JPS63172727A - Production of crosslinked polyester resin - Google Patents

Abstract

PURPOSE:To obtain stably a crosslinked polyester resin of any desired degree of crosslinking, by esterifying a polycarboxylic acid component with a diol component and crosslinking the product while increasing the pressure in the reaction system with an increasing viscosity. CONSTITUTION:In an operation of esterifying or transesterifying a polycarboxylic acid component comprising 2-100mol%, based on the total carboxylic acid component, tricarboxylic acid component (a) and at most 98mol%, based on the total carboxylic acid component, dicarboxylic acid compo nent (b) with a diol component (c) in an amount represented by the formula and forming crosslinkages while distilling the diol component (c) in a vacuum <=150mmHg, the rate of crosslinking is controlled by increasing the pressure in the reaction system with he increasing viscosity of the polymer. Although the rate of removal of the diol component (c) by distillation depends on the pressure and temperature in the reaction system, the degree of vacuum is prefer ably 150mmHg or below in consideration of the pressure conditions for stopping the reaction system.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing a saturated polyester resin having a crosslinked structure.

<Prior Art and Problems> Saturated polyester resins have conventionally been used in a wide range of fields, including fibers, films, molding materials, paints, adhesives, and various binders for toners. Among these, many attempts have been made to use crosslinked materials in paints, adhesives, toners, and the like to improve hardness, adhesive strength, and offset properties. However, it is difficult to produce crosslinked polyester resins using the esterification or transesterification methods that have been proposed in the past. This is because the reaction must be stopped when the polymer reaches a suitable melt viscosity, but in conventional methods using esterification or transesterification, the temperature of the reaction system is rapidly lowered as a means of stopping the reaction. There are two possible methods: or adding water or alcohol to the reaction system to stop the gelation reaction. This is because it is difficult to moderate this gelation reaction and stop it at a desired degree of crosslinking by any method. In this situation, the above gelation reaction can be controlled,
At present, there is a desire for an excellent method for producing polyester having a desired degree of crosslinking.

<Problems to be Solved by the Invention> The purpose of the present invention is to provide a method for producing polyester μ resin stably without rapid gelation reaction and having a desired degree of crosslinking, that is, to control the reaction rate; It is an object of the present invention to provide a method for producing a crosslinked polyester resin in which the reaction is stopped when the polymer reaches a desired degree of crosslinking.

<Means for solving the problems> - The gist of the present invention is (&) a trivalent carboxylic acid component of 2 mo/L/- or more and 100 mole or less based on the total carboxylic acid component; (b) Esterification of a polyvalent carboxylic acid component consisting of a divalent carboxylic acid component of 98 mo/L/- or less based on the total carboxylic acid components and (c) a diol component in an amount shown by formula (1). After reaction or transesterification, 1
In the operation of forming a crosslinked product while distilling off the diol component (c) under a vacuum of 50-H9 or less, the pressure of the reaction system is increased in accordance with the increase in the viscosity of the polymer to substantially prevent the crosslinking reaction. To be in control.

The present invention provides a method for producing a characteristic crosslinked polyester resin.

4〉y〉α8(1+x) ...(1) (Formula (1)
y is the number I of hydroxyl groups in the diol component. ) In the present invention, a force with a valence of more than 5! A trivalent or higher carboxylic acid, an acid anhydride thereof, or a lower acid μ ester thereof is used as the boxylic acid component (a), and a compound having 3 or more hydroxyl groups in one molecule, One or more of the three or more carboxyl groups present is an acid anhydride, or one or more of the three or more carboxyl groups present in one molecule is an ester of a lower alcohol. There are many things that can be mentioned. Specifically 1.2.4
-benzenetricarboxylic acid, 1,2゜4+ychlorohexanetricarboxylic acid, 1.2.4-naphthalenetricarboxylic acid, 2. a7-naphthalene tricarboxylic acid, L2
．． 4-butanetricarboxylic acid, 1,2.5-hexanetricarboxylic acid, 1,2゜7,8-octanetetracarboxylic acid or their acid anhydrides or their ethyl esters, ethyl esters, propyl esters, isopropyl esters, etc. Examples include esters of lower alcohols with a boiling point of 200°C or less. In the present invention, the carboxylic acid component having a valence of 5 or more is used in the range of 2 moles or more and 100 moA/- or less relative to the total μ-ponic acid component, and if it is less than 2 moles, good crosslinked nodes are obtained. I can't.

Further, as the divalent carboxylic acid component (6), a divalent carboxylic acid, an acid anhydride thereof, or a lower oxyester thereof is used, and a compound having two VIW groups in one molecule. Alternatively, examples include acid anhydrides of these, or those in which one or more of the two hydroxyl groups present in one molecule is an ester of a lower alcohol, such as maleic acid, fumaric acid, Mesaconic acid, sitotsonic acid, itaconic acid, glutaconic acid, phthalic acid,
Isophthalic acid, terephthalic acid, V-chlorohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, malonic acid,
Somuic acid, its acid anhydride, or its monomethyl ester, dimethyl ester, monoethyl ester, siethyl ester, monopropyl ester, diderobi ester, methyl ethyl ester, ethyl propyl ester, etc. with a boiling point of 200°C or less Examples include lower alcohol-p monoesters and diesters.

The diol component (c) used in the present invention is a compound having two hydroxyl groups in one molecule, and specific examples include niethylene glycol, diethylene glycol μ, triethylene glycol ~, propylene glyco-A/1j-propane. Geo-~
, 1,4-butanedio-μ, cyclohexane dimetatool, neopentyl glycol, hexamethylene diol ~
, bispheno-/L'A1 hydrogenated bispheno-/L'A.

Polyoxypropylene (2,0)-2,2-bis(4-
Hydroxyphenylene lv) propane, polyoxyethylene (90)-2,2-bis(4-hydroxyphenylene/I/
) Propane, 2.2'-(1,4-phenylenebisoki V)bisethano-/L/, 1.1'-dimethy/M-2,
2'-(1,4-phenylenebisoki V)bisethano-
I's 1.1.1; 1/-tetofumethi p-2,2
'-(1,4-phenylenebisoki V)bisethanol is mentioned.

With this invention, we are going all out! Mixing a diol component and a carboxylic acid component in a range that satisfies the above formula (1) with respect to the total amount of a carboxylic acid component, that is, a carboxylic acid with a valence of 5 or more and a divalent carboxylic acid component, and heating and increasing the temperature. A diesterification reaction or transesterification reaction is carried out. At this time, an esterification catalyst or a transesterification catalyst used in a normal esterification reaction or transesterification reaction, such as sulfuric acid, titanium butoxide, dibutyltin oxide, magnesium acetate, manganese acetate, etc., can be used as necessary.

In the present invention, the condition is that no gelation reaction occurs during the esterification reaction or transesterification reaction, and the amount of diol component (c) added must satisfy the above formula (1). It is.

Next, water or lower alcohols are removed by distillation from the reaction system by esterification reaction or transesterification reaction, and then the pressure of the reaction system is reduced to 15011IIH9 or less so that the diol component (c) is not removed by distillation from the reaction system. A condensation reaction is carried out from In addition, for polymerization, commonly known polymerization catalysts,
For example, titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide,
Germanium oxide, zinc acetate, etc. can be used.

In this reaction, the viscosity increases as the diol component (c) is removed by distillation, but when a certain viscosity is reached, a gelation reaction begins to occur and the viscosity of the polymer rapidly increases. At this time, the pressure in the reaction system is increased in accordance with the increase in polymer viscosity due to the gelation reaction, and when the desired degree of crosslinking is reached while easing the reaction, the reaction system is brought under a pressure that substantially stops the reaction. By doing so, it becomes possible to produce a polyester resin having an arbitrary degree of crosslinking. That is, the present invention provides a method for easily producing a polyester resin having a desired degree of crosslinking by alleviating the rapid increase in viscosity after the gelation point is reached by controlling the pressure of the reaction system.

Incidentally, the distillation removal of the diol component (c) is determined by the pressure and temperature of the reaction system, but considering the pressurizing conditions of the reaction system to substantially stop the reaction, the degree of vacuum is preferably 150 μH9 or less, Particularly preferred is 30 ■Hg or less.

Hereinafter, the present invention will be specifically explained with reference to Examples.

<Example 1> Trimellitic anhydride, terephthalic acid, and ethylene glycol were charged into a reactor having a distillation column according to the composition shown in Table 1.

(The numbers in the table represent parts by weight) Djibouti is added to the reaction vessel! When tin oxide was added at α03 mo/'% based on the total acid component, and the internal temperature was kept at 220°C and the stirring speed was kept at 20 Or, p, m, and the esterification reaction was carried out under normal pressure, water started to distill out. After about 5 hours, the inside of the reaction system became transparent and the distillation of υ water stopped. The torque meter for the stirrer at this time was an α9 Yuichikuni. Next, the internal temperature was set to 235°C, and the stirring rotation speed was set to 20 Or, p, m.
When the pressure inside the reaction system was reduced to 1.0wHg, ethylene glycol was distilled out from inside the reaction system, and the stirring torque gradually increased until about 1.5 hours later, when the stirring torque reached 1.0wHg. At the time when 2 kliF-100 was reached, gelation began and the stirring temperature began to rise rapidly. At this time, when the pressure of the reaction system was changed to 1 O-Ell, the rate of increase in stirring torque became slow, and about 2.6 hours after ethylene glycol began to distill, the stirring torque reached 1 Okg.
- cm was reached. At this time, the pressure in the reaction system was set to normal pressure, and stirring was continued in that state for about 1 hour.

As a result, the stirring torque remained almost constant at 505 kliF-cm. Figure 1 shows the results.

This example shows that the degree of crosslinking of the polymer, that is, the stirring torque, or the viscosity, can be easily controlled by controlling the pressure within the reaction system, and that the gelation reaction can be substantially stopped.

<Example 2> Trimeriz F acid anhydride, terephthalic acid, and ethylene glycol were used and charged into a reaction vessel equipped with a distillation column according to the composition shown in Table 1. The esterification reaction was carried out under normal pressure for about 5 hours under the same catalyst, temperature conditions, and stirring speed as in Example 1. The stirring rate when water stopped distilling out of the reaction system was 19 kli-yt. Next, the pressure in the reaction system was increased to 1. The pressure was reduced to OmHJil, and ethylene glycol was distilled off under the reduced pressure. As diethylene glyco〃 is distilled out of the reaction system, the stirring torque gradually increases, and about 1.
After 5 hours, when the stirring torque reached 1.2 hours, gelation started and the stirring torque began to rise rapidly. At this time, when the pressure in the reaction system was changed to 10 wa Ell, the rate of increase in stirring torque was slow and reached 50 yum in about 1 hour. At this time, when the pressure in the reaction system was further changed to 2O-H9, the rate of increase in the stirring rate became slow again. In addition, the opening bale stirring torque is approximately 1 hour &
When Okg -3 is reached, the pressure inside the reaction system is returned to normal pressure. ! Stirring was continued for about 1 hour. As a result, the stirring torque was 5.0 knee 1, which was a substantially constant value.

This example shows that it is possible to control the stirring torque, that is, the viscosity, after the gelation point is reached by controlling the pressure within the reaction system; in other words, it is possible to control the gelation reaction.

<Example 3> 1.2. ``18-octane tetofukanic acid, terephthalic acid, and 1,4-butanediol were used and charged into a reaction vessel having a distillation column according to the composition shown in Table 2.

Table 2 (The numbers in the table indicate parts by weight.) In addition, titanium butoxide was added to the total acid component by Q, 03
Add mo/%/ti, internal temperature 250℃, stirrer rotation speed 20
The esterification reaction was carried out using Or, p, m under normal pressure. Approximately 4 hours after water began to distill out, the mixture in the reaction vessel became transparent υ, and approximately 5 hours later, water distillation stopped, and at this time the stirring torque was α9kl? -(.Next, the internal temperature was set to 240°C, and the pressure inside the reaction system was reduced to 1.0 μHg, and 1.4-butanediol was distilled out under the reduced pressure.1. .The stirring torque when 4-butanedio-y started to distill out was 1.0 kg -〇.
As 4-butanediol was distilled off, the stirring torque increased, and 2 hours after 1.4-butanediol started distilling off, the stirring torque was 1.1 kg-cm, and 4 hours later, it was 1.2 kl. When the temperature reached -51, gelation started and the stirring torque began to rise rapidly. At this time, when the pressure inside the reaction system was set to 1 O-Ell, the rate of increase in stirring torque became slow. After about a further 1.5 hours, the stirring torque reached 2.5 kl-hundred. At this time, when the pressure inside the reaction system was set to 20 mHfi, the rate of increase in stirring torque became slow again, and the rate of increase in stirring torque became 6.0 kl in about 1.5 hours.
-an has been reached. At the same time, the pressure inside the reaction system was brought to normal pressure, and stirring was continued in that state for about 1 hour. As a result, the stirring rate was 6. , Okg-crs, which showed almost constant values. The results are shown in Figure 2.

This example shows that even when a tetravalent carboxylic acid is used, it is possible to control the stirring torque that reaches the gelation point, that is, the viscosity, by the pressure within the reaction system. In other words, it is possible to control the gelation reaction. is possible.

<Example 4> Trimellitic anhydride, terephthalic acid, ethylene glycol
μ was used and charged into a reaction vessel equipped with a distillation column according to the composition shown in Table 1. The esterification reaction was carried out under normal pressure for about 5 hours using the same catalyst, temperature conditions, and stirring rotation speed as in Example 1. The stirring torque when water stopped distilling from the reaction system was 0.9 kg -3. Next, the reaction pressure in the reaction system was reduced to 1.0 xi H9, and ethylene glycol was distilled out under the reduced pressure. As ethylene glycol-y was distilled out of the reaction system, the stirring torque gradually increased, and about 1.5 hours after ethylene glycol started to be distilled out, gelation occurred when the stirring torque reached 1.1 kg-cm. Since the stirring torque started to increase rapidly, the pressure of the reaction system was increased at a rate of 15 M Fi p per minute.

At this time, the stirring torque gradually increased and reached 50 klil-1 after about 2 hours, so the pressure of the reaction system was returned to normal pressure and stirring was continued in that state for about 1 hour. As a result, the stirring torque was 50 ym-, which was a nearly constant value. The results are shown in FIG.

In this example, by continuously controlling the pressure inside the reaction system, it is possible to control the viscosity of the agitation after reaching the gelation point, in other words, it is possible to control the gelation reaction. is possible.

<Example 5> Trimethyl trimellitate, dimethyl terephthalate, ethylene glycol, and Neobenchi Nlj Recall were used and charged into a reaction vessel having a distillation column according to the proportions shown in Table 3.

Further, titanium oxide was added at α03mol/L/% based on the total carboxylic acid components, and the internal temperature was 230°C and the stirring rotation speed was 2.
When the transesterification reaction was carried out for 5 hours under normal pressure while maintaining the pressure at 0 Or, p, m, methanol no longer came out from the distillation column. At this time, the stirring torque was 17 kl-cm. Next, the internal temperature was set to 235°C and the stirring speed was set to 20 Or, p,!
D, the pressure of the reaction system was reduced to 1.0 Hy, and the diol component was distilled out under the reduced pressure. As the diol component is distilled out from the reaction system, the stirring torque gradually increases, and when the stirring torque reaches 1.5 kg-cm, the gelation reaction begins and the stirring torque rapidly increases, so that the reaction system When the pressure was increased at a rate of 18-H9 per minute, the viscosity gradually increased, and after about 3 hours, the stirring torque reached 5 kg-1, so the pressure of the reaction system was returned to normal pressure and the reaction stopped. It was confirmed that

In this example, even when using the transesterification method, by continuously controlling the pressure inside the reaction system, it is possible to control the viscosity of the stirrer after the gelation point is reached. In other words, it shows that the gelation reaction can be controlled.

<Comparative Example 1> Trimellitic anhydride, terephthalic acid, and ethylene glycol were used and charged into a reaction vessel equipped with a distillation column according to Table 1. The esterification reaction was carried out under normal pressure for about 5 hours using the same catalyst, temperature conditions, and stirring rotation speed as in Example 1.

When the water distilled from the reaction system has stopped, the stirring top is O.
，? There were Yum pieces. Next, the pressure inside the reaction system was increased to 101Hf.
The pressure was reduced to i, and ethylene glycol was distilled off under the reduced pressure. As ethylene glycol was distilled out from the reaction system, the Xu JK stirring torque increased, and approximately 1.5 hours after ethylene glycol began to distill out, the stirring torque reached 1.2 kg-cm, and the stirring stopped with the start of the gelation reaction. The torque increased rapidly and reached 50 yen. At this point, the pressure in the reaction system was returned to normal pressure, and stirring was continued for about 1 hour. As a result, the stirring torque temporarily increased and finally reached &7 kl-ctyz. This indicates that even if an attempt is made to stop the gelation reaction, the reaction proceeds beyond the desired stirring rate ((5O)C9-eIR). The results are shown in Figure 4.

Comparative Example 2> 39.0 parts of trimellitic anhydride, 516 parts of terephthalic acid, and 57.8 parts of ethylene glycol/I/ were placed in the same reaction vessel as in Example 1, and α03 mole was added to the total p-boxylic acid component. Add fi19G dibutyltin oxide and bring the internal temperature to 230°C.
The esterification reaction was carried out under normal pressure while keeping the rotational speed of the stirrer at 20 degrees r, p, m.

Two hours after water began to distill from the distillation column, a gelation phenomenon occurred and the viscosity of the reactant began to rise rapidly, so the reaction vessel was cooled with water, but the reaction temperature could not be lowered in time and the gelation phenomenon occurred. , the stirrer stopped after about 6 minutes. As a result, it was impossible to take out the reactants, and normal production of crosslinked polyester μ resin was not possible. The results are shown in Figure 5.

<Effects of the Invention> The method of the present invention allows the gelation phenomenon to be controlled, which could not be achieved with conventional methods, that is, the rapid increase in stirring torque that occurs during the reaction can be alleviated, and the reaction can be carried out at the target stirring torque. As a result, it is possible to obtain a polyester resin with a target degree of crosslinking in a package, and it is possible to provide crosslinked polyester μ resins that meet the purposes of various uses. is extremely large.

[Brief explanation of the drawing]

Figures 1 to 5 are Example 1.3.4 and Comparative Example 1, respectively.
．． 2 shows the changes over time in the stirring torque and internal pressure of the polymerization system in No. 2. In the figure, ■ indicates the internal pressure curve, and ■ indicates the stirring torque curve, respectively. Part 1 @ Anti-forget/Tokoro Width 2 Car 2 times UjiByIf Seki (hrλ Figure 3 reaction time (hr) Figure 4 Reaction time (/u-ra Figure 5 Reaction time (hr) Procedure amendment book 1986 4 20th of the month

Claims (1)

Scope of Claims: (a) a trivalent carboxylic acid component of 2 mol% or more and 100 mol% or less based on the total carboxylic acid component; (b) a divalent carboxylic acid component of 98 mol% or less based on the total carboxylic acid component; After carrying out an esterification reaction or transesterification reaction with a polyhydric carboxylic acid component consisting of a carboxylic acid component and the diol component (c) in an amount represented by formula (1), the diol component (c) is reacted under a vacuum of 150 mmHg or less. A method for producing a crosslinked polyester resin, which comprises substantially controlling the crosslinking reaction rate by increasing the pressure of the reaction system in accordance with the increase in the viscosity of the polymer in an operation of forming a crosslinked state while removing the polymer by distillation. 4>y>0.8(1+x)...(1) (In formula (1), y is y = number of hydroxyl groups in the diol component/number of carbonyl groups in all carboxylic acid components x is x = component ( The number of carbonyl groups derived from a)/the number of carbonyl groups in the total carboxylic acid component.)