JPS5925379A - Xylene derivative, its preparation and cured article consisting of xylene derivative as main agent - Google Patents

Abstract

NEW MATERIAL:A xylen-alpha,alpha'-diyl-bis [3,5-disubstituted-1,3,5-triazin-2,4,6-(1H, 3H, 5H)-trione] derivative of formula I [R is -CH2CX=CH2, -COCX=CH2 or -(CH2)n YCOCX=CH2 (X is H or CH3; Y is O or S; n is 1,2 or 3)]. USE:A raw material for homopolymer, modifying agent for thermosetting resins, crosslinking assistant for acrylic resins, etc. PROCESS:A compound of formula II is reacted with a compound of formula III(Z is Cl, Br or I) in a solvent, e.g. dimethylformamide (DMF) in the presence of basic substance to give the aimed compound of formula I .

Description

Detailed Description of the Invention The present invention relates to the following general formula [■] (In formula [I], R is -0H20X==OH2, -Co
(1!X=OH, or -(0 horse)flYCOCx=
Represents CH2. f, -W L.

X represents H or OH3, Y represents 0 or S, and n represents l, 2 or 3. ) Xylene-α,α′-diylrubis [3,!
-Disubstituted-/,j,J--triazine-,2,! , ,
4(/H,3H,jH)-)ion] derivative, a method for producing the same, and a cured product containing the derivative as a main ingredient.

Conventionally, di-substituted in cyanurates have been used as homopolymers or as modifiers or crosslinking agents for other polymers. However, because di-substituted in cyanurates leave -NH- groups in their molecules, the polymerization rate is slow, and the resulting hard resins are brittle, lack surface smoothness, and crack. There were some drawbacks, such as the tendency to cause

Therefore, it has been difficult to use it as a material for electrical insulators, interlayer insulating films, or sealing resins for elements such as ICs.

The present invention was completed after extensive research aimed at this purpose.

That is, the present invention provides general formula [■] B [Formula (I]), R CH2CX=OH2, -000X
:OH2 or -(CH2)nYCOCx=CH2. KLX is H or CH3, Y is O or S
, and n represents /, ko, or 3. ) Gysilene-α,α′-Ci/l/-bis[3
, s.

Xylene-α, α represented by the above general formula [■] of the present invention
′-diyl-bis[3,! -di-substituted-7,3. ! -triazine-λ,≠6(/H,JH,jH)-)ion] derivative has the general formula [Ill (formula [■]), where the substituent R is -C!H20X=OH2, -
coax=CH2, matach-(CH2)nYCoCx=
CI (represents 2. However, X is H or OH3, Y is O
or S, and n represents 1.2 or 3. ) A di-substituted in cyanurate represented by the following general formula [C formula [where X represents a chlorine atom, a bromine atom, or an iodine atom]. ) It is produced by reacting with α,α'-quidyl dihalide shown in the following.

The compound represented by the general formula CI'l of the present invention is an aprotic polar solvent such as N, N/-dimethylformamide (hereinafter abbreviated as "DMF"), N, N'-dimethylacetamide, N, N /-dimethylsulfoxide, N,N'-diethylformamide, N,N/-diethylacetamide, N-methylpyrrolidone, tetramethylurea, hexamethylphosphoramide, acetonitrile, etc., with a basic substance such as potassium hydroxide. ,
It can be obtained by carrying out the above reaction in the presence of potassium carbonate, sodium hydroxide, sodium carbonate, or an organic basic substance having no active hydrogen, such as pyridine or triethylamine.

α represented by the above general formula [■] which is a reaction component of the present invention
, α′-Examples of pheasant dihalides include α, α′-
Cyclo-O-xylene, α, α'-dichloro-m-xylene, α, α'-dichloro-p-xylene, α, α'
-Dibromu 0-xylene, α, αI-Sybromu m-
xylene, α, α′-dibromo-p-xylene, α, α
′-shorto〇-xylene, α, α′-shorto m
-xylene, α, α'-short p-xylene, and the like. Further, different halogen atoms may be bonded to the xylyl group.

The molar ratio of the disubstituted isocyanurate, which is a reaction component of the present invention, and the α,α'-quizylene dihalide represented by the general formula [■] is theoretically 2,
For 0 mole, α, α′-quidyl dihalide is /, Q
Although it is a mole, a range of 2.0 to 1.0% is practical.

When the molar ratio of the disubstituted incyanurate and α,α′-quidyl dihalide is less than 2, when separating the target product represented by the general formula [■] from the reaction solution after the reaction, Unreacted α,α'-quizylene dihalide is separated along with the target product, making the purification process of the target product complicated. On the other hand, with di-substituted yne annulate, α, α′-
The molar ratio with pheasant dihalide is 2. If it is larger than 1, the amount of di-substituted isocyanurate becomes excessive and is not economical. The molar ratio of the disubstituted isocyanurate and α,α'-quidyl dihalide is 2.0-. 2. In the case of /, the unreacted di-substituted isocyanurate can be easily removed by washing the reaction solution after the reaction with an aqueous alkali-11 solution, making it easy to purify the desired product.

The reaction between the disubstituted isocyanurate of the present invention and α, α'-quidyl dihalide is carried out at a temperature of 1410°C or higher, and ζ is generally 1410°C or lower. It is better to do this. 1410
If the temperature is higher than 0.degree. C., a side reaction of polymerization of vinyl groups occurs, making it difficult to obtain the desired product in good yield. On the other hand, below aO<0>C, the reaction rate is slow. The reaction time is usually about 150 minutes, and the end point of the reaction can be confirmed by an analytical means such as gas chromatography by detecting the disappearance of the peak of the raw material σ); P dihalide.

After the reaction under the above conditions, the solvent is distilled off under normal pressure or reduced pressure, and the compound represented by the general formula (Il) of the present invention is extracted from the residue with an organic solvent, and the reaction salt is removed. The organic solvent referred to above refers to the above-mentioned general formula [
The compound represented by the general formula [I] of the present invention has a large distribution ratio, is almost incompatible with water, and the salt generated in the reaction does not dissolve, but the compound represented by the general formula [I] of the present invention appears to be soluble. Any suitable solvent may be used, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene, chloroform, carbon tetrachloride, and methylene chloride. Further, if necessary, the compound represented by the general formula CI') of the present invention can be obtained by further applying a conventional purification method for organic compounds.

Xylene-α,α′-diyl-bis obtained in the present invention [
3,j-disubstituted-/, 3. j-triazine-,2,
p,A-(/H,3H,,tH)-trione] derivative has a highly reactive vinyl group and a triazine ring skeleton with excellent heat resistance in the molecule, so it is a homopolymer. It is useful not only as a modifier for thermosetting resins such as unsaturated polyester resins and diallyl phthalate resins, but also as a crosslinking aid for acrylic resins, polyethylene resins, vinyl chloride, etc.

The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Diallylisocyanurate, 202 g C1 mol), α
, α'-dichloro〇-xylene, 1' 7.3 g (
0,! ;mol] and potassium carbonate2. g (o, t mol) and further 2 ooml of DMF as a solvent were charged, the temperature was raised while stirring, and the reaction was carried out at a reaction temperature of /Q°C for 90 minutes. At this point, the absence of the raw material α,α'-dichloro○-xylene was confirmed by thin layer chromatography, and then, after distilling off DMF under reduced pressure, q o ml of chloroform was added to the reaction product to produce the desired product. Extracted things.

This extract was washed with a 10% aqueous sodium hydroxide solution,
Next, after washing with water and drying with magnesium sulfate, the solvent was distilled off to obtain 0-xylene-α with a purity of 9r%,
α′-diyl-bis[3,j-di(2-propenyl)
'+3+tartriazine-2. ≠, 7-(/H, J
23, 4 g (yield based on pheasant dihalide, 2%) of white crystals of H,jH)-trione were obtained. A portion of this was used as a sample for analysis, and about 2 portions were recrystallized with twice the amount of isopropanol to obtain white needle-like crystals with a purity of 100%. This is hereinafter referred to as compound/.

In a reactor similar to Example/, diallylisocyanurate, 230 g (/, 1 mol), α, α'-dibromo m
- 13 g (o, 3 mol) of xylene and 79 g (0,7 mol) of potassium carbonate, DMFlooo as solvent
ml was charged and reacted for 20 minutes at 100° C. with stirring.

Next, DMF' was distilled off under reduced pressure, and 70θml of methylene chloride was added to the reaction product to extract the desired product. After washing this extract with a 10% aqueous sodium hydroxide solution and then with water,
By drying with magnesium sulfate and then distilling off the solvent, m-xylene-α,α′-diyl-bis[3,j-di(,2-propenyl)′+3+j] with a purity of 9Ir% was obtained.
- Triazinko, &, A - (/'H, JH, TaH)
-trione]O-g (yield 3%) was obtained. This is hereinafter referred to as a compound.

Example 3 In a reactor similar to Example 1, 230 g (/, 1 mol) of diallylisocyanurate, α, α'-dibromo p
-xylene/3.2 g (0.3 mol) and potassium carbonate, 79 (0.7 mol), solvent D M F /
, 200 ml was charged, stirred, and reacted at 0°C for 0 minutes. The subsequent operations were carried out in the same manner as in Example 1, and p-xylene-α,α'-diylrubis [31j
-G(2-propenyl)=1.3. r-) riazine-
2,≠,I,−(/H', JH.

tH)-trione] white crystals 2μ2g (yield 3%)
was gotten. Approximately 20 pieces of this will be used as samples for analysis.
Recrystallization was performed with twice the amount of methanol to obtain white needle-shaped crystals with a purity of 100%. This is hereinafter referred to as compound 3.

Examples/Infrared absorption spectra, nuclear magnetic resonance spectra, and nuclear magnetic resonance spectra of the compounds obtained in Examples 3 and 3. Example ≠ Dimethallyl in cyanurate obtained by reacting isocyanurate and methallyl chloride in a DMF solvent,
20ri1 (1 mol), α,α'-dichloro-p-xylene I 7. ! fl (0,3 mol) and potassium carbonate? , 2.2 g (o, t mol), plus DM as solvent
yi2oOml was charged into the reaction apparatus used in Example 1, and reacted for several minutes at 710° C. with stirring. The subsequent operations were carried out in the same manner as in Example 1, p-xylene-α, α
'-Si Rubis [3,j-di(l-methylvinyl)
-/, 3. ! ;-1 Riajinko, ≠, (, (zH, J
H,jH)-trione] was obtained. This is hereinafter referred to as a compound.

Example! In a DMF solution of 1 mol of incyanuric acid, 0 to 770
3 λl 1 l (1 mol) of an esterified product of bis(,2-hydroxyethyl) isocyanurate and acrylic acid obtained by blowing 2 mol of ethylene oxide at a temperature of ,3
mol), and potassium carbonate g(o, t mol),
Then, DMFlooml was charged as a solvent into the reaction apparatus used in Example/1, and the reaction was carried out at 90° C. for 70 minutes with stirring.

The subsequent operations were the same as those in Example/P-xylene-
α,α′-diyl-bis[3,r-di(ethyl acrylad)-1,3,! −Triazineco, μ+'('
H+3HT+H)-trione] was obtained.

This is hereinafter referred to as compound j.

Example 6 Dimethacryloyl isocyanurate obtained from dicyaglysocyanurate and methacrylic acid chloride
! /l (1 mol) and α, α'-dibromo p-xylene / 32 g (0, J-mol) and potassium carbonate g 2.2 g
(o, t mol) DMF/100ml was charged in each section and reacted at 0°C for 70 minutes. The subsequent operations were carried out in the same manner as in Example/, p-xylene-α,α'-diyl-bis[
3,j-G(methacryloyl)-/,J,j-toIJAjinko,g,a-(/H,JH,tH)-
) Lion] was obtained. This is hereinafter referred to as Compound B.

Example 7 Bis(3-mercaptopropyl)isocyanurate obtained by hydrolyzing bis(3-acetothiopropyl)in cyanurate obtained by the reaction of Lydia C-lysocyanurate and thiol acetic acid with acrylic acid chloride. 311 g (1 mol) of 3,j-bis(acrylicthiocarboxydipropyl)isocyanurate, which is a reaction product, α,α
'-dibromo p-kijirenz 3.2g (0.6 mol)
and potassium carbonate g2. 9 (o, A mol) and DMF/λooml as a solvent were charged and reacted at 0° C. for up to minutes.

The subsequent operations were carried out in the same manner as in Example 1. t-triazine, 4Z, & -(/H,3H,jH)-trione]
I got it. This is hereinafter referred to as compound 7.

Examples &, Compounds obtained in J-, J and 7, j
The infrared absorption spectra and elemental analysis values of , Otsu and 7 are shown in Table 2. As a result, it was confirmed that each product was the final product described in the example.

Example ♂ p-xylene-α,α′-diyl- obtained in Example 3
Bis[3,j-di(2-propenyl]-1,3,r-
Triazineco, pi, 7 (/H,,?H,jH)-
Dicumyl peroxide o, ig was added to Trion] log, and this was dissolved in acetone log. When this solution was applied onto a mild steel plate and heated at 160°C for 30 minutes, a smooth cured film with a thickness of 30 microns and no cracks was obtained.

Example 100 parts by weight of vinyleste/14 resin obtained by reacting bisphenol A type epoxy resin and methacrylic acid, p-xylene-α,α'-diyl-bis[3,j-
G(,!-propenyl)-/, 3. j-) Riajinko, μ, Otsu-(/H, JH,, tH)-trion]AO
A resin composition was obtained by adding MIk part and 7 parts by weight of dicumyl peroxide.

Examples IQ and l/ Each polyester resin obtained by reacting inphthalic acid and terephthalic acid with maleic anhydride and propylene glycol (PBj/r manufactured by Hitachi Chemical Co., Ltd., containing 1.10% styrene and styrene &j%) 100 parts by weight,
p = xylene to α′-diylrubis [3,
j-di(2-propenyl) -/, 3. j -triazine-2゜μ, 6-(lH13H,tH)-)ion]
Each resin composition was obtained by adding 1 part by weight of lOO and 1 part each of dicumyl peroxide.

In the above examples, each composition indicated by IQ, // is o, lr
A coated cloth having a resin content of approximately μO wt % was prepared by impregnating a glass cloth treated with Aminoran with a thickness of H. Then,
Layer each coated cloth one by one and apply pressure to ~<tok
g/crll, molding temperature/30°C, after curing for 60 minutes, 1
Post-curing was performed at 10° C. for 120 minutes to produce a laminate.

Table 3 shows the results of measuring the characteristics of the resins and laminates sampled from each coated fabric thus produced. In addition,
In the table, the weight loss starting temperature is the weight loss starting temperature when heating in air at a heating rate of t°C/min and measuring the weight loss characteristics.
The weight loss at ttoo°C is the rate of weight loss when aOO°C is reached. The bending strength is the retention rate at each temperature with respect to the bending strength at 2J°C.

Table 3 1tl a Nippon Kasei Co., Ltd. Agent Patent Attorney Hase - 1 other person =505

Claims (1)

[Claims] (1) In the general formula (Il bar 0 formula [■], R bar 0H20X=OH,, -000X
==OR2, Matha-(CH2)nYOocx=c'H
2wo clothes were wasted. ri r t. X represents H or OH3, Y represents 0 or S, and n represents l, 2 or 3. ) Xylene-α shown in
, α′-diyrubis [3,! -di-substituted-/, J, j-
) Riazine 11, ge, t-(lH,!H,zH) -)
[Rion] derivative. (2. The xylene derivative described in claim 1 is O
-xylene-α,α′-diyl-bis(J, r-disubstituted-1,3,j-triazine-λ,t,ot-(lH,J
H, tH) -) ion] is a xylene derivative. (3) The xylene derivative described in claim 1 is m
-xylene-α,α′-diyl-bis[3,Z-disubstituted-/, 3. j-triazine-2,4t, J-(
/ II, jH, J′I() -trione]. (4) The xylene derivative according to claim 1 is p
-xylene-α,α′-diyl-bis[: J, z-
Di-substituted-l, 3. j-triazine-2,! , A-(
lH, 3H, ΔJ)-trione]. (5) General formula [■] B (Formula J [■) Medium, i-law R bar CH2Cx=CH2
, -aoax=aH2, Mataha-CaH2)nYaoc
represents x=aH. Tag: x is H or OH3, Y
teeth. or S, and n represents no, ko, or 3. ) In the general formula [匪 [formula [■]], 2 represents a chlorine atom, a bromine atom, or an iodine atom. ] xylene-α,α'-diyl-bis[3,j-disubstituted-/, 3. J-) Method for producing riazine-2,pi,A-(/H,3H,jH)-trione] derivative. (6) A xylene derivative, wherein the α,α'-quizylene dihalide according to claim j is 0-α,α'-quizylene dihalide. (7) A xylene derivative in which the α,α'-quizylene dihalide according to claim j is m-α,α'-kyzylene dihalide. (8) A xylene derivative in which the α,α'-quidyl dihalide according to the second claim of the claims is p-a, α'-quidyl dihalide. (9) General formula CI") bar0 formula [:I'] in, R bar0H2CX=OH2, -a
oax=am, or -(OH2)nYOOCX2O
Represents H. X represents H or CH3, Y represents 0 or S, and n represents l, 2 or 3. )
,j-di-substituted-1,3,j-) riajinko, pi, 6