JPH07300444A - New acrylic monomer and its production - Google Patents

Abstract

PURPOSE:To provide a new acrylic monomer having a chain carbonate structure in an ester residue and useful as a raw material for the production of a polymer having chain carbonate pendant groups by copolymerization. CONSTITUTION:This acrylic monomer is a compound expressed by formula I (R<1> is H or methyl,; R<2> and R<3> each is a 2-8C alkylene chain; R<4> is a <=20C primary alcohol residue; (m) is O-6; (n) is l-100). The compound of formula I can be produced by the transesterification reaction of a monoalcohol of formula II with a reactive derivative of acrylic acid or methacrylic acid (e.g. a lower alkyl ester) in the presence of a catalyst (e.g. a protonic acid). The reaction is preferably carried out at a temperature between the boiling point of the by-produced methanol, etc., and 150 deg.C while removing the by-produced methanol, etc., from the system to shorten the reaction time and prevent the polymerization. Polymers copolymerized with the monomer have improved physical properties such as oilresistance, heat-resistance and low-temperature impact resistance.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel (meth) acrylic acid ester-based monomer having a chain carbonate structure in an ester residue and a method for producing the same.

The physical and chemical properties of polymers of (meth) acrylic acid esters are governed by the ester residue which serves as the pendant group for the polymer. The present invention provides an acrylic polymer having a carbonate structure in an ester residue, which can give a polymer produced by copolymerization unique properties based on the structure.

DISCLOSURE OF THE INVENTION In accordance with the present invention , Formula I

[Chemical 3] (Wherein R ¹ is hydrogen or methyl, R ² and R ³ are independently an alkylene chain having 2 to 8 carbon atoms, R ⁴ is a primary alcohol residue having up to 20 carbon atoms, m is 0 or 1 to 6) An integer, n is an integer of 1-100.) Is provided. The present invention also relates to a method for producing the acrylic monomer. This method has the formula II

[Chemical 4] A monoalcohol having (wherein R ² , R ³ , R ⁴ , m and n are the same as above) is acylated with a reactive derivative of acrylic acid or methacrylic acid.

Preferred Embodiment A method for synthesizing an acrylic monomer according to the present invention will be described in detail according to steps. 1. Formula II of monoalcohol

[Chemical 5] Is a alcohol of the formula R ⁴ OH (R ⁴ is as defined above), or a lactone adduct of the alcohol,

[Chemical 6] (In the formula, m is an integer of 1 to 6, and R ³ and R ⁴ are the same as above.)

[Chemical 7] It can be synthesized by ring-opening (polymerizing) the aliphatic cyclic carbonate.

Alcohols of the formula R ⁴ OH include methyl alcohol, ethyl alcohol and n-, in which R ⁴ is an alkyl group.
Propyl alcohol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, isobutyl alcohol, hexanol, 2-ethylhexanol, stearyl are, etc., ethylene glycol monomethyl ether and ethylene glycol monoethyl in which R ⁴ is a glycol monoalkyl ether residue. ether is diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, allyl alcohol R ⁴ is alkenyl, propargyl alcohol R ⁴ is alkynyl, R ⁴ is benzyl alcohol is aralkyl.

The lactone adducts of these alcohols can be synthesized by a conventional method by ring-opening the lactone, which is typically ε-caprolactone, with the alcohol. It is also possible to produce a monofunctional polycaprolactone oligomer obtained by ring-opening addition polymerization of ε-caprolactone using the alcohol as an initiator. Epsilon-caprolactone is preferred, but enanthlactone, β-propiolactone, dimethylpropiolactone, butyrolactone, γ-valerolactone, γ-caprolactone, γ-caprylolactone, crotlactone, δ-valerolactone, δ-caprolactone, etc. Can also be used.

The other raw material, cycloaliphatic carbonate, is a method of depolymerizing a polymer obtained by the reaction of glycol and dialkyl carbonate (JP-A-2-5).
6356), or by reacting the corresponding alkylene oxide with carbon dioxide. The cyclic carbonate has a 5-membered ring, a 6-membered ring or a 7-membered ring structure, and specific examples thereof include ethylene carbonate as a 5-membered ring, 1,3-propylene carbonate as a 6-membered ring and neopentyl glycol carbonate (5,5 −
It may also be named dimethyl-1,3-dioxan-2-one. ) And 7-membered rings include 1,4-butanediol carbonate and the like. Neopentyl glycol carbonate is preferred. The reason is that this compound can be synthesized from a commercially available raw material in a relatively short step, is stable under normal conditions, but is relatively mild in the presence of a catalyst under relatively mild conditions. This is because a ring-opening addition reaction occurs with.

The charged amount of the cycloaliphatic carbonate with respect to the monoalcohol or the lactone adduct thereof may be 1: 0.5 or more in molar ratio. When charged in excess of 1: 1, at least part of the cyclic carbonate undergoes ring-opening addition polymerization.

Examples of the catalyst used in the ring-opening addition reaction of a cyclic carbonate include organic tin compounds such as dibutyltin oxide, dibutyltin dilaurate, monobutyltrichlorotin, dibutyldichlorotin, tributylmonochloros, and hydroxybutyltin oxide, as well as primary chloride. Tin, stannous bromide, stannous iodide, etc. can be used. Furthermore, phosphotungstic acid and silicotungstic acid can also be used. Also, Amber List 1
Strong acid cation exchange resin such as 5E, hydrogen fluoride, hydrogen chloride, hydrogen bromide, sulfuric acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, etc. Sted acids are mentioned. Further, examples of the Bronsted acid anion onium salt include nitrogen, sulfur, phosphorus or iodo onium salts. Below are some typical examples.

(I) Quaternary ammonium salt type compound: N, N-dimethyl-N-benzylanilinium antimony hexafluoride N, N-diethyl-N-benzylanilinium boron tetrafluoride N, N-diethyl-N -Benzylpyridinium antimony hexafluoride N, N-diethyl-N-benzylpyridinium trifluoromethanesulfonic acid N, N-dimethyl-N- (4-methoxybenzyl) pyridinium antimony hexafluoride N, N-diethyl-N- (4 -Methoxybenzyl) pyridinium antimony hexafluoride N, N-diethyl-N- (4-methoxybenzyl) toludinium antimony hexafluoride N, N-dimethyl-N- (4-methoxybenzyl) toludinium antimony hexafluoride (ii) Sulfonium salt type compound: triphenylsulfonium tetrafluoride Boron Fluoride Triphenylsulfonium Antimony Hexafluoride Triferel Sulfonium Arsenic Hexafluoride ADEKA CP-66 (Asahi Denka Kogyo) ADEKA CP-77 (Asahi Denka Kogyo) Tri (4-methoxyphenyl) sulfonium hexafluoroarsenic diphenyl (4-Phenylthiophenyl) sulfonium arsenic hexafluoride (iii) Phosphonium salt type compound: ethyltriphenylphosphonium antimony hexafluoride Tetrabutylphosphonium antimony hexafluoride (iv) Iodonium salt type compound: diphenyliodonium hexafluoride arsenic di -4-Chlorophenyliodonium arsenic hexafluoride Di-4-bromophenyliodonium arsenic hexafluoride Di-p-tolyliodonium arsenic hexafluoride Phenyl (4-methoxyphenyl) iodonium arsenic hexafluoride

The anionic components of the above-mentioned onium salts include, for example, acetic acid, propionic acid, octanoic acid, lauric acid, stearic acid and other aliphatic carboxylic acids, benzoic acid and other aromatic carboxylic acids, benzenesulfonic acid, toluenesulfone. An acid, an aromatic sulfonic acid such as dodecylbenzenesulfonic acid, or an onium salt substituted with an anionic component such as perchloric acid may be used.

Alkali alkali metals such as n-butyllithium and sec-butyllithium, Li- and Na
Alkali metal alcoholates such as-, K-ethylate, -butyrate, -isobutyrate, -t-butyrate and -octylate are also effective catalysts. In addition, diethylamine, triethylamine, dibutylamine, N,
Amines such as N-dimethylcyclohexylamine, dimethylbenzylamine, hexamethylenetetramine, 1,8-diazabicyclo [5,4,0] -7-undecene are also effective catalysts.

The amount of catalyst added is 1 ppm to 50,000.
ppm, preferably 5-5000 ppm.

When the amount of the catalyst added is less than 1 ppm, the polymerization reaction rate is extremely slow and has no practical meaning.
On the other hand, if it exceeds 50,000 ppm, many side reactions due to decarboxylation or transesterification occur, which is not preferable.

The reaction temperature depends on the type of the starting monoalcohol and the catalyst, but is generally room temperature to 15
The temperature is 0 ° C.

The reaction is solvent-free or aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl isobutyl ketone, halogenated hydrocarbons such as dichloromethane and dichloroethane, and tetrahydrofuran. , An ether such as 1,4-dioxane, or an aprotic organic solvent such as acetonitrile, nitrobenzene, or nitromethane.

The use of a solvent has the effect of lowering the viscosity of the reaction crude liquid in the system after completion of the reaction, and makes the temperature uniform during the reaction by making the system uniform. Is. The amount of the solvent used is 5 to 80% by weight, preferably 10 to 50% by weight.

When the amount of the solvent used is more than 80% by weight, the reaction becomes slow, which is not preferable. On the contrary, if the amount of the solvent used is less than 5% by weight, the effect of decreasing the viscosity is small.

Usually, in the reaction, the solvent, the monoalcohol, the cyclic carbonate compound and the catalyst are charged into the reactor, and then the temperature is raised to the above range.

The end point of the addition reaction of the aliphatic cyclic carbonate is carried out by gas chromatography, and usually the time point when the concentration of the aliphatic cyclic carbonate becomes 1% or less is regarded as the end point of the reaction.

2. The acrylic monomer of the present invention can be obtained by acylating the monoalcohol synthesized in the acylation step 1 with a reactive derivative of acrylic acid or methacrylic acid. Acylation can be achieved by transesterification using a lower alkyl ester of acrylic acid or methacrylic acid as the reactive derivative. Sulfuric acid for this reaction,
It is preferable to use a protonic acid such as p-toluenesulfonic acid, boron trifluoride, a Lewis acid such as stannous chloride, or a strongly acidic cation exchange resin such as Amberlyst 15E as a catalyst. Further, it is preferable to remove by-produced alcohol such as methanol to the outside of the system to proceed the reaction.

Acylation can also be achieved using halides of acrylic or methacrylic acid, preferably chloride. In this case, at least an equivalent amount of a tertiary amine such as pyridine, trimethylamine, triethylamine and tributylamine, or a secondary amine such as dicyclohexylamine is preferably present in order to bond by-produced hydrogen halide.

From the viewpoint of shortening the reaction time and preventing polymerization, the reaction is preferably carried out at a boiling point of not less than 150.degree. In order to prevent thermal polymerization of acrylic acid or methacrylic acid, polymerization inhibitors such as hydroquinone and its methyl ether, 2,4-dimethyl-6
-T-Butylphenol, 3-hydroxythiophenol, α-nitroso-β-naphthol, p-benzoquinone, 2,5-dihydroxy-p-quinone, copper salts, etc., especially added to the system in trace amounts of hydoquinone and its methyl ether. It is preferable to place it.

3. Purification of Monomers The reaction product can be purified by various methods. Generally, the reaction mixture is dissolved in an aromatic hydrocarbon solvent such as benzene, toluene, xylene, etc., an aliphatic hydrocarbon solvent such as hexane, heptane, octane, etc., an ester solvent such as ethyl acetate, butyl acetate, etc., and washed with water. preferable. When the reaction product contains an acid catalyst, it is washed with alkali before washing with water. If a cation exchange resin is used as the catalyst, it may simply be filtered. After washing or filtering, the liquid is subjected to vacuum distillation to remove the solvent and low boiling impurities. Needless to say, appropriate temperature and pressure should be selected according to the solvent used at this time.

The thus-obtained monomer is useful as a raw material for a polymer having chain carbonate pendant groups, either alone or by copolymerization with another monomer. For example, copolymerization with the acrylic monomer of the present invention can improve physical properties of the polymer such as oil resistance, heat resistance and low temperature impact resistance.

Example 1 (Ring Opening Reaction of Cyclic Carbonate) 84 g of methanol, 169 g of neopentyl glycol carbonate and 30.3 g of Amberlyst 15E3 as a reaction catalyst were placed in a four-necked flask equipped with a thermometer, a cooling tube and a stirrer. The reaction was carried out under reflux of methanol for 2 hours.

When the reaction was traced by NMR, the reaction rate of carbonate was 97.8%.

0.735 to 0.908 ppm by NMR
The peak seen at 1 supports the methyl group due to ring opening of neopentyl glycol carbonate, and the peak seen at 1.139 ppm supports the unreacted methyl group of neopentyl glycol carbonate. 3.129-3.162p
The peak seen at pm supports the methylene group adjacent to the terminal hydroxyl groups of the methanol adduct and the unreacted methyl group of methanol.

The peaks at 3.672 to 3.675 ppm are the methyl groups of the methanol adduct, 3.845.
The peak seen at 3.847 ppm is a methylene group due to ring-opening of neopentyl glycol carbonate, 4.0.
The peak at 79 ppm supports the methylene group of unreacted neopentyl glycol carbonate, and the resulting product is a product of neopentyl glycol carbonate ring-opened with methanol. Number of repeating units 0.5.

(Esterification) A neopentyl glycol carbonate adduct of methanol 5 was added to a four-necked flask equipped with a dropping funnel, an air introduction tube, a thermometer, a cooling tube, and a stirrer.
6 g, pyridine 27 g, 1,2-dichloroethane 50 g as a solvent, and hydroquinone monomethyl ether 0.0276 g as a polymerization inhibitor were added and stirred. 36 g of methacrylic acid chloride in the dropping funnel, 1,2 as the solvent
-36 g of dichloroethane was added and added dropwise over 30 minutes. The mixture was reacted at 20 ° C. for 3 hours while passing nitrogen.

When the reaction was traced by NMR, the reaction rate of the neopentyl glycol carbonate adduct of methanol was 67.4%.

0.810 to 0.992 ppm in NMR
The peaks seen in Figure 2 support the methyl groups of neopentyl glycol carbonate of the methacrylic acid ester and the methyl groups of the unreacted neopentyl glycol carbonate adduct of methanol. 1.877-1.927
The peak seen in ppm supports the methyl group of the methacrylic group of the esterified product and the methyl group of the methacrylic group of unreacted methacrylic acid chloride.

The peak at 3.129 ppm is a methylene group adjacent to the terminal hydroxyl group of the unreacted methanol adduct, and the peak at 3.318 ppm is a methylene group adjacent to the ester group of the esterified product. ~
The peak seen at 3.677 ppm supports the methyl groups of the esterified product and the unreacted methanol adduct. The peaks observed at 3.845 to 3.847 ppm are methylene groups of unreacted methanol adduct and 3.9.
The peak seen at 33 to 3.950 ppm supports the methylene group adjacent to the carbonate group of the esterified product.
The peaks seen at 5.673 to 6.041 ppm are presumed to be the methacrylic group of the esterified product and the methacrylic group of unreacted methacrylic acid chloride, and the obtained product was neopentyl of methanol due to methacrylic acid chloride. It is supported that the glycol carbonate adduct is an esterified product.

Example 2 (Ring opening reaction) Methanol 1 was added to the same reactor as in Example 1.
9.2 g, neopentyl glycol carbonate 390
g, and Amberlyst 15E14g as a reaction catalyst were put therein and reacted at 100 ° C. for 4 hours.

When the reaction was traced by NMR, the reaction rate of carbonate was 97.0%. The number of repeating units is 4.9.

(Esterification) Methanol neopentyl glycol carbonate 5 was placed in the same reactor as in Example 1.
200 g of a molar adduct, 29.7 g of pyridine, 50 g of 1,2-dichloroethane as a solvent, and 0.0693 g of hydroquinone monomethyl ether as a polymerization inhibitor were added,
It was stirred. 30. Methacrylic acid chloride in the dropping funnel.
6 g and 31 g of 1,2-dichloroethane as a solvent were added and added dropwise into the reaction vessel over 30 minutes. The mixture was reacted at 20 ° C. for 3 hours while passing nitrogen.

When the reaction was traced by NMR, the reaction rate of a 5 mol adduct of neopentyl glycol carbonate with methanol was 79.0%.

Example 3 (Ring Opening Reaction) In the same reactor as in Example 1, 7.4 g of n-butyl alcohol, 130 g of neopentyl glycol carbonate and 0.19 g of p-toluenesulfonic acid as a reaction catalyst were placed at 100 ° C. The reaction was carried out for 4 hours.

When the reaction was traced by NMR, the reaction rate of carbonate was 98.1%. 10 repeating units.

(Esterification) In a reaction apparatus similar to that of Example 1, 373.7 g of a 10-mole adduct of n-butyl alcohol with neopentyl glycol carbonate and 29.
7 g, 50 g of 1,2-dichloroethane as a solvent, and hydroquinone monomethyl ether 0.0 as a polymerization inhibitor.
693 g was added and stirred. 30.6 g of methacrylic acid chloride and 31 g of 1,2-dichloroethane as a solvent were placed in a dropping funnel, and the mixture was dropped into the reaction vessel over 30 minutes. The mixture was reacted at 20 ° C. for 3 hours while passing nitrogen.

When the reaction was traced by NMR, n-
The reaction rate of the 10-mol addition product of neopentyl glycol carbonate of butyl alcohol was 73.4%.

Example 4 (Ring opening reaction) In the same reactor as in Example 1, 60 g of isopropyl alcohol, 130 g of neopentyl glycol carbonate, and dibutyltin oxide as a reaction catalyst were used.
49 g was put and it was made to react at 60 degreeC for 8 hours.

When the reaction was traced by NMR, the reaction rate of carbonate was 96.4%. Number of repeating units 1.

(Esterification) In a four-necked flask equipped with an air introduction tube, a thermometer, a solvent distillation cooling tube, and a stirrer, 190 g of neopentyl glycol carbonate 1-mol adduct of isopropyl alcohol and 200 methyl methacrylate.
g, 1.9 g of p-toluenesulfonic acid as a reaction catalyst,
0.0117 g of hydroquinone monomethyl ether was added as a polymerization inhibitor, and the mixture was allowed to react at 100 ° C. for 6 hours while nitrogen was passed to remove the distillate.

When the reaction was traced by NMR, the reaction rate of a 1 mol adduct of neopentyl glycol carbonate with isopropyl alcohol was 81.2%.

Example 5 (Ring Opening Reaction) In the same reactor as in Example 1, 27.1 g of stearyl alcohol, 65 g of neopentyl glycol carbonate and 0.10 of triethylamine as a reaction catalyst were used.
g was added and the mixture was reacted at 60 ° C. for 8 hours.

When the reaction was traced by NMR, the reaction rate of carbonate was 96.0%. Repeat unit number 5.

(Esterification) In a reactor similar to that of Example 4, 92 g of a 5 mol adduct of neopentyl glycol carbonate of stearyl alcohol, 20 g of methyl methacrylate were added.
g, p-toluenesulfonic acid 0.19 as a reaction catalyst
g and 0.00336 g of hydroquinone monomethyl ether as a polymerization inhibitor were added and the reaction was carried out at 100 ° C. for 6 hours while purging nitrogen to remove the distillate.

When the reaction was traced by NMR, the reaction rate of a 5 mol addition product of neopentyl glycol carbonate of stearyl alcohol was 75.4%.

Example 6 (Ring Opening Reaction) In a reaction apparatus similar to that of Example 1, 1 mol adduct of n-butyl alcohol with 1 mol of ε-caprolactone was added.
g, neopentyl glycol carbonate 13 g, and p-toluenesulfonic acid 0.19 g as a reaction catalyst were put therein and reacted at 20 ° C. for 6 hours while passing air.

When the reaction was traced by NMR, the reaction rate of carbonate was 91.8%. 1 repeating unit of carbonate.

(Esterification) 15.9 g of a 1 mol adduct of neopentyl glycol carbonate of 1 mol adduct of ε-caprolactone of n-butyl alcohol, 10 g of methyl methacrylate and p as a reaction catalyst were placed in the same reaction apparatus as in Example 4. -Toluenesulfonic acid 0.095 g, hydroquinone monomethyl ether 0.0077 as a polymerization inhibitor
7 g was added and the reaction was carried out at 100 ° C. for 6 hours while purging nitrogen to remove the distillate.

When the reaction was traced by NMR, n-
The reaction rate of the neopentyl glycol carbonate adduct of 1 mol of ε-caprolactone adduct of butyl alcohol was 74.2%.

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[Procedure amendment]

[Submission date] June 7, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0005

[Correction method] Change

[Correction content]

Alcohols of the formula R ⁴ OH include methyl alcohol, ethyl alcohol and n-, in which R ⁴ is an alkyl group.
Propyl alcohol, isopropyl alcohol, n- butyl alcohol, t- butyl alcohol, isobutyl alcohol, hexanol, 2-ethylhexanol, etc. stearyl alcohol, ethylene glycol monomethyl ether R ⁴ is glycol monoalkyl ether residue, ethylene glycol monomethyl ethyl ether, diethylene glycol monomethyl ether is diethylene glycol monoethyl ether, allyl alcohol R ⁴ is alkenyl, propargyl alcohol R ⁴ is alkynyl, R ⁴ is benzyl alcohol is aralkyl.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

The end point of the addition reaction of the aliphatic cyclic carbonate is carried out by NMR or gas chromatography. Usually, the time point when the concentration of the aliphatic cyclic carbonate becomes 1% or less is regarded as the end point of the reaction.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

The reaction is aimed at shortening the reaction time and preventing polymerization.
The boiling point of methanol, which is a by-product of
It is preferably applied. Acylation can also be achieved using halides of acrylic or methacrylic acid, preferably chloride. In this case, it is preferable that at least an equivalent amount of a tertiary amine such as pyridine, trimethylamine, triethylamine, or tributylamine, or a secondary amine such as dicyclohexylamine is present in order to bond by-produced hydrogen halide.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takaaki Fujiwa, 4-chome, Kuma, Otake-shi, Hiroshima 13-5-402 (72) Inventor Takeharu Tabuchi 4-chome, 4-kuba, Otake, Hiroshima

Claims (6)

[Claims] 1. A compound of formula I (Wherein R ¹ is hydrogen or methyl, R ² and R ³ are independently an alkylene chain having 2 to 8 carbon atoms, R ⁴ is a primary alcohol residue having up to 20 carbon atoms, m is 0 or 1 to 6) An integer, n is an integer of 1 to 100). 2. m is 0 and R ² is 2,2-dimethyl-
The acrylic monomer according to claim 1, which is a 1,3-propylene chain and n is an integer of 1 to 20. 3. R ³ is a 1,5-pentylene chain, m is an integer of 1 to 3, and R ² is 2,2-dimethyl-1,3.
-Acrylic monomer according to claim 1, which is a propylene chain and n is an integer from 1 to 20. 4. Formula II: (In the formula, R ² and R ³ are independently an alkylene chain having 2 to 8 carbon atoms, R ⁴ is a primary alcohol residue having up to 20 carbon atoms, m is 0 or an integer of 1 to 6, and n is 1 to 100. Is a whole number of 4) and a reactive derivative of acrylic acid or methacrylic acid are reacted with each other. 5. The method for producing an acrylic monomer according to claim 4, wherein the reactive derivative of acrylic acid or methacrylic acid is a lower alkyl ester. 6. The method for producing an acrylic monomer according to claim 4, wherein the reactive derivative of acrylic acid or methacrylic acid is an acid halide.