JPH0859590A - Acrylonitrile dimer, acrylonitrile derivative, their production and polymerizable composition - Google Patents

Abstract

PURPOSE: To obtain the subject new compound useful as a raw material for various high molecular materials such as coatings or adhesives or a constituent for curing compositions, and capable of giving polymers having excellent resistance to heat, chemicals and oil, etc. CONSTITUTION: This new compound, acrylonitrile dimer of formula I, is obtained by reaction between acrylonitrile and formaldehyde in the presence of a tertiary amine at the charge molar ratio of pref. (6:40) to (10:90). The second objective acrylonitrile derivative can be obtained by reaction between acrylonitrile and formaldehyde in the presence of a tertiary amine at the charge molar ratio of (95:5) to (60:40). The third objective polymerizable composition containing >=50mol% of the acrylonitrile dimer has improved heat resistance, while, another version of the polymerizable composition containing >=50mol% of the acrylonitrile derivative and <20mol% of the acrylonitrile dimer has improved transparency.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel vinyl addition-polymerizable compound, that is, an acrylonitrile dimer having a specific molecular structure, which can be used as a raw material for producing various polymer materials and a constituent of a curable composition. Body or acrylonitrile derivative. The polymer obtained by vinyl addition polymerization of this acrylonitrile dimer and acrylonitrile derivative has excellent heat resistance, chemical resistance, oil resistance, cold resistance, mechanical strength, etc.
It can be used for various polymer materials such as adhesives and molded bodies.

[0002]

2. Description of the Related Art Since various functional groups can be introduced into an acrylic acid ester-based monomer through an ester bond, many derivatives have been synthesized up to now and used as raw materials for various functional polymer materials. in use. On the other hand, acrylonitrile cannot be introduced with a functional group through an ester bond, there are few derivatives reported so far, and it is industrially unavailable except for acrylonitrile and methacrylonitrile.

As a derivative of acrylonitrile, Japanese Examined Patent Publication No. 45-2361 discloses the synthesis of various α- (oxyalkyl) acrylonitriles by reacting acrylonitrile with an aldehyde using tricyclohexylphosphine as a catalyst. However, since the catalyst used in this method is expensive, its industrial application range is limited.

In Japanese Patent Laid-Open No. 61-134353, acrylonitrile or an acrylate ester is reacted with formaldehyde using a specific tertiary amine as a catalyst, and α-
The synthesis of (hydroxymethyl) acrylonitrile or α- (hydroxymethyl) acrylic acid ester is disclosed. European Patent No. 196708 describes that the yield of α- (hydroxymethyl) acrylonitrile is improved by carrying out this reaction under high pressure. Further, International Patent Publication No. 9181861 proposes a process in which the same reaction is carried out in a short time by using a microwave.

The above-mentioned α- (hydroxymethyl) acrylonitrile is interesting as an acrylonitrile having a hydroxyl group in its molecule, but its radical polymerizability is inferior to that of acrylonitrile, so that its application range is limited.

Further, US Pat. No. 4,999,410, [Macromolecules, Vol. 21, p. 545, (1989)] and [Macromolecules, Vol. 24, p. 2036, ( 1991)], in the synthesis of the above α- (hydroxymethyl) acrylic acid ester, an ether dimer is produced as a by-product by a dehydration reaction, and the dimer can be used as a cross-linking agent. When the solution polymerization of this dimer is carried out under appropriate conditions,
It is disclosed that a solvent-soluble cyclized polymer having a six-membered ring structure in the main chain and having excellent heat resistance can be obtained. But,
There is no description about specific description of acrylonitrile dimer, synthesis examples, and spectral data.

[0007]

Since acrylonitrile is inexpensive and excellent in polymerizability, and the resulting polymer is highly crystalline and excellent in chemical resistance, oil resistance, gas barrier property, etc., it is used as a raw material for general-purpose polymer materials. Used in large quantities. However, since the obtained polymer is crystalline, the transparency is poor, and the thermal stability is poor, so that it is used only as a small amount of a copolymerization component in applications other than synthetic fibers. Therefore, it has been considered that if an acrylonitrile-based monomer that gives an amorphous polymer having excellent heat resistance can be produced from an inexpensive raw material, it can be used for highly versatile applications not limited to synthetic fibers.

[0008]

DISCLOSURE OF THE INVENTION In view of the problems of the prior art, the present inventors have a weak point while keeping the excellent chemical resistance, oil resistance, gas barrier property and economical efficiency of acrylonitrile polymer. A method for improving transparency and heat resistance was investigated and attention was paid to a cyclized polymer. That is, in general, a cyclized polymer is excellent in heat resistance and transparency (amorphous), and by adding this feature to the properties of the acrylonitrile polymer itself, a unique resin material that solves the above problems Was estimated to be obtained.

Then, considering the synthesis of a novel acrylonitrile dimer represented by the following formula [A] (hereinafter simply referred to as "acrylonitrile dimer") as a raw material of the cyclized polymer, its production method is considered. As a result of diligent studies, it was possible to obtain the acrylonitrile dimer by reacting acrylonitrile and formaldehyde in the presence of a tertiary amine catalyst. CH ₂ ═C (CN) CH ₂ OCH ₂ C (CN) ═CH ₂ ... [A]

However, in addition to the target product, many products obtained by this reaction include an acrylonitrile derivative represented by the following formula [B] (hereinafter simply referred to as "acrylonitrile derivative") having a similar molecular structure. Was included. _{CH 2 = C (CN) CH} 2 OCH 2 CH 2 CN ... [B]

As a result of further studies, it was found that this derivative can be reduced by changing the charging ratio of acrylonitrile and formaldehyde. It was confirmed that the obtained high-purity acrylonitrile dimer was excellent in homopolymerization and copolymerizability, and that the polymer was very excellent in heat resistance, transparency, chemical resistance and oil resistance.

On the other hand, an acrylonitrile polymer is inferior in transparency because it is crystalline, and has a relatively high glass transition point. Therefore, when it is copolymerized with a diene monomer or an acrylate ester to give an oil resistant rubber, There was a problem that cold resistance was reduced. However, it has been found that the above-mentioned acrylonitrile derivative has excellent radical polymerizability, and the obtained polymer has oil resistance equivalent to that of acrylonitrile and has a glass transition point lower than that of acrylonitrile. Therefore, it was confirmed that when the acrylonitrile derivative was used as a copolymerization component, the glass transition point of the polymer was lowered, the transparency and the cold resistance were increased, and the above problems were solved.

This acrylonitrile derivative can be produced by reacting acrylonitrile and formaldehyde in the presence of a tertiary amine catalyst in the same manner as in the process for producing an acrylonitrile dimer. Further, by changing the charging ratio of acrylonitrile and formaldehyde, the yield of It turns out that the rate can be increased. Hereinafter, the present invention will be described in detail.

(Raw material) As acrylonitrile used as a raw material for the acrylonitrile dimer or acrylonitrile derivative of the present invention, acrylonitrile which is a commonly used industrial or reagent can be used. As the formaldehyde, hydrated formaldehyde usually called formalin, semi-acetal derived from formaldehyde and C _{1 to} C ₆ alcohol, paraformaldehyde which is a polymer of formaldehyde and the like can be used, but there are few side reactions. Therefore, paraformaldehyde is preferably used.

As the catalyst, a linear or cyclic aliphatic tertiary amine is used, and trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, N-methyldiisopropylamine, N, N
-Diethylisopropylamine, N, N-dimethylethylamine, N, N-dimethylpropylamine, tri-2
-Ethylhexylamine, N-methyldiethylamine,
N, N-dimethylbutylamine, N, N-dimethyl-
(2-Ethylhexyl) amine, N, N-propyl-
(2-Ethylhexyl) amine, N, N-butyl- (2
-Ethylhexyl) amine, N-methyl-di (2-ethylhexyl) amine, N-butyl-di (2-ethylhexyl) amine, 1,4-diazabicyclo- [2,2,2
2] -octane (hereinafter referred to as “DABCO”), pinocolin, quinodiline, etc. are used, among which D
ABCO, pinocolin and quinodiline are preferable because of their excellent yield and selectivity, and DA is more preferable.
BCO.

(Synthesis) The acrylonitrile dimer and acrylonitrile derivative of the present invention are acrylonitrile,
Formaldehyde and amine catalysts at room temperature to 2
It can be obtained by stirring and reacting in the temperature range of 00 ° C for several dozen minutes to several tens of hours. If necessary, a solvent inert to this reaction may be used. Various alcohols as solvents
And ketone solvents such as methyl ethyl ketone, aromatic solvents such as toluene, acetic acid esters, acetonitrile, tetrahydrofuran, dioxane and the like. The amount of these solvents used is preferably within 5 times the total amount of acrylonitrile, formaldehyde and amine catalyst. When it exceeds 5 times, the reaction rate is slow and it takes a long time to complete the reaction, which is not preferable.

The preferred reaction temperature is 50 to 150 ° C. If the reaction temperature is lower than 50 ° C, the reaction is slow, and if it exceeds 150 ° C, the amount of by-products increases and the yield decreases, which is not preferable. The amount of the amine catalyst added was 0. 0 based on the total amount of acrylonitrile, formaldehyde, amine catalyst and solvent.
3 to 20% by weight is preferable, and 1 to 10% by weight is more preferable.

In the production of acrylonitrile dimer, it is preferable that the charged molar ratio of acrylonitrile and formaldehyde is 60:40 to 10:90,
It is more preferably 50:50 to 15:85. When a formaldehyde polymer such as paraformaldehyde is used, it is converted to formaldehyde. When the amount of acrylonitrile used exceeds this range, the acrylonitrile derivative that is a by-product in this case increases, and when the amount of acrylonitrile used is less than this range, the yield of the target acrylonitrile dimer decreases. ,
Each is not preferable. As a method for charging acrylonitrile and formaldehyde, both components may be initially charged at once or after formaldehyde is initially charged at once.
A method of continuously charging acrylonitrile is recommended.
The latter charging method is preferable because the production of the acrylonitrile derivative is reduced by suppressing the acrylonitrile concentration during the reaction to a low level.

In the production of the acrylonitrile derivative, the charged molar ratio of acrylonitrile and formaldehyde is preferably 95: 5 to 60:40.
It is more preferably 0:10 to 60:40. When a formaldehyde polymer such as paraformaldehyde is used, it is converted to formaldehyde. When the amount of acrylonitrile used exceeds this range, the production efficiency is low because the amount of the target product is small relative to the total amount of raw materials used, and when the amount of acrylonitrile used is less than this range, a crosslinkable acrylonitrile dimer is produced. It is not preferable because it increases. As a method for charging acrylonitrile and formaldehyde, it is recommended to initially charge both components at once or to charge acrylonitrile initially at once and then continuously charge formaldehyde. The latter charging method suppresses the dehydration reaction of two molecules of α- (hydroxymethyl) acrylonitrile by suppressing the concentration of the intermediate product α- (hydroxymethyl) acrylonitrile to a low level, and a crosslinkable bifunctional compound. It is preferable because it reduces the amount of by-products produced.

The solution after the reaction is usually washed with acidic water to remove the amine catalyst, the low-boiling components are removed under reduced pressure, and the mixture is distilled under reduced pressure to prepare a mixture mainly containing acrylonitrile dimer and acrylonitrile derivative. A fraction can be obtained. By increasing the number of distillation stages, the acrylonitrile dimer and the acrylonitrile derivative can be separated. The ratio of the both can be known by gas chromatography (hereinafter referred to as "GC") or ¹ H-NMR spectrum.

However, since it is not easy to separate the two, it is preferable to use a composition containing a large amount of acrylonitrile dimer and a composition containing a large amount of acrylonitrile derivative as a practical raw material for polymerization depending on the purpose. That is, both are excellent in homopolymerizability and copolymerizability, but when an acrylonitrile dimer is used as a copolymerization component, the glass transition point of the resulting polymer can be significantly improved and the heat resistance can be improved. Further, when an acrylonitrile derivative is used as a copolymerization component, the glass transition point of the obtained polymer can be lowered and the transparency can be increased.

As a preferable polymerizable composition mainly containing acrylonitrile dimer, 5 parts of acrylonitrile dimer are used.
A polymerizable composition containing 0 mol% or more and the remainder mainly composed of an acrylonitrile derivative can be mentioned. At this time, a preferable molar ratio of the acrylonitrile dimer and the acrylonitrile derivative is 50:50 to 99: 1 and 60:40 to 9: 1.
9: 1 is more preferred. If the content of the acrylonitrile derivative exceeds 50 mol%, the heat resistance of the polymer is lowered, which is not preferable, and it is difficult to make the content of the acrylonitrile derivative less than 1 mol%, and even if it can be purified, It is not preferable because the cost for is large.

A preferred acrylonitrile derivative is a polymerizable composition mainly containing an acrylonitrile derivative.
The content of the acrylonitrile dimer, which is an impurity in this case, is 20 mol% or more, more preferably 20 mol% or more.
It is less than 10% by weight, particularly less than 10% by weight. When the content of the acrylonitrile dimer is 20 mol% or more, the crosslinking reaction easily occurs during the polymerization reaction.

(Solution Polymerization of Acrylonitrile Dimer) The acrylonitrile dimer of the present invention or the polymerizable composition containing the above-mentioned acrylonitrile dimer as a main component (hereinafter referred to as "dimer composition") is used. Radical solution polymerization at a low concentration gives a solvent-soluble polymer. Similar α-
Since a dimer of (hydroxymethyl) acrylic acid ester gives a cyclized polymer having a six-membered ring (tetrahydropyran ring) repeating unit in the main chain, a polymer from acrylonitrile dimer also has a similar ring structure. It is considered to be a polymer or a polymer having a cyclized unit as a main unit.

As the solvent for homopolymerizing the acrylonitrile dimer or dimer composition, any solvent can be used as long as it can dissolve the cyclized polymer to be produced, but dimethyl sulfoxide, dimethylformamide, dimethylacetamide or the like is preferable. used. When other solvent is used, it is preferable to use a mixed solvent with the above solvent in order to avoid clouding, precipitation and insolubilization during the polymerization.

The concentration of the acrylonitrile dimer is preferably 1 to 40% by weight, more preferably 3 to 30% by weight, based on the whole polymerization solution. If the concentration is less than 1% by weight, the polymerization rate is slow, and if it exceeds 40% by weight, crosslinking and gelation are likely to occur, which is not preferable. When the acrylonitrile dimer is continuously fed into the reaction system to reduce the substantial concentration of acrylonitrile dimer in the system, more than 40% by weight of acrylonitrile dimer may be used.

As the polymerization initiator, an azo-based or peroxide-based initiator such as α, α'-azobisisobutyronitrile (hereinafter referred to as "AIBN") used in ordinary radical polymerization is used. It is preferable to use 0.1 to 10% by weight with respect to the acrylonitrile dimer or the dimer composition. The polymerization temperature is preferably room temperature to 150 ° C, more preferably 50 to 120 ° C. The solution after polymerization is methanol.
The powdery cyclized polymer can be obtained by adding it to a low-boiling-point precipitating agent such as silane, and filtering and drying the produced white precipitate by a conventional method.

(Bulk Polymerization of Acrylonitrile Dimer)
The acrylonitrile dimer or dimer composition of the present invention has excellent radical polymerizability and is easily polymerized by a small amount of a radical initiator to give a cured product having a crosslinked structure. For example, a small amount of a usual peroxide initiator or an azo-based initiator may be added and the temperature may be maintained in a temperature range required for radical generation of the used initiator. When using a peroxide initiator, as a redox accelerator, an amine compound or a cobalt compound,
By using a vanadium compound or the like in combination, the temperature range of radical generation can be lowered, and curing at room temperature is possible. Also,
If a known photopolymerization initiator such as benzoin alkyl ether, benzophenone or acetophenone is added in a small amount, it can be cured with an active energy ray such as ultraviolet rays.

(Polymerization of Acrylonitrile Derivative) The acrylonitrile derivative of the present invention or the polymerizable composition containing the above-mentioned acrylonitrile derivative as a main component (hereinafter referred to as “derivative composition”) has excellent radical polymerizability and has a normal solution weight. The polymer can be easily obtained by a conventional method, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, or the like.

Any solvent may be used as a solvent for the solution polymerization of the acrylonitrile derivative or the derivative composition as long as it dissolves the resulting polymer, but dimethyl sulfoxide, dimethylformamide (hereinafter referred to as "DMF") or dimethylacetamide. Etc. are preferably used. If other solvents are used, white turbidity during polymerization
In order to avoid precipitation and insolubilization, it is preferable to use a mixed solvent with the above solvent.

As the polymerization initiator, an azo-based or peroxide-based initiator used in ordinary radical polymerization is used in an amount of 0.1 to 10 relative to the acrylonitrile derivative or the derivative composition.
It is preferred to use weight percent.

(Bulk Polymerization of Acrylonitrile Derivative)
As a method for obtaining a cured product by bulk polymerization, after adding a predetermined initiator, the temperature may be maintained in a temperature range necessary for radical generation of the used initiator. When using a peroxide initiator,
When a redox accelerator is used in combination with an amine compound, a cobalt compound, a vanadium compound or the like, the temperature range of radical generation can be lowered, and curing at room temperature is possible.
Further, by adding a small amount of a known photopolymerization initiator such as benzoin alkyl ether, benzophenone or acetophenone, it is possible to cure with active energy rays such as ultraviolet rays.

[0033]

When the acrylonitrile dimer of the present invention is solution-polymerized at a low concentration, a polymer which is soluble in N, N-dimethylacrylamide, dimethylsulfoxide and the like and has significantly improved heat resistance can be obtained. This improvement in heat resistance is significantly improved as compared with the cyclized polymer obtained from the dimer of acrylic acid ester. The reason for this is not clear, but it is considered that this polymer is a cyclized polymer having a rigid six-membered ring structure (tetrahydropyran unit) in the main chain, and this cyclized polymer has a high glass transition point. To be Therefore, when the acrylonitrile dimer of the present invention is copolymerized with a general-purpose vinyl monomer such as styrene and methyl methacrylate, the glass transition point of the vinyl copolymer can be significantly improved and the heat resistance can be improved.

When a small amount of a radical initiator is added to the acrylonitrile dimer of the present invention and bulk polymerization is carried out at an appropriate temperature, a transparent cured product excellent in heat resistance and the like can be obtained, but the polymer has a three-dimensional network structure. And has a higher glass transition point. The polymer obtained from the acrylonitrile derivative of the present invention is excellent in chemical resistance, oil resistance, barrier resistance, and cold resistance. The reason for this is not clear, but it is speculated that this derivative has a strong polarity similar to that of polyacrylonitrile and, in addition, its glass transition point is lower than that of acrylonitrile.

[0035]

EXAMPLES The present invention will be described more specifically by showing Examples and Comparative Examples below. In addition, the part described in each example means a weight part, and% means weight%.

Synthesis of acrylonitrile dimer Example 1 79.5 g (1.5 mol) of acrylonitrile (hereinafter referred to as "AN") and paraformaldehyde were placed in a glass flask equipped with a stirrer, a reflux condenser and a thermometer. (Hereinafter referred to as “PFA”) 45 g (1.5 mol (formaldehyde conversion amount; the same applies hereinafter) and DAB
3.7 g of CO was charged. The flask was immersed in an oil bath at 90 ° C. and stirred for 5 hours to complete the reaction. During the reaction
The reflux temperature rose from 65 ° C to 85 ° C. 15 reaction mixture
Dilute with 0 ml of methylene chloride and wash with 5% aqueous hydrochloric acid 3 times,
It was washed once with distilled water. The methylene chloride layer was dried over magnesium sulfate, the low-boiling fraction was distilled off under reduced pressure, and the fraction with a boiling point of 77 to 95 ° C./0.1 mmHg 53.
5 g was obtained.

The fraction was analyzed by GC to find that the acrylonitrile dimer was 62% and the acrylonitrile derivative was 3%.
It contained 8%.

Example 2 AN 53.0 g (1.0 mol), PFA 60 g
(2.0 mol) and DABCO (3.4 g) were used, the reaction and purification were carried out in the same manner as in Example 1, and the distillate 2 was used.
3.7 g were obtained. According to GC, it contained 78% of acrylonitrile dimer and 22% of acrylonitrile derivative.

Example 3 In a glass flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 15.9 g (0.3 mol) of AN, 45 g (1.5 mol) of PFA and DABCO were added.
3.7 g and 60 g of methyl ethyl ketone (hereinafter referred to as "MEK") were charged, and AN 63.
6 g (1.2 mol) was added. The flask was immersed in an oil bath at 90 ° C., AN of the dropping funnel was added dropwise over 4 hours, and the mixture was further stirred for 1 hour to complete the reaction. The reaction solution was treated and purified in the same manner as in Example 1 to obtain 46.5 g of distillate.
I got When the fraction was analyzed by GC, it contained 75% acrylonitrile dimer and 25% acrylonitrile derivative.

Example 4 106.0 g (2.0 mol) of AN, 30 g of PFA
(1.0 mol) and DABCO (4.1 g) were used, the reaction and purification were carried out in the same manner as in Example 1, and the distillate 5 was used.
Obtained 3.2 g. According to GC, it contained 41% acrylonitrile dimer and 59% acrylonitrile derivative.

Example 5 In a glass flask equipped with a stirrer, a reflux condenser and a thermometer, 106 g (2.0 mol) of AN and PFA were added.
9.0 g (0.3 mol) and DABCO 6.8 g were charged. The flask was immersed in an oil bath at 90 ° C., stirred and refluxed for 6 hours to complete the reaction. 21 g during the reaction
(0.7 mol) of PFA was added in 4 portions and added every hour. The reflux temperature rose from 74 ° C to 85 ° C. The reaction solution was diluted with 150 ml of methylene chloride, washed with a 5% hydrochloric acid aqueous solution three times and with distilled water once. The methylene chloride layer was dried over magnesium sulfate, and then the low-boiling components were distilled off under reduced pressure.
8 g of crude product was obtained. Further, by distillation under reduced pressure, a boiling point of 9
41.6 g of a fraction of 6 to 100 ° C./0.2 mmHg was obtained.

When the fraction was analyzed by GC, it was found that the acrylonitrile derivative was 65% and the acrylonitrile dimer was 3%.
It contained 5%.

Acrylonitrile dimer and acrylonite
Identification of Ril Derivative Example 6 A mixture of acrylonitrile dimer and acrylonitrile derivative (62:38) obtained in Example 1 was further distilled several times,
High-purity acrylonitrile dimer (purity 96 by GC
%) Was obtained. This acrylonitrile dimer was a colorless and odorless transparent liquid at room temperature, and had a viscosity of 8 cps at 25 ° C. measured by a B-type rotational viscometer. The boiling point is 85 to 90 ° C /
It was 0.1 mmHg, the refractive index was 1.469 (23 ° C.), and the specific gravity was 1.036 (20 ° C.).

Spectral analysis (mass spectrum, ¹ H-
NMR spectrum, ¹³ C-NMR spectrum and IR
The spectrum) confirmed the structure of the acrylonitrile dimer. The IR spectrum, ¹ H-NMR spectrum and ¹³ C-NMR spectrum are shown in FIGS. 1, 2 and 3, respectively.

Mass spectrum: m / z 149 ((M + H) ⁺ ) IR spectrum (cm ^-1 ): 2220 (CN), 1630
(C = C), 1100 ( C-O) 1 H-NMR spectrum _{(CDCl 3, ppm): δ4.15} (m, 4H, -C H 2 -), 6.10 (m, 4H, = C H ₂ ) ¹³ C-NMR spectrum (CDCl ₃ , ppm): δ69.5 ( -C H _2- ), 116.6 ( -C N), 119.1 ( C = CH ₂ ), 132.4 (= C H ₂ )

Example 7 The mixture of Example 5 was distilled several times to obtain a fraction containing an acrylonitrile derivative as a main component (purity by GC: 95%). The boiling point was 88 to 95 ° C./0.1 mmHg, and the refractive index was 1.456 (23 ° C.).

IR spectrum, mass spectrum, ¹ H-
The structure of the acrylonitrile derivative was confirmed by NMR and ¹³ C-NMR spectra. The IR spectrum, ¹ H-NMR spectrum and ¹³ are shown in FIGS. 4, 5 and 6.
A C-NMR spectrum is shown. ¹ H-NMR methylene peak intensity ratio (3.72 ppm and 4.16 pp
It was found from m) that the acrylonitrile dimer was substantially not contained.

Mass spectrum: m / z 137 ((M + H) ⁺ ) IR spectrum (cm ^-1 ): 2250 (CH ₂ -CN ), 2220 (= C- CN ), 1630 (C = C), 1100 (C-) O) ¹ H-NMR spectrum _{(CDCl 3, ppm): δ2.66} (t, 2H, -C H 2 -CN), 3.72 (t, 2H, O-C H 2 -CH 2), 4. 16 (m, 2H, = C -C H 2 -O), 6.08 (m, 4H, = C H 2) 13 C-NMR spectrum _{(CDCl 3, ppm) δ18.7 (} - C H 2 -CN _{), 65.2 (O- C H 2} -CH 2), 70.3 (= C- C H 2 -O), 116.8 (= C- C N), 117.5 (CH 2 - C N ), 119.4 ( C = CH ₂ ), 132.2 (= C H ₂ ).

Synthesis of acrylic acid ester dimer Comparative Example 2 A glass flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 129 g (1.5 mol) of methyl acrylate,
PFA 45 g (1.5 mol) and DABCO 9.8 g
Was charged. Immerse the flask in a 90 ° C oil bath and
The mixture was stirred and reacted for 8 hours. After that, 50 g of toluene was added, and azeotropic dehydration was carried out for 5 hours to carry out the reaction while removing distilled water from the reaction system. The distillation temperature is from 103 ° C to 125
Rose to ℃. The reaction solution was diluted with 150 ml of methylene chloride, washed with a 5% hydrochloric acid aqueous solution three times and with distilled water once. The methylene chloride layer was dried over magnesium sulfate, the low-boiling component was distilled off under reduced pressure, and the residue was dissolved in 2 liters of n-hexane.
Let stand overnight in a freezer at 15 ° C. The precipitated crystals are filtered
When dried, the dimer of MA (hereinafter referred to as "DMA")
35.0 g was obtained.

Comparative Example 3 150 g (1.5 mol) of ethyl acrylate, PFA45
g (1.5 mol) and DABCO of 9.8 g were reacted and washed in the same manner as in Comparative Example 2, and the dimer of EA (hereinafter referred to as “DEA”) 9 was obtained by vacuum distillation.
7.5 g was obtained.

Comparative Example 4 150 g of butyl acrylate (hereinafter referred to as "BA")
(1.5 mol), PFA 45 g (1.5 mol) and D
Using 11.9 g of ABCO, the reaction and washing were carried out in the same manner as in Comparative Example 2, and 105.5 g of a dimer of BA (hereinafter referred to as "DBA") was obtained by distillation under reduced pressure.

Solution polymerization and polymerization of acrylonitrile dimer
And copolymerization Examples 8 to 15 and Comparative Example 5 A mixture of the acrylonitrile dimer obtained in Example 1 and an acrylonitrile derivative (mixing ratio 62:38, hereinafter "DAN").
-60 ". ) And DAN-60 were distilled several times to have an acrylonitrile dimer content of 91% (hereinafter referred to as “DAN-90”), and the two kinds of the compositions shown in Table 1 were used alone at 80 ° C. for 5 hours. Polymerized or copolymerized with styrene (hereinafter referred to as "St"). The polymerization solution was precipitated in methanol, filtered and dried for purification. The glass transition temperature (hereinafter referred to as "Tg") of the obtained polymer is D
Determined by SC. DSC measurement was performed in a nitrogen stream at a heating rate of 10
C./min. The results are shown in Table 1.

[0053]

[Table 1]

From the results shown in Table 1, it can be seen that the copolymerization of the acrylonitrile dimer significantly increases the Tg of the St copolymer. Further, no endothermic peak indicating melting was observed in any DSC thermogram, and it was found to be an amorphous polymer. Further, according to the TG-DTA spectrum (performed at a temperature rising rate of 20 ° C./min in a nitrogen stream),
The thermal decomposition initiation temperature of the homopolymer obtained from DAN-90 is
It was 332 ° C.

Examples 16 to 17 and Comparative Examples 6 to 8 Copolymerization of DAN-90 and methyl methacrylate (hereinafter referred to as "MMA") in the same manner as in Examples 8 to 15,
And N-phenylmaleimide (hereinafter referred to as "PMI") and MMA were copolymerized. Table 2 shows the results.

[0056]

[Table 2]

From the results shown in Table 2, the heat resistance effect of the copolymerization of the acrylonitrile dimer was superior to that of PMI which is a typical heat resistance improving monomer, and the coloring was small. No endothermic peak indicating melting was observed in any of the DSC thermograms, indicating that the polymer was an amorphous polymer.

Solution polymerization of acrylonitrile derivative and
And copolymerization Example 18 A fraction containing an acrylonitrile derivative as a main component, which was obtained by distillation of the mixture of Example 1 (purity of 81 by GC).
%, Hereinafter referred to as "DAN-20". ) 1st copy, AIBN
80 parts of a solution consisting of 0.05 parts and 4 parts DMSO
The mixture was heated at 0 ° C. for 5 hours to obtain a polymer of acrylonitrile derivative. The polymer solution was precipitated in methanol, filtered, dried and purified, and the Tg of the obtained polymer was determined by DSC.
It was 6.2 ° C. No endothermic peak indicating melting was observed and it was found to be an amorphous polymer. Also, TG
-The DTA spectrum shows that the thermal decomposition initiation temperature is 257.
° C. From these results, it was found that the Tg and the thermal decomposition initiation temperature were significantly lower than the cyclized polymer obtained from the acrylonitrile dimer, and the heat resistance was poor.

Examples 19 to 20 and Comparative Examples 9 to 11 Distilled and refined products of acrylonitrile derivative (purity 95% by GC, hereinafter referred to as "DAN-5"), AN and BA are homopolymerized or copolymerized, followed by precipitation purification. -Vacuum drying was performed to obtain a polymer. The Tg of the obtained polymer was determined by DSC (in nitrogen stream, temperature rising rate: 10 ° C./min). Further, the solubility of the polymer in n-hexane and xylene was examined. The results are shown in Table 3.

[0060]

[Table 3]

Bulk Polymerization of Acrylonitrile Dimer Examples 21-24 and Comparative Examples 12-13 DAN-90, St, diallyl phthalate (commercially available diallyl orthophthalate monomer (diso-
Dup Monomer manufactured by Co., Ltd. Hereinafter referred to as "DAP". )), An unsaturated polyester as a prepolymer (Polyset 2100PT manufactured by Hitachi Chemical Co., Ltd.) was precipitated and dried in methanol, and St was removed. Hereinafter, referred to as “UP”) and diallyl phthalate prepolymer (Daiso- ( Manufactured by DAP A Co., Ltd., hereinafter referred to as "PDAP") was used to carry out bulk polymerization at a weight ratio shown in Table 4. Benzoyl peroxide as an initiator (hereinafter referred to as "BP
"O". 1) or 2 parts, and heat-treated at 80 ° C. for 2 hours and further at 100 ° C. for 3 hours to be cured. The amount of residual monomers in the cured product, the viscoelastic spectrum of the cured product, oil / solvent resistance, flexural strength and flexural modulus were evaluated by the following methods. The results are shown in Table 4.

Amount of remaining monomer : The cured product was abraded with a sand paper to be pulverized, and TG-DTA spectrum (in nitrogen stream, heating rate was 20 ° C./minute) was used.
The weight loss from room temperature to 250 ° C was taken as the residual monomer. Viscoelastic spectrum : Stretching method (10 Hz, heating rate 3 ° C)
The maximum value of loss elastic modulus (E " _max ) and the temperature of tan δ _max at (/ min) were measured. In the case of two values, two peaks appeared and the phases were microscopically separated. Oil / solvent resistance : Test piece of cured product (5 mm x 1 mm x 20)
mm) was immersed in 5 ml of a solvent (gasoline, xylene, MEK, chloroform) at 60 ° C. for 15 hours, and the appearance change and the weight increase rate were evaluated. In the change in appearance, "○" indicates no change, "X" indicates deformation, and "XX" indicates disintegration. Bending strength, bending elastic modulus : Based on JIS K6911, the bending strength (parallel to the layer) and the bending elastic modulus were measured under the following conditions.・ Dimensions of sample: width 9-10mm, height 3-3.2mm, length 80mm ・ Distance between fulcrums: 52mm ・ Load speed: 2mm / min

[0063]

[Table 4]

Solution polymerization of acrylic acid ester dimer
And bulk polymerization Comparative Examples 14 to 16 The three acrylic acid ester dimers synthesized in Comparative Examples 2 to 4 were homopolymerized and purified in the same manner as in Example 15, and the Tg of each cyclized polymer was measured by DSC. I asked for. The results are shown in Table 5. Bulk polymerization was carried out in the same manner as in Example 23, and E ″ _max and tan δ _max were determined by viscoelasticity measurement.
The results are shown in Table 5. From these results, it can be seen that the cured product obtained from the acrylonitrile dimer of the present invention has a higher glass transition temperature than the cured product of the acrylic ester dimer, and is significantly excellent in heat resistance and oil resistance. .

[0065]

[Table 5]

[0066]

INDUSTRIAL APPLICABILITY The acrylonitrile dimer and acrylonitrile derivative of the present invention can be synthesized by reacting acrylonitrile and formaldehyde in the presence of a tertiary amine at a specific charge ratio while suppressing the production of impurities. Therefore, purification by distillation etc. is easy.

The acrylonitrile dimer and acrylonitrile derivative of the present invention are odorless, low-viscosity transparent liquids and have excellent workability when used as a curable composition. In addition, because it has excellent radical polymerizability, it can be cured at low temperature and in a short time, and has excellent storage stability as compared with acrylic acid esters.

The solution polymer of the acrylonitrile dimer of the present invention has excellent heat resistance, and when the acrylonitrile dimer of the present invention is copolymerized with general-purpose vinyl monomers such as St and MMA, The Tg of the copolymer can be significantly improved and the heat resistance can be improved. The acrylonitrile dimer bulk polymer of the present invention is excellent in heat resistance, oil resistance, chemical resistance, gas barrier properties, hardness, abrasion resistance, mechanical strength, transparency, etc., and is a molding material, film, paint. -Can be used in a wide range of applications such as coating materials and adhesives. As described above, the acrylonitrile dimer of the present invention is industrially extremely useful as a raw material for various thermoplastic resins and thermosetting resins.

The acrylonitrile derivative of the present invention has excellent radical polymerizability, and the resulting polymer has the same excellent oil resistance as polyacrylonitrile and has a Tg of 57 ° C.
And low (polyacrylonitrile is 100-130
° C). Due to this property, the acrylonitrile derivative of the present invention is a raw material for an elastomer having excellent cold resistance and oil resistance,
It is industrially extremely useful as a raw material for various thermoplastic resins and thermosetting resins.

[Brief description of drawings]

FIG. 1 is an IR absorption spectrum diagram of a highly pure acrylonitrile dimer of the present invention (purity 96% by GC) obtained in Example 1.

FIG. 2 ¹ H—N of the high-purity acrylonitrile dimer
It is an MR spectrum figure.

FIG. 3 ¹³ C—N of the above high-purity acrylonitrile dimer
It is an MR spectrum figure.

4 is an IR absorption spectrum diagram of the highly pure acrylonitrile derivative of the present invention (purity 95% by GC) obtained in Example 5. FIG.

FIG. 5: ¹ H- of the above high-purity acrylonitrile derivative
It is a NMR spectrum figure.

FIG. 6 shows the above-mentioned highly pure acrylonitrile derivative ¹³ C-
It is a NMR spectrum figure.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C07B 61/00 300

Claims (7)

[Claims] 1. An acrylonitrile dimer represented by the following formula [A]: CH ₂ ═C (CN) CH ₂ OCH ₂ C (CN) ═CH ₂ ... [A] 2. An acrylonitrile derivative represented by the following formula [B]. _{CH 2 = C (CN) CH} 2 OCH 2 CH 2 CN ... [B] 3. The method for producing an acrylonitrile dimer according to claim 1, wherein acrylonitrile and formaldehyde are reacted in the presence of a tertiary amine. 4. The method for producing an acrylonitrile derivative according to claim 2, wherein acrylonitrile and formaldehyde are reacted in the presence of a tertiary amine. 5. The method for producing an acrylonitrile dimer according to claim 3, wherein the charged molar ratio of acrylonitrile and formaldehyde is 60:40 to 10:90. 6. The method for producing an acrylonitrile derivative according to claim 4, wherein the charged molar ratio of acrylonitrile and formaldehyde is 95: 5 to 60:40. 7. A polymerizable composition containing 50 mol% or more of the acrylonitrile dimer according to claim 1.