JP2869748B2 - Composition containing reactive monomer and method for producing the same - Google Patents

Description

The present invention relates to a composition containing a reactive monomer and a method for producing the same.

More specifically, the present invention relates to an industrially useful lactone-modified polyester compound having a liquid type side chain and a method for producing the same.

In recent years, the importance of various lactone polyester polyols for curing agents for acrylic paints and urethane foams has been increasing.

The reason is that they have excellent characteristics in weather resistance, mechanical properties, chemical resistance, and stain resistance.

Therefore, it has been used in all fields such as the automobile industry, the home appliance industry, and the building materials industry.

However, it is difficult to handle due to crystallization, etc.
Further, higher performance such as weather resistance is required.

<< Prior Art >> and << Problems to be Solved by the Invention >> These polycaprolactone polyols are easily crystallized as the number of added lactones increases. For example, a 6 mol adduct of lactone of trimethylolpropane is 10
If left for a long time at around ℃, it becomes a paste, so it is necessary to heat it to uniformity during use.

On the other hand, when the number of moles to be added further increases, solidification is carried out at room temperature, so that a long-time dissolving operation is required.

Further, when added for the purpose of modifying various coatings, there is a problem that the coating film becomes white due to crystallization.

On the other hand, when ε-caprolactone is subjected to ring opening addition, an ester bond is generated.

However, these ester bonds tend to hydrolyze when a trace amount of acid or alkali is present,
Improvement in hydrolysis resistance has also been required.

<< Object of the Invention >> In order to solve these problems, the present inventors have conducted intensive studies and found that β-methyl-δ-valerolactone, or trimethylcaprolactone or a mixture thereof and ε-caprolactone was used as a catalyst. The present inventors have found that a polyester polyol produced by ring-opening addition polymerization under the following conditions is extremely effective, and arrived at the present invention.

<< Means for Solving the Problems >> That is, the present invention relates to the following (I) [However, in the formula (I), R ^a and R ^b are hydrogen, methyl, ethyl, propyl, and butyl and can be arbitrarily replaced with each other, but not all are hydrogen at the same time. x1 and x2 are an integer of 1 to 7 y1 and y2 are an integer of 0 to 20 (however, y1 and y2 are not simultaneously 0) z; an integer of 1 to 4 R; an alkyl group having 1 to 20 carbon atoms ] A composition comprising a reactive monomer represented by the following: and "a compound having an OH group having 1 to 20 carbon atoms is subjected to ring-opening polymerization in the presence of a catalyst with at least two or more lactones. Equation (1) [However, in the formula (1), R ^a and R ^b are hydrogen, methyl, ethyl, propyl, and butyl and can be arbitrarily replaced with each other, but not all are hydrogen at the same time. x1 and x2 are an integer of 1 to 7 y1 and y2 are an integer of 0 to 20 (however, y1 and y2 are not simultaneously 0) z; an integer of 1 to 4 R; an alkyl group having 1 to 20 carbon atoms ] A method for producing a composition containing a reactive monomer represented by the formula:

 Hereinafter, the present invention will be described in detail.

The “composition containing a reactive monomer” of the present invention has 1 to 1 carbon atoms.
A lactone polyester polyol produced by ring-opening polymerization of a lactone monomer having at least one type of side chain using a monohydric to tetrahydric alcohol having 20 alkyl groups as an initiator.

In the compound represented by the formula (I) of the present invention, R ^a ,
R ^b is hydrogen, methyl, ethyl, propyl, or butyl, which can be arbitrarily substituted, but not all hydrogen at the same time.

This is because, for example, branched lactones such as β-methyl-δ-valerolactone and trimethylcaprolactone are essential components.

x1 and x2 are the number of alkylene groups or substituent-containing alkylene groups that vary depending on the lactone used, and take an integer of 1 to 7.

For example, if trimethylcaprolactone is used as the lactone component, x1 or x2 will be 5.

y1 and y2 are numerical values that vary depending on the ratio of the initiator and the lactone monomer used, and represent the degree of polymerization of each lactone portion.

 Specifically, it takes an integer of 0 to 20.

However, y1 and y2 never become 0 at the same time. This is because the main compound in the composition containing the reactive monomer of the present invention has at least one kind of lactone unit as an essential component.

y1 and / or y2 can be arbitrarily controlled by the use ratio of the initiator and the lactone monomer, but if it exceeds 20, the resulting composition (compound) has a too high molecular weight and contains a reactive monomer. It is not preferable because the composition cannot be used effectively.

z is the number of functional groups of the initiator. For example, when methanol is used as an initiator, it is 1; when trimethylolpropane is used, z is 3.

Specific examples of the monohydric to tetrahydric alcohol used as an initiator include OH groups such as pentaerythritol, trimethylolpropane, glycerin, diglycerin, trishydroxyethyl isocyanurate, diethylene glycol, ethylene glycol, ethanol, propanol, and methanol. Compounds having 1 to 4 are mentioned.

R in the formula (I) is a residue of the above initiator. The lactones as starting material components include ε-caprolactone, 3,3,5-trimethylcaprolactone, 3,5,5-trimethylcaprolactone, β-methyl-δ-valerolactone, and the like. Can be used.

Among the above lactone monomers, a lactone having an alkyl group other than ε-caprolactone, for example, a branched lactone such as β-methyl-δ-valerolactone and trimethylcaprolactone is an essential component.

Industrially, ε-caprolactone is mainly used, and 3,3,5-trimethylcaprolactone, 3,3
5,5-trimethylcaprolactone or β-methyl-δ
It is advantageous to add valerolactone in any proportion.

The ε-caprolactone, 3,3,5-trimethylcaprolactone, and 3,5,5-trimethylcaprolactone used in the present invention are produced by oxidizing cyclohexanone, 3,3,5-trimethylcyclohexanone by a Bayer-Villiger reaction using a peracid. can do.

In particular, 3,5,5-trimethylcaprolactone and 3,3,5-
Trimethylcaprolactone can be obtained as a mixture by reacting 3,3,5-trimethylcyclohexanone with peracid, but the mixture can be separated by various methods and polymerized alone or used as a mixture. .

β-methyl-δ-valerolactone is 2-hydroxy-
It can be produced using 4-methyltetrahydropyran as a raw material.

A polymer obtained by copolymerizing these with ε-caprolactone, which is a lactone monomer having no side chain, has a methyl group near the ester bond. Has an increased hydrophobicity and is less likely to be hydrolyzed.

It is also conceivable that the lactone having a methyl group is copolymerized to lower the crystallinity than the ε-caprolactone homopolymer, so that the melting point is lowered. Further, β-methyl-δ-valerolactone or trimethylcaprolactone alone or a mixture thereof can also be used.

On the other hand, it is conventionally known that ring-opening polymerization of β-methyl-δ-valerolactone proceeds with a strong alkali or strong acid catalyst, but a polyester polyol can be synthesized in a similar system.

On the other hand, when ε-caprolactone and β-methyl-δ-valerolactone and / or trimethylcaprolactone are copolymerized, the reaction can be performed without necessarily using a strong alkali or strong acid catalyst.

If a strong alkali or strong acid catalyst remains and mixes into a paint or the like, it is not preferable because it imparts corrosive properties to the base material.

Therefore, it is necessary to perform a removal operation by washing with water or an adsorbent, but this is not an advantageous method for an industrial process because a catalyst removal step is included.

The lactone is reacted at 1 to 20 per mole of hydroxyl group. The lactones used can be used alone or in combination of two or more.

Examples of catalysts used for ring-opening polymerization of lactones include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate; organotin compounds such as tin octylate, dibutyltin oxide and dibutyltin laurate; stannous chloride; Stannous halides such as stannous halide and stannous iodide, heteropolyacids of phosphotungstic acid, and acetyl acetate of zinc can be used.

However, the addition of a large amount of such a metal compound often has an adverse effect when used as a polyester polyol.

Further, metal catalysts such as magnesium chloride, magnesium methoxide, magnesium ethoxide, and aluminum isopropoxide and aluminum butoxide can be used.

The amount of the catalyst used is 1000 ppm to 0.01 ppm, preferably 200 p
From pm to 0.1 ppm. When the used amount is 1000 ppm, it is possible to increase the reaction rate.

However, it may adversely affect the final product, and may require a removal operation, which is not preferable.

On the other hand, when the content is 0.01 ppm or less, the catalytic effect is small and much time is required for completing the reaction, so that it is not an economically advantageous method.

On the other hand, strong bases such as n-BuLi, sec-BuLi and ter-BuLi can be used. Further, the reaction can be performed using an ion exchange resin such as Amberlyst.

The optimum reaction temperature differs depending on the catalyst used.

The lactone addition reaction when using tin, titanium, magnesium, aluminum or the like can be carried out at a temperature in the range of 50 to 250 ° C.

When the temperature is lower than 50 ° C., the reaction rate is low, and when the temperature is higher than 250 ° C., the degree of coloring is increased, and the decomposing reaction easily occurs, which is not preferable.

On the other hand, when using BuLi or amber list, 50-150 ° C
It is preferable to carry out in.

In particular, when valerolactone-containing polymerization is carried out, valerolactone has a reverse reaction of returning to a monomer rather than a polymer, so that a reaction at a high temperature is not necessarily advantageous.

The reaction may be carried out without a solvent or in an inert solvent having no active hydrogen such as toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone (when using a catalyst such as BuLi, a ketone solvent is used. Desirably is better).

The use of the inert solvent is effective in lowering the viscosity of the reaction crude liquid in the system after the completion of the reaction, and also facilitates temperature control during the reaction.

Whether or not an inert solvent is used can be arbitrarily selected according to the purpose of use of the reactive monomer composition of the present invention.

That is, it can be used for products that may contain a solvent such as a paint.

Further, the inert solvent may be added later to the crude reaction solution after the completion of the reaction.

The amount of the inert solvent used is 5 to 80% by weight, preferably,
10 to 50% by weight.

However, a solvent having an ester bond is not preferred. This is because a transesterification reaction occurs with the ester group of the polylactone during the reaction, and a lactone polymer not bonded to the polyfunctional polyol may be formed.

When stannous chloride is used as the catalyst, an ester-based solvent can be used since the transesterification reaction is hardly promoted.

 It is preferable that the raw material used has as little moisture as possible.

The moisture in the polyfunctional alcohol used is 0.001-1.0%,
The water content in the lactone is desirably in the range of 0.001 to 0.02%.

This is because water in the raw material opens the lactone during the reaction, increases the acid value of the product, and adversely affects the product.

A lactone modified product of an alcohol having a high acid value, that is, a reactive monomer which is a main component in the composition of the present invention itself has poor water resistance and is liable to undergo hydrolysis.

In addition, the water reacts with the metal catalyst used in the lactone ring-opening reaction to deactivate the catalyst.

Therefore, when the raw material contains a large amount of water, it is preferable to distill only water by heating under reduced pressure or to dehydrate with a dehydration adsorbent such as molecular sieve before starting the reaction by introducing a catalyst.

In this reaction, the content of unreacted ε-caprolactone is preferably less than 1%.

However, the other lactones used in the copolymerization at that time are less reactive than ε-caprolactone, so that the
Some tens of percent may remain.

These unreacted lactones can be regarded as a solvent and need not be particularly removed.

 The reaction is preferably performed under nitrogen.

This is because mixing of air causes coloring of the product.

 The order of charging the raw materials in the reaction is arbitrary.

 When the reaction is terminated under the above conditions, the desired product can be obtained as a mixture of (a) a lactone monomer, (b) a polyfunctional polyester polyol, (c) a catalyst, and (d) an inert solvent.

 Generally, this can be used as it is.

If necessary, the catalyst can be removed by a treatment such as neutralization or adsorption.

The unreacted lactone monomer (a) may be separated by a known method such as distillation.

<< Effect of the Invention >> According to the present invention, a liquid lactone-based polyester polyol which is difficult to crystallize can be obtained, and a great improvement can be obtained in terms of ease of handling and whitening of the product.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

Example 1 2.0 L equipped with a nitrogen inlet tube, a thermometer, a cooling tube, and a stirrer
In a four-neck flask, trimethylolpropane 342.2 gr, ε-
1630 gr of caprolactone, 291.1 gr of β-methyl-δ-valerolactone, and 3.25 gr of stannous chloride (1% ε-caprolactone solution) were charged and reacted at 170 ° C for 13 hours.

0.23% of ε-caprolactone and 3.84% of β-methyl-δ-valerolactone remained.

 The sample had the following properties:

APHA 40 vis (cp / 45 ° C.) 357 Acid value (mgKOH / g) 1.55 Hydroxyl value (〃) 182.4 ¹ H-NMR spectrum of the product of Example 1 (No. 1)
FIG. 2) and IR spectrum (FIG. 2) were measured.

^{The 1} H-NMR spectrum was obtained by measuring at room temperature in CDCl ₃ using a JNM-EX90 spectrometer of JEOL Ltd.

In this spectrum, the multiplet of δ 0.8 to 1.2 (ppm) is assigned to hydrogen of methyl group, and the multiplet of δ 3.5 to 3.8 is assigned to methylene hydrogen of methylol group. Other peaks are specific to caprolactone polyester.

IR spectra coating on NaCl plates with IR-435 of Shimadzu Corporation, obtained by measuring the absorption of a carbonyl group was observed in the absorption and 1727 cm ^-1 of OH groups to 3428cm ^-1.

From the above results, this product is represented by the following chemical formula.

[However, R is the following And / or And n + m is approximately 6.] Examples 2 to 5 A reaction was carried out in the same manner as in Example 1 under the conditions shown in Table 1 to obtain a liquid lactone-based polyester polyol.

In Table 1, TMP: trimethylolpropane CL-M: ε-caprolactone MVL: β-methyl-δ-valerolactone Reaction time: time Gas chromatography was used to measure residual monomers.

Comparative Example-1 Trimethylolpropane (318.4 gr), ε-caprolactone (1681.6 gr), and tetrabutoxytitanium (1% heptane solution) (2.0 g) were charged into an apparatus similar to that of Example-1, and charged at 170 ° C.
Allowed to react for hours.

Viscosity (cp / 25 ° C) 1451 Acid value (mgKOH / g) 0.63 Hydroxyl value (mgKOH / g) was 198.6.

 The crystallization speed of this and Examples 1 to 5 was compared.

Each liquid was taken in a 100-ml sample bottle, and the turbidity was measured at 0 ° C. As a result, the product obtained in Comparative Example was whitened on the first day, whereas the product of Example 1 was whitened on the seventh day. The product of Example 2 became cloudy for the first time on the fourth day.

The product of Example 5 developed a slight haze on the second day.
The products of Examples 3 and 4 did not develop turbidity by day 7.

Example -6 The same procedure was performed as in Example 1 except that 342.2 gr of trimethylolpropane, 1200 gr of ε-caprolactone and 440 gr of trimethylcaprolactone were used.

ε-caprolactone 0.20% trimethylcaprolactone 4.0% A composition that remained was obtained.

 The properties were as follows.

APHA 40 vis (cp / 45 ° C) 340 Acid value (mgKOH / g) 0.80 Hydroxyl value (mgKOH / g) 190.0 Example-7 136 g of pentaerythritol and 342 g of ε-caprolactone
r, β-methyl-δ-valerolactone 114gr, 1%, SnCl
0.6 g of ₂ (ε-caprolactone solution) was added and reacted at 170 ° C. for 10 hours.

0.1% of ε-caprolactone and 3% of β-methyl-δ-valerolactone remained.

From the remaining lactone, a product was obtained in which about 3.8 mol lactone was added per 1 mol of pentaerythritol.

APHA 30 OH value 370.0 Acid value 0.2 Liquid (20 ° C).

Comparative Example 2 A reaction was performed under the same conditions as in Example 7 except that 434-gr of ε-caprolactone was used without using β-methyl-δ-valerolactone.

The obtained product became cloudy, but kept in a liquid state without further crystallization.

[Brief description of the drawings]

FIG. 1 is a chart of ¹ H-NMR spectrum measured for the product obtained in Example 1, and FIG. 2 is a chart of the IR spectrum.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08G 63/08 C08L 67/04 CA (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. The following formula (I) [However, in the formula (I), R ^a and R ^b are hydrogen, methyl, ethyl, propyl, and butyl and can be arbitrarily replaced with each other, but not all are hydrogen at the same time. x1 and x2 are an integer of 1 to 7 y1 and y2 are an integer of 0 to 20 (however, y1 and y2 are not simultaneously 0) z; an integer of 1 to 4 R; an alkyl group having 1 to 20 carbon atoms ] The composition containing the reactive monomer represented by these. 2. A compound having an OH group having 1 to 20 carbon atoms, which is subjected to ring-opening polymerization of at least two kinds of lactones in the presence of a catalyst. [However, in the formula (I), R ^a and R ^b are hydrogen, methyl, ethyl, propyl, and butyl and can be arbitrarily replaced with each other, but not all are hydrogen at the same time. x1 and x2 are an integer of 1 to 7 y1 and y2 are an integer of 0 to 20 (however, y1 and y2 are not simultaneously 0) z; an integer of 1 to 4 R; an alkyl group having 1 to 20 carbon atoms ] The manufacturing method of the composition containing the reactive monomer represented by these. 3. The composition according to claim 1, wherein R of the compound represented by formula (I) is a residue of trimethylolpropane. 4. The method according to claim 2, wherein the compound having an OH group having 1 to 20 carbon atoms is trimethylolpropane. 5. The method according to claim 2, wherein the lactone is at least one selected from β-methyl-δ-valerolactone and trimethylcaprolactone. 6. The method for producing a composition according to claim 2, wherein the catalyst is a compound containing at least one of tin, titanium, tungsten and zinc.