JPS5920251A - Novel bisallyl carbonate and bis beta-methylallyl carbonate - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [phi is group of formula II (X is H, Cl or Br; n is 1-4), group of formula III (A is isopropenyl or sulfone), etc.; R is H or CH3]. EXAMPLE:1,4-Bis(hydroxyethoxy)benzene bisallyl carbonate. USE:Lens of eyeglasses, camera lens, and other material for optical element; crosslinking agent for unsaturated polyester, and additive-type flame retardant for plastics. When the compound of formula I or its mixture with other monomer is cast and radically polymerized, a resin having excellent transparency, hardness, refractive index and stability to ultraviolet radiation can be obtained. PROCESS:The compound of formula I can be prepared by using the compound of e.g. formula IV (e.g. hydroquinone) as a raw material, reacting the compound with ethylene oxide under pressure in the presence of a catalyst comprising triethylamine, and reacting the intermediate compound of formula V with allyl chloroformate, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel bisallyl carbonate and bisβ
-Relating to methylallyl carbonate.

Novel bisallyl carbonate and bis β-
Methyl allyl carbonate has the general formula (1) (where X
is hydrogen, chlorine or bromine, A is an isopropenyl group or a sulfone group, n is an integer of 1 to 4), and R is hydrogen or a methyl group.

Novel bisallyl carbonate and bis β-
When methylallylcarbonate-1 is subjected to radical cast polymerization alone or in combination with other monomers, a resin with good translucency, hardness, refractive index, and ultraviolet stability can be obtained, and can be used for eyeglass lenses, It is collectively useful as an accumulator when making camera lenses and other optical elements. It can also be used as a crosslinking agent for unsaturated polyesters, and these bisallyl carbonates and bisβ-
Bis(dihalogenoglopyru) carbonate and bis(dihalogeno-β-methylglobyl) carbonate obtained by reacting methylallyl carbonate with chlorine or bromine are also useful as additive flame retardants for plastics.

Specific examples of the bisallyl carbonates and bisβ-methylallyl carbonates of the present invention include the following compounds. That is, 1,4-his(hydrokine ethoxy)benzene bisallyl carbonate,
1.4-bis(hydroxyethquine)benzenebisβ-
Methylallyl carbonate, 2.5.5.6-tetrachloro-1,4-bis(hydroxoethoxy7)benzenebisallyl carbonate, 2. 5,6-tetrachloro-1,4-bis(hydroxyethoxy)benzene bisβ
-Methylallyl carbonate, 2.3.5.6-tetrabromo-1,4-bis(hydroxyethoxy)benzenebisallyl carbonate, 2.3.5.6-tetrabromo-1,4-bis(hydroxyethoxy)benzenebis β-methylallyl carbonate, 1,5-bis(hydroquine ethoxy/)penquinbis71J carbone-1.
1.6-bis(hydroxyethoxy)benzenebisβ-
Methylallyl carbonate, 2,4,5,6-tetrachloro-1,3-bis(hydroquinethoquino)benzenebisallyl carbonate, 2,4,5,6-titrachloro-1,3-bis(hydroquine) quinethoxy)benzenebisβ-methylallyl carbonate, 2,4゜5.6-titrabromo 1,3-bis(hydroquine)quin)benzenebisallyl carbonate, 2,4゜5.6-titrabromo 1,6-bis (Hydroquine)ki7) Benzene β-methylallyl carbonate, 1,5-bis(hydroxyethoxy)naphthalene bisallyl carbonate, 1
,5-bis(hydroxyethoxy)naphthalenebisβ-
Methylallyl carbonate-1, 1,6-bis(hydroquinetoquine) naphthalene bisallyl carbonate, 1,
6-His(Hydroquinethoxy)naphthalenebisβ-methylallyl carbonate, 1,6-Bis(Hydroquinethoxy)naphthalenebisβ-methylallyl carbonate, 1,7-Bis(hydroxyethoxy)naphthalenebisallyl carbonate ), 1,7-bis(hydroxyethoxy7)naphthalenebisβ-methylallyl carbonate, 2
, 6-bis(hydroxyethoxy)naphthalenebisallyl carbonate, 2.6-bis(hydroxyethoxy)
Naphthalene bis β-methylallyl carbonate, 2,7
-bis(hydroxyethoxy)naphthalenebisallyl carbonate, 2.7-bis(hydroxyethoxy)naphthalenebisβ-methylallyl-phonate, 4.4'-
Bis(hydroxyethoxy)diphenylpropane bisallyl carbonate, 4.4'-bis(hydrokinethoxy)diphenylpropane bisβ-methylallyl carbonate, 3.3', 5.5'-tetrachloro-4,4'
- His(Hydroquinethoxy) diphenylpropane bisallyl carbonate, s, s', 5,5'-tetrachloro-4,4'-bis(hydroquinethoxy) diphenylpropane bis β-methylallyl carbonate, s,
3: s, s'-tetrabromo-4,4'-bis(
Hydroxyethoxy) diphenylpropane bisallyl carbonate, 6ζ5,5'-tetrabromo-4,4
'-Bis(hydroxyethoxy)nphenylpropane hisβ-methylallyl carbonate, 4.4'-bis(hydrokinethoxy)diphenylsulfonebisβ-methylallyl carbonate, Ro, Ro/s,! 5'-tetrachloro4.4'-bis(hydroquine) diphenylsulfone bisallyl-phonate, 3, 5,
5'-tetrachloro-4,4'-bis(hydroxyethquine)diphenylsulfonebisβ-methylallyl-
Honate, 3.3: 5.5'-tetrabromo-4,4
'-bis(hydroxyethquine) 7 phenylsulfone bisallyl carbonate, 3: 5,5'-tetrabromo-4,4'-bis(hydrogyaethoxy) diphenylsulfone bis β-methylallyl carbonate, etc. .

Such a compound of the present invention (1) An aromatic compound having two hydroxyl ethoxy groups obtained from an aromatic compound having two hydroxyl groups or its nuclear halogen substituted product and allyl chloroformate or β-methyl Obtained by reaction with allyl chloroforme 1.

Novel bisallyl carbonate and bis β-
The aromatic compound having two hydroxyl groups used in the production of methylallyl carbonate is a compound represented by the following formula.

(wherein, Resorcinol, Tetrachlororesol 7nol, Tetrachlororesorcinol, Tetrachlororesol 7nol, 1
, 5-dihydroxynaphthalene, 1,6-dihydroxy/
Naphthalene, 1,7-dihydroxy/naphthalene, 2,6
-dihydroxynaphthalene, 2.7-dihydroxynaphthalene, bisphenol A1, tetrachlorobisphenol A1, tetrabromobisphenol A1, bisphenol S1, tetrachlorobisphenol S1, atrabromobisphenol S, and the like.

An aromatic compound having two hydroxyl groups represented by the following formula (in the formula, X is hydrogen, chlorine-j is bromine, A is improhenyl group, matahasulfone group, and is an integer from 1 to 4) as an intermediate raw material, and allyl chloroformate or β-methylallyl chloroform is used as an intermediate raw material. mate to obtain the novel bisallyl carbonate and bisβ-methylallyl carbonate of the present invention.

The above intermediate raw materials and allyl chloroformate or β-
Although the reaction with methylallyl chloroformate can be carried out without using a solvent, it is preferable to use a solvent that does not have reactivity with hydroxyl groups or chlorocarbonate groups, such as hydrocarbons such as hexane, cyclohexane, and benzene, and methylene. Use halogenated hydrocarbons such as chloride, chloroform, and carbon tetrachloride, and ketones such as acetone, methyl ethyl ketone, and cyclohexanone.

The reaction is carried out by solvent-free distillation or in the above-mentioned solvent, using a known hydrochloric acid scavenger, such as trialkylamine, per mole of the intermediate raw material.
While stirring, add 2 to 6 molar equivalents, preferably 2 to 3 molar equivalents, of pyridine, soda carbonate, caustic soda, etc.
While keeping the temperature of the reaction solution at -10 to 50°C, preferably 0 to 60°C, 2 to 6 mol, preferably 2 to 6 mol of allyl chloroformate or β-methylallyl chloroformate was added dropwise. ~80℃, preferably 20~
It is heated to 50°C. After the reaction is completed, the reaction solution is cooled, washed with dilute hydrochloric acid and then with dilute aqueous alkali solution, and when a solvent is used, the solvent is distilled off to obtain bisallyl carbonate and bisβ-methylallyl carbonate of the present invention. .

In addition, bisallyl carbonate-1 and bisβ of the present invention
-Another method for synthesizing methylallyl carbonate is
The above-mentioned intermediate raw material is subjected to a chloroformation reaction using an excess of Tsumesuge in advance, and the excess phosgene is distilled off to obtain an aromatic compound having two chlorocarbonate groups. It can also be obtained by reacting with lyl or β-methylallyl alcohol, but the synthesis conditions in this case are the same as those for the synthesis of the intermediate raw material and allyl chloroforme-1 or β-methylallyl chloroformate. Synthesize in accordance with .

Examples are shown below. Note that in the examples, "part" indicates a weighing part, and "ch" indicates weight %.

Example 1 198 parts of 1.4-bis(hydroxyethoxy)benzene was dissolved in 50 parts of chloroform, 24.2 parts of triethylamine was added, and 25 parts of allyl chloroformate was added over 2 hours while stirring and maintaining the temperature at 5 to 10°C. dripped.

After heating at 45 to 50°C for 6 hours, the reaction solution was poured into a separating funnel and washed with dilute hydrochloric acid and then water. The pale yellow organic layer obtained was dried with calcium chloride, treated with activated carbon, and concentrated under reduced pressure. Concentration gave a white solid. This is recrystallized from benzene to form white flaky crystals 1,
225 parts of 4-bis(hydroxyethoxy)benzene bisallyl carbonate were obtained.

Melting point 93-95℃ CH Elemental analysis value (%) 59.56 638 calculation value (to)) 59.01 6.05 (C□l]H
220B) NltllRδcpcj! 34. +5 (4H, t),
4.41-468 (4H, m), 5.21] ~5.4
0 (4H, m), 5.75-6.15 (2H, I
T+), 6.85 (4H, s) Example 2 1.5-bis(hydroxyethoxy)naphthalene 24B
was dissolved in 100 parts of acetone, 19.5 parts of pyridine was added, and 285 parts of β-methylallyl chloroformate was added dropwise over 2 hours while stirring and maintaining the temperature at 5 to 10°C. After heating at 50 to 55°C for 6 hours, the reaction solution was concentrated under reduced pressure, and 200 parts of toluene was added to dissolve the solution. The solution was poured into a separating funnel, washed with dilute hydrochloric acid and then with water, and the resulting pale yellow organic After drying the layer with calcium chloride, the active layer was treated with charcoal and concentrated under reduced pressure to obtain a white solid.

This is recrystallized from toluene to form a white amorphous crystal 1
, 5-bis(hydroxyethoxy)naphthalenebisβ-
28 parts of methylallyl carbonate were obtained.

Melting point 112-115°C CH Elemental analysis value (%) 64,75 6.48 Calculated value (%) 64. F35 6. ! +5(”24
As H280B) NMRa (!DOJ! 37.35 (6H, m), 4.
85 (4H, d), 4.58-4.38 (81 (,
m), 3.90 (4H, S), 1.65 (6H
, S) Example 6 5.
<5.5'-Tetrabromo-4, Ebis(hydroxyethoxy)diphenylpro 74,766 parts and 150 parts of chloroform were carried out in the same manner as in Example 1, and white amorphous crystals, s, s, 5'- 58 parts of tetrabromo-4,4'-bis(hydroxyethoxy)cyphenylpronochloride pisallyl carbonate were obtained.

Melting point 76-78℃ c'l ('13r Elemental analysis value (%) 40.59 only 5 40.5
7 Calculated value (ch) 40.53 3.53 39.9
5 (as C2,7H28Br408) NMRδcI) aJ31.60 (6H,S), 4.2
0 to 4.30 (4H, t), 4.48 to 4.68' (8
H, m), 5.20-5.40 (4H, m), 5
．． 70 ~ 6.15 (2) (, Iη) , 7.30 (4
H,s) Example 4 3.3 parts in place of 198 parts of 1,4-bis(hydroxyethoxy)benzene and 50 parts of chloroform in Example 1
? The procedure was carried out in the same manner as in Example 1 except that '5.5'-tetrachloro-4,4'-bis(hydroxyethoxy)diphenylsulfof-4, 6 parts and 150 parts of chloroform were used. White amorphous crystals were obtained. 3.45 parts of 5.5'-tetrachloro-4,4'-bis(hydroxyethoxy)diphenylsulfone bisallyl carbonate were obtained.

Melting point 58-61℃ CHC1S Elemental analysis value (%) 44.13 3.32 21.
83 5.01 Calculated value (related) 44,73 3.4
4 22.014.9B (C24H22Ct401oS
) NMRδ. circle. p3160 (6H,s),
4.25-4.35 (4H, t), 4.48-4.6B
(8H, m), 5.20-5.40 (4H, m)
, 5.70-6.15 (2H, m) , 7.25
(4H, s) Reference Example 1 A mixture of 100 parts of 3, s', 5,5'-tetrabromo-4,4'-bis(hydroxyethoxy)diphenylpropane and 10 parts of benzoyl peroxide was made into a glass for lens molding. Pour into a mold consisting of a mold and a polyethylene gasket, and heat at 80°C for 24 hours.
Copolymerization was carried out by holding at 00°C for 2 hours.

The resin is then removed from the mold and the resulting lens is translucent.
The hardness was also good, and the refractive index measured by an Atsube refractometer was nD-1601. In addition, the lens was set in a Tsujizaometer (WE-8UN-IX!-1 model manufactured by Toyo Rika Co., Ltd.) equipped with a sunshine carbon arc lamp, and after 1,500 hours, the lens was removed and the hue was compared with the lens before testing. As a result, no change in hue was observed.

Reference Example 2 6,3: 32 parts of 5'-tetrachloro-4,4'-bis(hydroxyethoxy)diphenylsulfone bisallyl carbonate was dissolved in 200 parts of chloroform,
While cooling the content liquid to a temperature of 20 to 30℃,
After dropping 80 parts of bromine and reacting at 40°C for 1 hour, the reaction solution was washed with water, and the organic layer was concentrated under reduced pressure to obtain a pale yellow solid, 3, (5,5'-tetrachloro-4,4 ′-Bis(hydrokinoethoxy)diphenylsulfone bis(
108 parts of 2,3-siflomoglobir) carbonate were obtained. After uniformly mixing 15 parts of the powder obtained by pulverizing this solid, 100 parts of polystyrene, 5 parts of antimony trioxide, and 05 parts of Tinuvin P (manufactured by Ciba Geigy) as an ultraviolet absorber, the mixture was molded into a cylinder at one temperature using an injection molding machine. 200-2
30℃, injection pressure BOOOKg10d, mold temperature 60℃
A test piece was prepared. The obtained test piece was subjected to ASTM-D6
As a result of testing using 35 test methods, the test piece reached the "non-flammable" stage, and the test piece was taken out after 150 hours using a weather meter equipped with a Nanshine carbon arc lamp, and tested before testing. As a result of comparing the hue of the sample, there was only a slight change in hue, indicating good results as an additive flame retardant for polystyrene.

Claims (1)

[Claims] 1) Represents the general formula (1) (where X is hydrogen, chlorine or bromine, A is an isopropenyl group or a sulfone group, and n is an integer from 1 to 4), bisallyl carbonate and bisβ-methylallyl carbonate represented by (R represents hydrogen or a methyl group).