0.01 to about 10%, preferably about 1 to about 8%, more preferably about 2 to about 5% by weight based on the total weight of the reactants.

The polyesters produced by the process of the present invention are relatively low molecular weight carboxyl or hydroxyl which can be linear or optionally branched by the addition of the aforementioned trifunctional or polyfunctional branching agents. It can be used as a precursor in the production of functional polyesters. It is particularly useful to add a branching agent to the reaction mixture if a relatively low molecular weight carboxyl or hydroxyl functional polyester is desired. Suitable branching agents include trifunctional or polyfunctional reactants. The trifunctional or multifunctional reactant can be hydroxyl, acid or anhydride functional. Particularly suitable trifunctional or polyfunctional reactants include, but are not limited to, trimellitic anhydride, trimethylolpropane, glycerin, triethylolpropane, and pentaerythritol and combinations thereof.

If polyfunctional compounds are desired, they may be present at about 0.
01 to about 10% by weight, preferably about 0.1 to about 7% by weight, more preferably about 0.1 to about 10% by weight.
It is used in an amount of 1 to about 5% by weight. These polyesters are useful in coatings and adhesives. Accordingly, the present invention also relates to materials such as metals, paper and paperboard, and synthetic polymers coated with one or more of the foregoing polyester compositions.

The above C₁~ C_ThreeAlkyl tin compounds are also simple esterifications and ester exchanges.
It can be used as a catalyst in exchange reactions. Thus, another embodiment of the present invention
A boxyl compound and a secondary alcohol in a catalytically effective amount of at least one C₁~ C _Three A process for producing an ester comprising reacting in the presence of an alkyltin catalyst.
Related.

The secondary alcohol used in the method of the present invention preferably has about 2 to about 40 carbon atoms. Preferred alcohols have about 3 to about 20, preferably about 3 to about 8 carbon atoms. Examples of suitable secondary alcohols include 2-propanol, 2-butanol, cyclohexanol and cyclohexylmethanol. The esters produced by the method of the present invention can include a mixture of a secondary alcohol and a primary alcohol that does not contain a secondary hydroxyl group.

Like the polycarboxyl compounds used in the production of polyesters, the carboxyl compounds used in the production of esters can be aliphatic, cycloaliphatic or aromatic, with or without unsaturation. Is also good. Also suitable are their anhydrides and lower, for example, C ₁ -C ₈ alkyl esters. Suitable aromatic carboxyl compounds can be derived from ring systems similar to the polycarboxyl compounds described above. The carboxylic acid group can be substituted directly on the aromatic ring or a part of the alkyl group substituted on the ring. In addition, the aromatic ring may have one or more functional groups, such as halogen, amino, cyano, nitro and C1-C20.
Can be further substituted with alkyl, alkoxy and alkylthio groups of
The aromatic carboxyl compound preferably has about 7 to about 20, more preferably about 8 to about 12 carbon atoms.

[0034] Aliphatic and cycloaliphatic carboxyl compounds can be derived from saturated, monounsaturated and polyunsaturated carboxylic acids. These acids may be straight or branched chain and may be substituted with one or more of the groups listed above as suitable for aromatic ring substitution. Aliphatic and cycloaliphatic carboxyl compounds preferably have about 2 to about 40 carbon atoms, more preferably about 3 to about 26 carbon atoms.

Propionic acid, butyric acid, cyclohexanecarboxylic acid and benzoic acid are particularly preferred carboxylic compounds useful in the simple esterification and transesterification methods of the present invention. Preferred C ₁ -C ₃ alkyltin catalysts for this esterification are the same as those described above. The molar ratio between the secondary alcohol and the carboxyl compound can be varied over a wide range, with a molar ratio of 1: 1 being particularly preferred. However, in some cases it may be advantageous to include an excess of secondary alcohol. As with the polyester-forming reaction, this reaction can be carried out in a melt or solution.

[0036] disclosed in the following examples the way of example the present invention, but they should not be construed as limiting the present invention. All reactions were performed in 2-liter flasks equipped with thermocouples, automatic stirrers, and oil-heated partial condensers connected to water-cooled condensers for collection and esterification water weighing. The reactor is equipped with a C
Computer controlled by AMILLE ™ automatic data collection and control software. All variables, for example, the upper heating rate
, Column temperature, reaction temperature, and stirring speed were the same. For each example, three identical polyesters were produced simultaneously. Each contained a different organotin compound as a catalyst. The reaction rate was measured by monitoring the acid number of the reaction mixture until the desired degree of reactivity was achieved. First order rate constants for Example 1 were obtained from a plot regression analysis of the natural log (Ln [acid]) of acid concentration versus time.

Example 1 The following reactants were charged to three 2 liter flasks. Grams moles 2,2,4-trimethyl-1,3-447.5 3.06 propanediol (TMPD) trimethylolpropane (TMP) 19.5 0.22 isophthalic acid (IPA) 182 1.1 adipic acid (AD 160) Organotin catalyst 0.05% by weight of total charge (based on% Sn in organotin catalyst)

Three organotin catalysts were evaluated. Reaction flask organic tin catalyst gram % Sn 1 dibutyltin oxide 0.90 0.43 2 butylstannoic acid 0.75 0.43 3 dimethyltin oxide 0.60 0.43

The reaction mixture was heated to 150 ° C. at a constant rate of 2 ° C./min until all reactants had melted. The reaction mixture was then heated at a constant rate of 2 ° C./min to 215 ° C.
It was kept at the same temperature until an acid number of less than was obtained. The relative activity of the three organotin catalysts was determined by monitoring the acid number of the reaction mixture during the last 4 hours of the polyesterification. The acid number versus time results are shown in Table I and plotted in FIG.

[0040]

[Table 1]

For each catalyst to be evaluated, first order rate constants obtained by regression analysis of Ln [acid] versus time are shown in Table II and plotted in FIG.

[0042]

[Table 2]

From these results, dimethyltin oxide shows a two-fold increase in the esterification rate as compared to dibutyltin oxide, and a 50% increase in the reaction rate as compared to butylstannoic acid. It can be seen that the method has been significantly improved.

Example 2 The following reactants were charged to two 2 liter flasks. G mol of 1,2-propanediol 232.86 3.06 (propylene glycol, PG) trimethylolpropane (TMP) 19.5 0.22 isophthalic acid (IPA) 182 1.1 adipic acid (AD) 160 1.1 Organotin catalyst 0.05% by weight of total charge (based on% Sn in organotin catalyst)

Two organotin catalysts were evaluated. Reaction flask organic tin catalyst gram % Sn 1 butylstannic acid 0.75 0.43 2 dimethyltin oxide 0.60 0.43

The reaction mixture was heated to 150 ° C. at a constant rate of 2 ° C./min until all reactants had melted. The reaction mixture is then heated at a constant rate of 2 ° C./min to 190 ° C.
It was kept at the same temperature until an acid number of less than was obtained. The relative activity of the two organotin catalysts was determined by monitoring the acid number of the reaction mixture during the last 3 hours of the polyesterification. The acid number versus time results are shown in Table III and plotted in FIG.

[0047]

[Table 3]

For each catalyst to be evaluated, first order rate constants obtained by regression analysis of Ln [acid] versus time are shown in Table IV and plotted in FIG.

[0049]

[Table 4]

These results also indicate that the lower alkyl organotin oxide increased the rate by 50% with glycols containing secondary hydroxyl groups when compared to butylstannone chains,
Thus, it can be seen that the prior art method is significantly improved.

Comparative Example 1 The following reactants were charged to three 2-liter flasks. Gram mole neopentyl glycol (NPG) 654.67 6.2853 Trimethylolpropane (TMP) 93.52 0.697 Isophthalic acid (IPA) 519.95 3.130 Adipic acid (AD) 457.13 3.128 Organotin Catalyst 0.05% by weight of total charge (based on% Sn in organotin catalyst)

[0052] Three organotin catalysts were evaluated. Reaction flask Organotin catalyst gram % Sn 1 Dibutyltin oxide 1.79 0.86 2 Butylstanonic acid 1.50 0.86 3 Dimethyltin oxide 1.16 0.86

The reaction mixture was heated to 150 ° C. at a constant rate of 2 ° C./min until all reactants had melted. The reaction mixture is then heated at a constant rate of 2 ° C./min to 230 ° C.
It was kept at the same temperature until an acid number of less than was obtained. The relative activity of the three organotin catalysts was determined by monitoring the acid number of the reaction mixture during the last 4 hours of the polyesterification. The acid number versus time results are shown in Table V and plotted in FIG.

[0054]

[Table 5]

The data summarized in Table V and plotted in FIG. 5 show that no improvement in esterification rate is observed when the diol contains only primary hydroxyl groups, regardless of the organotin catalyst.

Comparative Example 2 The following reactants were charged to two 2-liter flasks. Grams moles of 2-butyl-2-ethyl-1,3-489.0 3.06 propanediol (BEPD) trimethylolpropane (TMP) 19.5 0.22 isophthalic acid (IPA) 182 1.1 adipic acid (AD 160) Organotin catalyst 0.05% by weight of total charge (based on% Sn in organotin catalyst)

Two organotin catalysts were evaluated. Reaction flask organic tin catalyst gram % Sn 1 butylstannic acid 0.75 0.43 2 dimethyltin oxide 0.60 0.43

The reaction mixture was heated to 150 ° C. at a constant rate of 2 ° C./min until all reactants had melted. The reaction mixture was then heated at a constant rate of 2 ° C./min to 215 ° C.
It was kept at the same temperature until an acid number of less than was obtained. The relative activity of the two organotin catalysts was determined by monitoring the acid number of the reaction mixture during the last 2 hours of the polyesterification. The acid number versus time results are shown in Table VI and plotted in FIG.

[0059]

[Table 6]

These results show that when the diol contains a primary hydroxyl group, no improvement in the esterification rate is observed.

[Brief description of the drawings]

FIG. 1 is a plot of acid number versus time showing the effect of an organotin compound on the IPA / AD / TMP / TMPD high solids polyester resin production process during the last 4 hours of polyesterification.

FIG. 2 shows the natural logarithm of the acid concentration (Ln [acid]) versus time showing the effect of the organotin compound on the IPA / AD / TMP / TMPD high solids polyester resin production process during the last 4 hours of polyesterification. It is a plot.

FIG. 3 is a plot of acid number versus time showing the effect of an organotin compound on the IPA / AD / TMP / PG high solids polyester resin production process during the last three hours of polyesterification.

FIG. 4 shows the natural logarithm of the acid concentration (Ln [acid]) versus time showing the effect of the organotin compound on the IPA / AD / TMP / PG high solids polyester resin production process during the last 3 hours of polyesterification. It is a plot.

FIG. 5 is a plot of acid number versus time showing the effect of organotin compounds on the IPA / AD / TMP / NPG polyester resin production process during the last 4 hours of polyesterification.

FIG. 6 is a plot of acid number versus time showing the effect of an organotin compound on the IPA / AD / TMP / BEPD polyester resin production process during the last 2 hours of polyesterification.

──────────────────────────────────────────────────続 き Continued on front page F-term (reference) 4J029 AA03 AB04 AC01 AC02 AD02 AE01 AE02 AE11 AE13 BA03 BA07 BA08 BA10 BD04A CB04A CB05A CB06A CD05 FC05 GA13 HB01 HB02 HB06 JB171 JC751 JF371 KB02 KB05 KD09 KE

Claims (19)

[Claims] 1. A method for producing a polyester from a polyol having a secondary hydroxyl group, comprising: (a) at least one polyol containing at least one secondary hydroxyl group; (b) polycarboxylic acid, polycarboxylic acid At least one polycarboxyl compound selected from acid anhydrides, lower alkyl esters of polycarboxylic acids or mixtures thereof; and (c) C ₁ -C ₃ alkyltin salts of carboxylic acids; C ₁ -C ₃ alkyl esters non acid; oxide C ₁ -C ₃ alkyl tin; halogenated C ₁ -C ₃ alkyl tin; selected from and mixtures thereof, a catalytically effective amount of at least one C ₁ -C ₃ alkyl tin compounds A method comprising reacting 2. The method of claim 1, wherein the molar ratio of the polyol to the polycarboxyl compound is from about 0.5 to
2. The method of claim 1, wherein the value is about 1.5. 3. The method according to claim 1, wherein the reaction is carried out as a melt of a polyol and a polycarboxyl compound. 4. The method according to claim 3, wherein the reaction temperature is from about 160 ° C. to about 280 ° C. 5. The method according to claim 1, wherein the reaction is an aromatic hydrocarbon, ether, sulfone, ketone,
The method according to claim 1, which is carried out in a solvent selected from sulfolane, sulfoxide, and mixtures thereof. 6. The method according to claim 1, wherein the polyol compound containing at least one secondary hydroxyl group is a diol and the polycarboxyl compound is a dicarboxyl compound. 7. The dicarboxyl compound is terephthalic acid; isophthalic acid;
Adipic acid; 1,4-cyclohexanedicarboxylic acid; dimethyl-terephthalate; phthalic anhydride; maleic anhydride; or a mixture thereof, and the diol is 1,2-propanediol; 1,2-butanediol; 2,4-cyclohexanediol; 2,2,4,4-tetramethylcyclobutanediol;
The method according to claim 6, which is 2,4, -trimethyl-1,3-pentanediol; or a mixture thereof. 8. (a) The C ₁ -C ₃ alkyltin salt of a carboxylic acid is represented by the following formula: (I) (R) ₂ Sn (O ₂ CR ¹ ) ₂ (II) RSn (O ₂ CR ¹ ) ₃ ( _{III) (R) 2 Sn (} O 2 CR 1) Y ( wherein, R may be the same or different, be a C ₁ -C ₃ alkyl; R ^1, which may be the same or different, C ₁ ~ C ₂₀ alkyl or C ₃ -C ₁₄ aryl, alkaryl or cycloalkyl group; Y has a _{halogen); (b) C 1 ~C} 3 alkyl static non acid formula RSn (O) OH (C) wherein the C ₁ -C ₃ alkyltin oxide is of the formula (R) ₂ SnO, wherein R may be the same or different, (D) a C ₁ -C ₃ alkyltin halide having the formula (R) _n Sn (X) _{3 -n} , wherein
R is the same or different and is as defined above; n is 1 or 2; and X is halide. 9. The method of claim 1, wherein the (a) C ₁ -C ₃ alkyltin salt of a carboxylic acid is dimethyltin diacetate, diethyltin diacetate, dipropyltin diacetate, dimethyltin dilaurate, methyltin trilaurate, ethyltin trilaurate, propyltin trilaurate. Or a mixture thereof; (b) the C ₁ -C ₃ alkylstannoic acid is methylstannoic acid, propylstannoic acid, ethylstannoic acid or a mixture thereof; and (c) the C ₁ -C ₃ alkyltin oxide is oxidized. Dimethyltin, diethyltin oxide, dipropyltin oxide, methylethyltin oxide, ethylpropyltin oxide, methylpropyltin oxide or mixtures thereof; and (d) the halogenated C ₁ -C ₃ alkyltin is methyl trifluoride Tin, dimethyltin dichloride, diethyltin dichloride, dipropyltin dichloride, dichloride Chiruechiru tin, ethylaluminum propyl tin dichloride The method of claim 8 wherein dichloride methylpropyl tin or mixtures thereof. 10. The (a) C ₁ -C ₃ alkyltin salt of a carboxylic acid is dimethyltin diacetate; (b) the C ₁ -C ₃ alkylstannoic acid is methylstannoic acid; ₁ -C ₃ alkyl tin be oxidized dimethyl tin; and and (d) of claim 9 halogenated C ₁ -C ₃ alkyl tin is dimethyltin dichloride. 11. The method according to claim 10, wherein the C ₁ -C ₃ alkyltin compound is dimethyltin oxide. 12. A polyester produced by the method according to claim 1. 13. A process for producing an ester from an alcohol having one secondary hydroxyl group, comprising: (a) at least one secondary alcohol; (b) a carboxylic acid, carboxylic anhydride or lower carboxylic acid. at least one carboxylic compound selected from alkyl esters; and (c) C ₁ ~C ₃ alkyl tin salt, C ₁ -C ₃ alkyl static non acid of the carboxylic acid, oxide C ₁ -C ₃ alkyl tin halide C ₁ -C ₃ alkyl tin and selected from the group consisting of a mixture thereof, the method comprising the step of reacting at least one C ₁ -C ₃ alkyl tin compound a catalytically effective amount. 14. The method according to claim 14, wherein the secondary alcohol is 1,2,3-trihydroxypropane;
1,2,4-butanetriol; 1,2,6-trihydroxyhexane; 1,3
Or a mixture thereof, and the carboxyl compound is 1,2,4-benzenetricarboxylic anhydride; 1,2,4-benzenetricarboxylic acid; 1,3,5-cyclohexanetricarboxylic acid; or 14. The method according to claim 13, which is a mixture thereof. 15. The method according to claim 13, wherein said reaction is carried out in a solvent selected from aromatic hydrocarbons, ethers, sulfones, ketones, sulfolane, sulfoxides and mixtures thereof. 16. (a) The C ₁ -C ₃ alkyltin salt of a carboxylic acid is represented by the following formula: (I) (R) ₂ Sn (O ₂ CR ¹ ) ₂ (II) RSn (O ₂ CR ¹ ) ₃ ( _{III) (R) 2 Sn (} O 2 CR 1) Y ( wherein, R may be the same or different, be a C ₁ -C ₃ alkyl; R ^1, which may be the same or different, C ₁ ~ (B) a C ₂₀ alkyl group or a C ₃ -C ₁₄ aryl or cycloalkyl group; Y is a halogen); (b) a C ₁ -C ₃ alkylstannoic acid having the formula RSn (O) OH wherein , R is as previously defined); (c) wherein the C ₁ -C ₃ alkyltin oxide is of the formula (R) ₂ SnO, wherein R may be the same or different and is as defined above. And (d) the C ₁ -C ₃ alkyltin halide is of the formula (R) _n Sn (X) _{3 -n} , wherein
R is the same or different and is as defined above; n is 1 or 2; and X is halide. 17. (a) The C ₁ -C ₃ alkyltin salt of a carboxylic acid is dimethyltin diacetate, diethyltin diacetate, dipropyltin diacetate, dimethyltin dilaurate, methyltin trilaurate, ethyltin trilaurate, propyltin trilaurate Or a mixture thereof; (b) the C ₁ -C ₃ alkylstannoic acid is methylstannoic acid, propylstannoic acid, ethylstannoic acid or a mixture thereof; (c) the C ₁ -C ₃ alkyltin oxide is oxidized Dimethyltin, diethyltin oxide, dipropyltin oxide, methylethyltin oxide, methylpropyltin oxide, ethylpropyltin oxide or mixtures thereof; and (d) the halogenated C ₁ -C ₃ alkyltin is methyl trifluoride Tin, dimethyltin dichloride, diethyltin dichloride, dipropyltin dichloride, disalt Methylethyl tin, ethylaluminum propyl tin dichloride The method of claim 16 which is a dichloride methylpropyl tin or mixtures thereof. 18. (a) the C ₁ -C ₃ alkyltin salt of a carboxylic acid is dimethyltin diacetate; (b) the C ₁ -C ₃ alkylstannoic acid is methylstannoic acid; ₁ -C ₃ alkyl tin be oxidized dimethyl tin; and and (d) of claim 17 halogenated C ₁ -C ₃ alkyl tin is dimethyltin dichloride. 19. The method according to claim 18, wherein the C ₁ -C ₃ alkyltin compound is dimethyltin oxide.