JP2548009B2 - Method for producing reactive polymer compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION “Industrial field of application” The present invention relates to an ethylene-based reactive polymer compound which is cured by ultraviolet rays, radiation or heat and can be used for molded articles, images, paints, inks, adhesives and the like. The present invention relates to a new manufacturing method.

"Prior Art" An ethylene-based reactive polymer compound having a repeating unit represented by the following general formula [IV] (hereinafter abbreviated as "this polymer") (Here, the substitution position of the substituent is arbitrary, and R ₁ represents the same group as described above.) Is described in JP-A-60-71604, JP-A-60-248704, or a collection of polymer articles. Vol. 43, No. 12, 901, etc.

According to these known documents, the present polymer is a vinylphenol represented by the following general formula [I]. (Here, the substitution position of the hydroxyl group is arbitrary.) Is polymerized by a known method to obtain polyvinylphenol having a molecular weight suitable for the purpose, and then haloalkyl vinyl ether X-R represented by the following general formula [II] _{1 -O-CH = CH 2 ......} [II] ( here, X is shows a chlorine atom or a bromine atom, R ₁ is. showing the same groups as previously described) has been prepared by reacting.

However, according to the above method, it is difficult to use the polyvinylphenol after the polymerization for the reaction with the haloalkyl vinyl ether unless it is first separated, purified, and redissolved, and the method becomes complicated. Moreover, in order to improve the reaction rate as always in reactions involving polymers, long-time reactions and special means are required, and in the above-mentioned polymer collections, the usual ones represented by KOH and the like are used. Despite the use of a dehydrohalogenating agent and a special catalyst such as a phase transfer catalyst, the reaction rate was low, and the residual phenolic hydroxyl groups tended to reduce the kaolin polymerization ability afterwards. .

Further, since the polyvinyl phenol produced by the known method has a wide molecular weight distribution, the polymer produced from the polyvinyl phenol does not show such excellent image forming ability even when it is used for the above-mentioned applications.

"Problems to be solved by the invention" As a result of the present inventors' studies in view of the above points, if the vinylphenols and haloalkyl vinyl ethers are directly reacted in the presence of a suitable catalyst and a suitable phenol, The inventors have found that the vinyl groups of the hynylphenols are preferentially polymerized preferentially and the vinyl groups of the haloalkyl vinyl ethers do not substantially react, and as a result, the present polymer can be efficiently obtained and the present invention has been achieved.

"Means for Solving Problems" That is, the present invention provides a vinylphenol represented by the general formula [I] and a haloalkyl vinyl ether represented by the general formula [II] as a basic alkali metal compound. The method for producing a reactive polymer compound represented by the above general formula [IV] is characterized in that a fuwenol represented by the following general formula [III] is allowed to coexist in the reaction in the presence.

(Here, the substitution position of the hydroxyl group is arbitrary.) When the compound represented by the general formula [IV] is produced, the phenols represented by the general formula [III] naturally react with the haloalkyl vinyl ethers. However, this reaction product is different from the original object of the method of the present invention. Further, the same reaction as the method of the present invention can be carried out without the coexistence of the above-mentioned phenols, but if the coexistence is not carried out, the polymerization of the above-mentioned vinylphenols will proceed and the yield of the target polymer Is reduced, or polyvinylphenol having a relatively low molecular weight is mixed. However, when the above phenols coexist,
Although the detailed reason is unknown, the production of polyvinylphenol is extremely suppressed.

Further, the molecular weight distribution of the present polymer obtained by the method of the present invention also tends to be narrow, and it provides a preferable effect when it is used for the purpose described below.

Examples of the compound represented by the general formula [I] that can be used in the method of the present invention include orthovinylphenol, metavinylphenol, and paravinylphenol. Considering their reactivity and the like, paravinylphenol is It is preferably used.

As the compound represented by the general formula [II], chloroethyl vinyl ether, bromoethyl vinyl ether, chloropropyl vinyl ether, bromobutyl vinyl ether and the like are preferably used. The general formula [II
The phenols represented by [I] include methylphenols, ethylphenols, propylphenols,
Butylphenols and phenylphenols can be exemplified.

Furthermore, examples of the basic alkali metal compound include sodium hydroxide, potassium hydroxide, sodium carbonate, lithium carbonate, potassium bicarbonate and the like.

In carrying out the method of the present invention using these compounds, the reaction sequence is not particularly limited, and they may be put in the reactor at once at the start of the reaction, and in some cases, haloalkyl vinyl ethers may be added. Vinylphenols and phenols may be added simultaneously to the reactor.

Regarding the usage ratio of vinylphenols and phenols, the former weight is 10% of the total weight of both.
Alternatively, the polymer compound of the present invention can be obtained even if the amount is less than that, but it should be 20% or more in view of the object of the present invention. Further, the amount of the haloalkyl vinyl ethers used is preferably equal to or more than 10 moles based on the total moles of the former two, and it is not necessary to use more than 10 moles.

As described above, coexistence of a basic alkali metal compound as a dehydrohalogenating agent is essential for this reaction, and examples of these include caustic soda, caustic potash, sodium carbonate,
Examples thereof include sodium bicarbonate. The amount used may be equimolar or more and 4 mol or less with respect to the total mol of the two kinds of phenols, and it is not necessary to use more than 4 mol.

A solvent is not always necessary for this reaction, but it may be preferable to use a solvent depending on the type of raw material compound used and the like. In such a case, there is no particular limitation as long as it is inert to the reaction, but aromatic hydrocarbons such as benzene and toluene, organic polar solvents such as dimethylformamide and dimethylsulfoxide, and ethylene glycol monoalkyl ethers. Ethers such as dioxane and dioxane are preferred.

In carrying out this dehydrohalogenation reaction, the use of a catalyst is not essential, but in view of shortening the reaction time, prevention of side reactions, etc., it is preferable to use a catalyst, so-called phase transfer catalyst. Is more effective. Examples of this catalyst include quaternary ammonium salts and crown ethers.

Thus, from the reaction mixture after the reaction, the solvent is used when a solvent is used, and the ether is used when the haloalkyl vinyl ether is used in excess of the other two, respectively, by a known means such as distillation. If it is excluded by using, a reaction mixture in which the hydroxyl group derived from the raw material is substantially a vinyloxyalkyloxy group is obtained.

Next, the present polymer is separated from the mixture, and it can be easily separated by using the difference in solubility between the present polymer and the compound derived from a phenol in an organic solvent. In general, the polymer is almost insoluble in lower aliphatic alcohols, and other reaction products are well soluble.
It can be easily separated using this alcohol.

The present polymer precipitated and separated by such a method may be isolated by a known operation such as filtration and drying.

The molecular weight of the present polymer produced by the method as described above can be appropriately selected by changing the reaction time or changing the temperature, but the weight average molecular weight is preferably 50.
It is preferably 00 or more.

Although the reason for this polymer produced by the method of the present invention is not clear, the molecular weight distribution becomes narrow, and the ratio of the weight average molecular weight (Mw) to the viscosity average molecular weight (Mn) is usually 1.6 or less. Many, and a narrow molecular weight distribution like this brings about a preferable effect for the following applications.

If the molecular weight distribution of the present polymer is narrowed, the obtained resin molded product becomes more homogeneous, the viscosity at the time of melting becomes smaller, the handling thereof becomes easier, and the solubility in a solvent is significantly improved.

As described above, the present polymer has, for example, a vinyl group which reacts with light irradiation, and can be used as a photosensitive resin raw material for forming a printed image by this irradiation.

As is well known, various resins suitable for the above-mentioned applications have been proposed, but the present polymer completes the crosslinking reaction in a short time,
Moreover, it is not affected by oxygen at all, and as described above, the molecular weight distribution of the present polymer tends to be narrow, so that finer particles are extremely suitable when an image is required,
It has performance superior to conventional photosensitive resins.

As is apparent from the structure of the polymer, it goes without saying that it can be used as a raw material for thermosetting resin.
It can be used as a resin for printed circuits.

As described above, the present invention provides a method for producing a reactive polymer compound that can be an extremely useful resin raw material.

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

Example 1 150 g of toluene was added to 150 g of a mixture of p-ethylphenol 65%, p-cresol 4%, phenol 1% and p-vinylphenol 30%, and a reflux condenser, a stirrer,
Place in 1 flask equipped with drop load and thermometer.
120 g of sodium hydroxide was further added thereto, the internal temperature was adjusted to 50 ° C., and then a solution of 36.5 g of tetrabutylammonium bromide dissolved in 325 g of 2-chloroethyl vinyl ether was added dropwise over 1 hour.

After the dropping was completed, the internal temperature was kept at 60 ° C. and the reaction was continued for 5 hours to complete the reaction. Then, about 300 g of water was added and the mixture was stirred and allowed to stand. The separated organic layer was washed with water and distilled under the conditions of 20 to 80 ° C./70 to 20 mmHg to recover water, solvent and unreacted 2-chloroethyl vinyl ether. The obtained mixed composition is 25 ~
It was liquid at 35 ° C.

Methanol was added to the liquid mixture, and the mixture was stirred well and then filtered to separate the methanol-insoluble portion. This operation was repeated twice to obtain 81 g of a solid product at room temperature.

Gel permeation chromatography (GPC) analysis of this product revealed that the product was a polymer compound with one peak, and its number average molecular weight was 5530.
The weight average molecular weight was calculated to be 7850. The ratio (Mw / M
n) was 1.42.

Furthermore, in the infrared absorption spectrum of this polymer compound, no absorption centered at 3400 cm ^-1 based on the phenolic hydroxyl group was found, while absorption peaks based on the vinyl group were found at 1610 cm ^-1 and 980 cm ^-1. Was given. Also, large absorption peaks based on ether groups were observed at 1240 cm ^-1 and 1200 cm ^-1 .

^{From the 1} H-NMR and ¹³ C-NMR analysis results, it was confirmed that the polymer compound was poly (4-vinyloxyethoxy) styrene according to the above general formula [IV].

The yield of the obtained polymer compound was 85.3% with respect to the p-vinylphenol used.

Example 2 A mixed solution of 56% m-cresol, 1% phenol, 2% p-ethylphenol, 1% p-cresol and 40% p-vinylphenol was used as a raw material, and potassium hydroxide was used instead of sodium hydroxide. Example 1 was repeated using benzyl ethyl ammonium chloride as the catalyst.

The polymer was separated and purified from the mixture after the reaction using methanol.

As a result of analysis by the same method as in Example 1, it was found that this polymer had a target structure.

The number average molecular weight calculated from GPC analysis was 6050, the weight average molecular weight was 8600, and the (Mw / Mn) was 1.42. The yield of this polymer was 85 g, and the yield based on the p-vinylphenol used was 89%.

Example 3 150 g of a mixture of 70% p-ethylphenol, 6% p-cresol, 2% phenol and 22% p-vinylphenol was used without a solvent, and the reaction was carried out by dripping for 2 hours and aging for 6 hours. The temperature was maintained at 50 ° C. and the method described in Example 1 was repeated.

The precipitate separated and purified using methanol was used in Example 1.
When analyzed in the same manner as described above, this was found to be the present polymer. The yield was 46 g, and the yield based on the p-vinylphenol used was 88%.

The number average molecular weight was 6370, the weight average molecular weight was 8790, and the Mw / Mn was calculated to be 1.38.

Examples 4 to 6 Using the raw materials and the like shown in Table 1, the reaction was carried out according to the method described in Example 1, and the results are shown in Table 2.

Comparative Example 1 A mixture of 200 g of toluene and 150 g of p-vinylphenol was mixed with the same apparatus as in Example 1 using sodium hydroxide.
120 g was added and the internal temperature was kept at 50 ° C., and a solution prepared by dissolving 36.5 g of tetrabutylammonium bromide in 325 g of 2-chloroethyl vinyl ether was added dropwise over 1 hour. After the dropping was completed, the internal temperature was kept at 60 ° C., the reaction was continued for 5 hours, and then the reaction was terminated.
After completion of the reaction, sodium chloride, water, the solvent and unreacted chloroethyl vinyl ether were removed in the same manner as in Example 1 to obtain 195 g of a solid product at room temperature.

The reaction mixture was analyzed by GPC and a spectrum with two broad main peaks was obtained. Infrared absorption spectrum showed absorption by phenolic hydroxyl group.

The mixture was separated using methanol, toluene and hexane, and the infrared spectrum of the separated product was found to be a mixture of the present polymer containing about 10% of poly (p-vinylphenol). The weight average molecular weight of this polymer is 9850, the number average molecular weight is 4030, and Mw / Mn is
Calculated as 2.44.

"Effect of the invention" The method of the present invention provides a novel method for producing vinyloxyethoxypolystyrenes useful as a raw material for a photosensitive resin, and the compound produced by this method is produced by a conventionally known method. Has better performance.

Claims (3)

(57) [Claims] 1. A vinylphenol represented by the following general formula [I]: (Here, the substitution position of the hydroxyl group is arbitrary.) A haloalkyl vinyl ether represented by the following general formula [II] is used as X—R ₁ —O—CH═CH ₂ ... [II] (where X is Represents a chlorine atom or a bromine atom, and R ₁ represents an alkylene group having 2 to 4 carbon atoms.) When reacting in the presence of a basic alkali metal compound,
A method for producing a reactive polymer compound represented by the following general formula [IV], which comprises allowing phenols represented by the following general formula [III] to coexist. (Here, the substitution position of the hydroxyl group is arbitrary.) (Here, the substitution position of the substituent is arbitrary, and R ₁ represents the same group as described above.) 2. The vinylphenol is p-vinylphenol, R ₁ is a 1,2-ethylene group, and R ₂ is an alkyl or aryl group having 1 to 15 carbon atoms. A method for producing the reactive polymer compound according to the item. 3. The method for producing a reactive polymer compound according to claim 1 or 2, wherein the weight average molecular weight is 5000 or more and the ratio of the weight average molecular weight to the number average molecular weight is 1.6 or less. .