JPH04272921A - Allyl ester oligomer - Google Patents

Abstract

PURPOSE:To provide an allyl ester oligomer which is excellent in curability and moldability and gives a cured article remarkably improved in resistance to heat and impact when compared with a conventional diallyl phthalate resin. CONSTITUTION:An allyl ester oligomer which has terminal allyl groups, a specified mol.wt., and a specified iodine value and is prepd. by the polycondensation of a dicarboxylic ester with a nitrogen-contg. polyol in an amt. of 1/3-1/50 of that of the ester and, if necessary, another polyol.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to a novel allyl ester oligomer. More specifically, the present invention relates to a novel allyl ester oligomer that has excellent curing properties and whose cured product has excellent physical properties such as heat resistance, impact resistance, and adhesiveness.

0002

[Prior Art] Allyl resins, which are mainly composed of prepolymers derived from diallyl orthophthalate, diallyl isophthalate, and diallyl terephthalate, have been known to have excellent retention of electrical properties at high temperatures and high humidity. It has been used extensively in electrical and electronic applications that require high reliability, and has a long track record. The above-mentioned allyl resin also has excellent dimensional stability, heat resistance, moisture resistance, water resistance, and other properties, but has the drawbacks that the manufacturing method is complicated and it is expensive. Furthermore, although it has excellent electrical properties, it has the disadvantage of poor mechanical properties such as impact resistance and bending strength. Furthermore, allyl ester oligomers having an allyl ester group at the end and the following structure in which the interior is derived from a polyvalent saturated carboxylic acid and a polyvalent saturated alcohol are also known. CH2=CHCH2O(CORCOOBO)nCORC
0OCH2CH=CH2 Here, R represents an organic residue derived from a polyvalent saturated carboxylic acid, and B represents an organic residue derived from a polyvalent saturated alcohol. In this case, if terephthalic acid, which has excellent symmetry, is used as the polyvalent saturated carboxylic acid, a cured product with very excellent physical properties can be obtained. However, these allyl ester oligomers have a slow curing speed, and although they have excellent mechanical properties as a thermosetting resin, they have the disadvantage of inferior impact resistance when compared to thermoplastic resins such as engineering plastics. Ta.

0003

[Problems to be Solved by the Invention] The object of the present invention is to solve these problems and to provide an allyl ester oligomer which has excellent curability and whose cured product has excellent physical properties such as heat resistance, impact resistance, and adhesiveness. The goal is to provide the following.

0004

[Means for solving the problem] As a result of intensive research to achieve the above object, we have found that an allyl ester oligomer synthesized using a nitrogen atom-containing polyol as a part of the raw material has excellent curability and hardness. The inventors discovered that the product also has excellent physical properties such as heat resistance, impact resistance, and adhesiveness, leading to the present invention.

[0005] The oligomer according to claim 1 of the present invention is obtained by using a raw material consisting of the following (a), (b) and optionally (c) in the presence of a transesterification reaction catalyst as expressed by the following relational formula (1). The number average molecular weight (Mn) in terms of polystyrene measured by GPC (gel permeation chromatography) is 500 to 500, obtained by charging and reacting at a molar fraction and distilling off allyl alcohol.
00, and the weight average molecular weight (MW) is 1000~
1,000,000, and the degree of unsaturation expressed as an iodine value measured by the Wijs method is 10 to 180. Raw material (a) CH2=CHCH2OCOR'COOCH2CH
=CH2 (b) Nitrogen-containing polyol (c) HOZ-(OH)X However, R' is an organic residue derived from a divalent carboxylic acid having 2 to 12 carbon atoms, and Z is represents an organic residue having 2 to 20 carbon atoms derived from a polyol having hydroxyl groups of 1 or more and 8 or less. Relational expression (1) a /b = 50/1 ~ 4/3 However, a,
b represents the molar fraction of raw materials (a) and (b), respectively.

[0006] The oligomer according to claim 2 of the present invention undergoes the following (a'), (b), (d) in the presence of a transesterification catalyst.
) and, if necessary, (c) at a molar fraction expressed by the following relational formula (1)', react with them, and distill off ROH.
Polystyrene equivalent number average molecular weight (Mn) measured by permeation chromatography method is 500 to 5.
0000, and the weight average molecular weight (MW) is 100
0 to 1,000,000, and the degree of unsaturation expressed as an iodine number measured by the Wijs method is 10 to 18.
It is an oligomer having an allyl ester at the terminal, which is characterized by 0. Instead of the diallyl ester of dicarboxylic acid (a), the corresponding diester of dicarboxylic acid with a lower aliphatic alcohol having 1 to 3 carbon atoms (a') and allyl alcohol (d) are used as raw materials,
It is an oligomer produced by an industrially more useful method of reacting while distilling off lower aliphatic alcohol ROH. Raw material (a') ROCOR'COOR (b) Nitrogen-containing polyol (c) HOZ-(OH)X (d) Allyl alcohol where R is an organic residue derived from a lower alcohol having 3 or less carbon atoms, R' is an organic residue derived from a divalent carboxylic acid having 2 to 12 carbon atoms, and Z is x+1 (
x represents an organic residue having 2 to 20 carbon atoms derived from a polyol having a hydroxyl group (1 or more and 8 or less). Relational expression (1)' a '/b = 50/1 to 4/3, where a' and b are raw materials (a') and (b), respectively.
represents the mole fraction of

The oligomer according to claim 3 of the present invention is characterized in that the nitrogen atom-containing polyol (b) as a raw material is at least one selected from the group consisting of ammonia, a primary amine, and an alkylene oxide adduct of isocyanuric acid. The allyl ester oligomer according to claim 1 or 2, characterized in that:

[0008] The oligomer according to claim 4 of the present invention is characterized in that the alkylene oxide adduct of isocyanuric acid is tris(2-hydroxyethyl) isocyanurate [3 moles of ethylene oxide adduct of isocyanuric acid]. It is the allyl ester oligomer described in 3.

[0009] The degree of unsaturation expressed in terms of iodine value measured by the Wijs method refers to the number of grams of iodine that can be added per 100 grams of oligomer, and is a guideline for the concentration of double bonds present in the polymer. In the case of an allyl ester oligomer, it can be used as a guideline for the number of allyl ester groups present at the terminal. If this degree of unsaturation is large, the number of allyl groups present at the end is too large,
There is a problem that distortion occurs during the curing reaction, resulting in a decrease in mechanical properties. On the other hand, if the degree of unsaturation is too low, the number of allyl groups present at the end will be too small, making it impossible to carry out the curing reaction effectively, resulting in poor heat resistance, impact resistance, and adhesive properties of the cured product. However, there is a problem that physical properties such as solvent resistance are deteriorated. Therefore, the allyl group concentration is
The degree of unsaturation expressed as an iodine value measured by the method (js) should be in the range of 10 to 180, more preferably 25 to 120.

The preferred molecular weight range of the allyl ester oligomer of the present invention is 500 to 50,000, more preferably 500 to 15,000 in terms of polystyrene equivalent number average molecular weight (Mn) measured by GPC (gel permeation chromatography) method. The weight average molecular weight (MW) is 1,000 to 1,000,000, preferably 1,000 to 70,000, and the MW/Mn ratio is 1.2.
~40.0. If the molecular weight is too large, the moldability and curability will decrease, and if the molecular weight is too small, the physical properties such as impact resistance of the cured product will decrease. Therefore, the molecular weight of the allyl ester oligomer of the present invention is Must be within the above range.

Examples of the nitrogen atom-containing polyol (b) used as a raw material in the present invention include ammonia, primary amines, and alkylene oxide adducts of isocyanuric acid. Specific examples of alkylene oxide adducts of ammonia and primary amines include triethanolamine, diethanolamine, bis(2-hydroxyethyl)merylamine, bis(2-hydroxyethyl)laurylamine, and tris(2-hydroxypropyl)amine. and so on. Specific examples of the alkylene oxide adduct of isocyanuric acid include an adduct of isocyanuric acid with 3 moles of ethylene oxide, a 3 mole adduct of isocyanuric acid with propylene oxide, and an adduct of 4 moles or more of propylene oxide.

(b) In addition to the nitrogen atom-containing polyol, raw materials used in the present invention include (a) CH2=CH
CH2OCOR'COOCH2CH=CH2, (a'
) ROCOR'COOR, (d) allyl alcohol, and (c) HOZ-(OH)X, which is used as necessary. Here, the divalent saturated carboxylic acids that give R' include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, β-methyladipic acid, pimelic acid,
Corkic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid,
Dodecanedicarboxylic acid, 1,2- or 1,3- or 1,4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, diphenyl-p,p'-dicarboxylic acid, diphenyl-m,m'-dicarboxylic acid ,1,
4- or 1,5- or 2,6- or 2,7-naphthalene dicarboxylic acid, diphenylmethane-p,p'-dicarboxylic acid, diphenylmethane-m,m'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid , p-phenylene diacetic acid, p-carboxyphenylacetic acid, methyl terephthalic acid, tetrachlorophthalic acid and the like. Among these, highly symmetrical divalent saturated carboxylic acids such as terephthalic acid and 2,6-naphthalene dicarboxylic acid provide particularly high physical properties.

[0013] Examples of dihydric saturated alcohols that give Z include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1 , 5-pentanediol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, undecamethylene glycol, dodecamethylene glycol, tridecamethylene glycol, eicosamethylene glycol, hydrogenated bisphenol-A, 1,6 -hexanediol, 1,4-cyclohexanedimethanol, 2-ethyl-2,5-
Addition of ethylene oxide to saturated glycols consisting only of carbon such as pentanediol, 2-ethyl-1,3-hexanediol, and styrene glycol, and diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, and bisphenol-A. Also included are dihydric saturated alcohols containing an ether group, such as propylene oxide adducts of bisphenol-A, and glycols containing bromine, such as dibromoneopentyl glycol. Among these, diols such as ethylene glycol, neopentyl glycol, and 1,4-butanediol which together with terephthalic acid, 2,6-naphthalene dicarboxylic acid, and the like yield polyesters with high crystallinity, provide particularly high physical properties. In addition, when glycols such as propylene glycol, 1,3-butanediol, and dipropylene glycol are used, they have good compatibility with polymerizable monomers, and the curing reaction can be carried out in various forms, making them preferred raw materials. . Examples of trivalent or higher polyhydric saturated alcohols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol.

[0014] Regarding the amount of these to be used, it is necessary to use them under certain restrictions regarding the ratio of the nitrogen atom-containing polyol and (a) or (a'). In other words, if a large amount of nitrogen atom-containing polyol is used, there is a problem that gelation easily occurs if the polyol has three or more functionalities;
Difunctional materials such as amine-alkylene oxide adducts have the problem that the crosslinking density is too low and that the curing agent tends to be abnormally decomposed. On the other hand, if the amount of the nitrogen atom-containing polyol used is small, the resulting cured allyl ester oligomer becomes brittle and cannot be put to practical use. Therefore, it is desirable to use the molar ratio of (a) or (a') to the nitrogen atom-containing polyol in the range of 50/1 to 4/3, more preferably 20/1 to 3/1.

[0015] In addition, the diol and polyol (c) can be used as appropriate for the purpose of adjusting the residual monomer concentration and viscosity, but in order to obtain an allyl ester oligomer with an allyl ester at the end, divalent saturated carboxylic acid It is necessary to use less hydroxyl groups in nitrogen atom-containing polyols and other polyhydric alcohols than carboxyl groups in nitrogen atom-containing polyols and other polyhydric alcohols. Furthermore, if the usage ratios of these functional groups are too close, the molecular weight of the produced allyl ester oligomer will increase significantly, making it impossible to carry out the curing reaction. Therefore, the ratio of carboxyl group/hydroxyl group is from 20/19 to 9/1, more preferably 16/1.
It is desirable to fall between 15 and 6/1.

[0016] The transesterification catalyst used is as follows:
Conventionally known transesterification catalysts can be used, but particularly preferred are alkali metals, alkaline earth metals, oxides thereof, weak acid salts, Mn, U,
Zn, Cd, Zr, Pb, Ti, Co and Sn oxides, hydroxides, inorganic acid salts, alcoholates, organic acid salts, organic tin compounds such as dibutyltin oxide, dioctyltin oxide, dibutyltin dichloride, etc. . The amount used should be such that allyl alcohol can be distilled off at an appropriate rate, although it will vary depending on the catalyst activity. Generally 0.0001 to 1% by weight, particularly preferably 0.001% by weight, based on the diallyl or dialkyl ester.
It is preferable to use about 0.1% by weight.

As an embodiment of the reaction, transesterification is carried out by heating above the boiling point of allyl alcohol when a diallyl ester is used, and above the boiling point of the lower alcohol when using a dialkyl ester of a lower alcohol. In order to advantageously produce oligomers, the produced allyl alcohol or lower alcohol is distilled out of the reactor by reactive distillation. Generally, the reaction is carried out under normal pressure or increased pressure, but it is also effective to increase the conversion rate of the reaction and to quickly distill off allyl alcohol or lower alcohol by reducing the pressure in the reaction system. As mentioned above, when diallyl ester is used, allyl alcohol cannot be effectively distilled off if the reaction temperature is below the boiling point of allyl alcohol, and if the temperature is too high, thermal polymerization may occur. Generally, the temperature is between 100 and 300℃.
temperature, more preferably from 130 to 250°C.

When a dialkyl ester of a lower alcohol is used, the lower alcohol to be produced and the allyl alcohol to be reacted have close boiling points, so if the reaction is heated too high from the beginning, the allyl alcohol will distill out together with the lower alcohol. There is a risk of it being stored away. Therefore, in addition to installing an efficient rectification column, the reaction temperature is generally between 80 and 150 degrees Celsius in the initial stage of the reaction, more preferably between 90 and 130 degrees Celsius, and after most of the lower alcohol has been distilled off. Between 100 and 300°C, more preferably 13
It is better to select a temperature between 0 and 250°C. The amount of allyl alcohol used in this case is required to be at least 0.2 molar equivalent relative to the dialkyl ester, and usually at least 0.5 molar equivalent, preferably at least 1 molar equivalent. However, if too much excess is used, excess allyl alcohol must be removed and the reaction rate will not necessarily become faster.
It should be kept below the molar equivalent. Further, depending on the reaction temperature, a polymerization inhibitor such as hydroquinone may be allowed to coexist in the reaction solution.

Various methods can be used to take out the oligomer after the reaction is completed. For example, it is possible to purify the produced allyl ester oligomer by removing the monomer by distillation or reprecipitation, but it is usually possible to use it even in the presence of diallyl ester monomers that are produced as by-products during the reaction or used as raw materials. This is more advantageous from an industrial standpoint. In addition, for the purpose of adjusting viscosity,
It is also possible to actively add a diallyl or triallyl monomer, and examples of such diallyl or triallyl monomers include diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl adipate, triallyl isocyanurate, and triallyl trimeryl. tate, diallyl 2,6-naphthalene dicarboxylate, diallyl endic acid, and the like.

[0020] Further, other polymerizable monomers may be added to carry out the polymerization as long as the physical properties and curability after polymerization are not impaired. Examples of such polymerizable monomers include aromatic vinyl compounds, (meth)acrylic acid and its esters, unsaturated dibasic acids and their derivatives, saturated aliphatic or aromatic carboxylic acid vinyl esters and their derivatives, ( Examples include vinyl cyanide compounds such as meth)acrylonitrile, unsaturated hydrocarbons, and halogenated unsaturated hydrocarbons. Examples of aromatic vinyl compounds include styrene, α-substituted styrenes such as α-methylstyrene, α-ethylstyrene, and α-chlorostyrene, and nuclear substitutions such as fluorostyrene, chlorostyrene, bromostyrene, chloromethylstyrene, and methoxystyrene. There is styrene. Examples of (meth)acrylic acid and its esters include acrylic acid, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate. Examples of unsaturated dibasic acids and their derivatives include dialkyl esters of maleic acid such as dimethyl maleate and diethyl maleate, dialkyl esters of fumaric acid such as dimethyl fumarate and diisopropyl fumarate, N-phenylmaleimide, N- Examples include maleimides such as cyclohexylmaleimide and acid anhydrides such as maleic anhydride.

Vinyl esters of saturated aliphatic or aromatic carboxylic acids and their derivatives include vinyl acetate, vinyl propionate, vinyl benzoate, vinyl n-butyrate, and the like. Examples of unsaturated hydrocarbons include 1-hexene, 1-octene, and 4-vinylcyclohexene. Examples of halogenated unsaturated hydrocarbons include vinyl chloride and vinyl bromide. Further, crosslinkable polyfunctional monomers can also be used, such as diallyl carbonate, diethylene glycol diallyl carbonate, divinylbenzene,
Difunctional crosslinking monomers such as neopentyl glycol di(meth)acrylate and divinyl adipate; trifunctional monomers such as trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, diallyl maleate, and diallyl fumarate. The above crosslinking monomers can be mentioned. Additionally, polymers with double bonds such as unsaturated polyesters can be used as well as reactive monomers.

The oligomer of the present invention may contain fillers, polymerization accelerators, polymerization inhibitors, internal mold release agents, coupling agents, etc., as desired, as in the case of conventional diallylphthalate resins and unsaturated polyesters. , pigments, flame retardants, and other additives can be blended within a range that does not impair the properties of the oligomer to improve the molding processability or the physical properties of the molded article.

[0023] The method for molding the oligomer of the present invention is as follows:
The same known molding methods and molding conditions as those for conventional diallyl phthalate resins can be applied as they are. That is, a casting method in which the oligomer of the present invention is injected into a mold and cured, an injection molding method or a transfer molding method in which the oligomer is heated to a fluid state, and then placed in a mold and heated to harden; A compression molding method in which the oligomer is cured by heating and pressurizing in a mold, the oligomer is dissolved in a suitable organic solvent, impregnated into a fibrous sheet, and the resin is heated in a dryer under pressure if necessary in the fibrous sheet. A laminate molding method in which the oligomer is cured, a coating method in which a fine powder or solution of the oligomer is applied to a substrate and cured on the substrate, and a printing paper or the like is impregnated with the oligomer solution, and after drying, it is heated and pressed onto the substrate. An example of a molding method is a decorative board molding method in which the resin is cured by heating. As the heating temperature for curing during molding, a temperature of about 60 to about 220° C. can be exemplified. In addition, when using pressurized conditions, the pressure is as follows:
A pressure of about 5 to 1000 kg/cm2 can be exemplified.

[0024] Also, unlike conventional diallylphthalate resins, some of the oligomers of the present invention are liquid at room temperature, and can be molded in the same manner as liquid unsaturated polyester. It has become possible to widen the scope of use. The oligomer of the present invention can be used as a molding material in the following wide range of fields by taking advantage of its good curability and formability. for example,
Connectors, motor commutators, governors, coil bobbins, relays, switches, terminal boards, ignitions, breakers, sockets, sliding resistor binders,
Electrical and electronic fields such as printed wiring boards, encapsulating materials for electronic parts and elements, coil encapsulation and other insulating materials in light to heavy electrical fields; Also, for example, plastic brake pistons and other mechanical fields; for example, tableware and other It is useful as a molding material in the field of daily necessities; for example, in the field of medical materials such as trays and containers that require chemical or steam sterilization.

Furthermore, the oligomer is impregnated or applied onto a fibrous sheet such as paper, non-woven fabric, glass cloth, etc. in the presence or absence of a solvent, and the oligomer is pressed and cured onto a wood, paper, metal or other inorganic substrate, or The pre-cured product is applied to the above-mentioned base material in the form of a decorative board and is useful for various building materials, furniture, interiors, cabinets, kitchen equipment, axles, ship interior materials, and other fields. In addition, if the oligomer is impregnated into wood and cured as it is or diluted with a solvent, it becomes a wood-plastic composite (so-called WPC),
It can be used in fields such as floorboards, decks, sheds, architectural structural materials, and sporting goods, and can also be used as a laminate made by impregnating and laminating glass cloth or other fibrous sheet structures, which require various properties at high temperatures and high humidity. For example, terminal plates, wedges for motors, insulation collars, slot armors, coil separators, etc., rotating machine related fields, duct pieces, barriers, terminal plates, etc.
It is useful in fields related to stationary machines such as operating rods, panels such as switchboards, printed wiring boards, PC insulation supports, etc. Furthermore, it has excellent dimensional stability even under drastic changes in temperature and humidity, and requires good mechanical strength. Fields that require chemical resistance, such as laser domes, missile blades, rocket nozzles, jet aircraft air ducts, etc.; fields that require chemical resistance, such as parts of various chemical equipment; and weather resistance, such as antennas, skis, ski poles, fishing rods, etc. Fields that require strength, chemical resistance, and mechanical strength, other paints, materials for molds for molding other resins, hot stamping resins, UV curing inks, materials for lenses and other optical applications, glass fibers, carbon fibers. It can be used in a wide range of applications, such as as a binder for lithography, and as a resin for resist films in lithography using light, electron beams, or X-rays.

[0026]

[Examples] The present invention will be explained in more detail below, but the present invention is not limited to these Examples unless it departs from the gist of the present invention. Example 1 1200 g of diallyl terephthalate (hereinafter abbreviated as DATP) was placed in a 2 liter three-necked flask equipped with a distillation device.
Tris(2-hydroxyethyl)isocyanurate 10
6.1 g of propylene glycol, 247.2 g of propylene glycol, and 0.3 g of dibutyltin oxide (abbreviated as DBO) were charged and heated to 180° C. under a nitrogen stream to distill off the allyl alcohol produced. When about 320g of allyl alcohol was distilled out, the pressure inside the reaction system was reduced to 50mmHg.
The distillation rate of allyl alcohol was increased. After the theoretical amount of allyl alcohol had distilled off, heating was continued for an additional hour. Thereafter, the pressure was reduced using a vacuum pump to distill off residual allyl alcohol, and 1100 g of allyl ester oligomer was obtained. Table 1 shows the results.

Examples 2 to 5 and Comparative Examples 1 to 2 Allyl ester oligomers were synthesized in substantially the same manner as in Example 1, except that the raw materials and the molar ratio of the charged materials were different. In addition, as a comparative example, tris(2-hydroxyethyl)isocyanurate (TH
Allyl ester oligomer was synthesized in almost the same manner as in Example 1 except that glycerin was used instead of EIC (comparative example 1), and tris(2-hydroxyethyl)isocyanurate (THEIC) was synthesized in substantially the same manner as in Example 1. Table 1 also shows the results of allyl ester oligomers synthesized in substantially the same manner as in Example 1 (Comparative Example 2), except that no substitute for ) was used (Comparative Example 2).

[0028] Dicumyl peroxide 2 is further added to these allyl ester oligomers as a radical polymerization initiator.
mixed phr. The obtained composition was placed on a heating plate at 160° C., and the time until it stopped becoming stringy was measured, which was determined as the gel time. Further, a predetermined amount of the composition obtained above was taken, and cast polymerization was carried out at 130° C. using a cellophane-lined glass plate.
After curing for 1 hr, after-curing was performed at 160° C. for 5 hr. The physical properties of the obtained molded product were determined according to JIS K-69.
Measurement was carried out according to 11. These results are also shown in Table 1.

The allyl ester oligomer in Table 1 was analyzed by the following method. A) Method for measuring and determining iodine value Accurately weigh 0.25 to 0.35 g of allyl ester oligomer, put it in a 200 ml iodine flask, and
Add ml of chloroform to completely dissolve the sample. To this, add exactly 20 ml of wijs reagent (dissolve 7.9 g of iodine trichloride and 8.2 g of iodine in 200 to 300 ml of glacial acetic acid, then mix both solutions to make 1 liter) using a whole pipette. Next, 10 ml of a 2.5% mercuric acetate solution in glacial acetic acid was added, and the mixture was left in the dark for 20 minutes to complete the reaction. I made a new 20% KI for this.
Add 5 ml of the solution and use 1% starch solution as an indicator.
Titrate with 0.1N Na2S2O3 standard solution. A blank test will also be conducted at the same time. A: 0.1 N-Na2 S2 O3 required for blank test
Number of ml of solution B: 0.1 N-Na2S required for this test
2 Number of ml of O3 liquid f: 0.1 N-Na2 S2
O3 liquid titer s: number of grams of sample

B) Method for measuring and determining Mn and Mw by GPC method Mn and Mw in terms of polystyrene are measured by GPC. SHODEX column AC-80P, 802, 80
4 and 806 were connected in series in this order, chloroform was used as the solvent, the temperature was 25°C, and the flow rate was 1.0 ml.
/min. ■ First, use at least 10 types of commercially available standard polystyrenes whose average molecular weights are known, calculate the retention time of each along with the DAT monomer, and approximate the relationship between average molecular weight and retention time using a cubic curve or a broken line. A calibration curve was created. (2) Dissolve 20 mg of the sample in 20 ml of chloroform, and inject 0.5 ml into the column through the line filter using a loop injector. Excluding the data of the residual monomer portion from the obtained elution curve data, Mn and Mw are determined by automatically calculating in a data processing machine such as Shimadzu CR-3A based on the calibration curve prepared in (2). Here, the peak was divided at 10 second intervals, the molecular weight at each division point was Mi, and the height of the peak was Hi, and the calculation was performed using the following formula. Mz was calculated using the following formula.

Example 6 In a 3-liter three-necked flask equipped with a rectifier, 946.3 g of dimethyl terephthalate, 106.1 g of tris(2-hydroxyethyl) isocyanurate, 247.2 g of propylene glycol, and 566.0 g of allyl alcohol were added.
g and 0.5 g of dibutyltin oxide were charged and heated to 150° C. under a nitrogen stream, and the generated methanol was distilled off. In addition, allyl alcohol entrained with methanol was added to the reactor in an amount equal to the distilled amount. When the theoretical amount of methanol (312 g) was distilled off, the reaction temperature was raised to 180° C. and allyl alcohol was distilled off. When about 300 g of allyl alcohol was distilled off, the pressure inside the reaction system was reduced to 50 mmHg to accelerate the distillation rate of allyl alcohol. After almost all the distillate disappeared, the pressure was reduced using a vacuum pump and maintained for another 1 hour to distill off residual allyl alcohol, and the reaction product was cooled to obtain 1100 g of allyl ester oligomer.

Examples 7 to 12 Allyl ester oligomers were synthesized in substantially the same manner as in Example 1 using various nitrogen atom-containing polyols. Table 2 shows the results of measuring the physical properties of this allyl ester oligomer in the same manner.

[Table 1]

[Table 2]

[0033]

[Effect of the invention] The allyl ester oligomer of the present invention is
As a raw material for synthesis by polycondensation reaction, a nitrogen atom-containing polyol is used in a range of 1/3 to 1/50 of the dicarboxylic acid ester, which is the other raw material, and other polyols are used as necessary. It is an allyl ester oligomer with an allyl group at the end, which has a specific molecular weight and iodine value, and is synthesized using Diaryl as a raw material, and has excellent curability and moldability. Dramatically improved heat resistance compared to resin,
Because it has impact resistance, it can be used in fields that require constant speed curing and moldability, such as molding materials, decorative laminates, electronic and electrical materials, and paints, and its industrial value is enormous.

[Table-1]

Claims (4)

[Claims] Claim 1: In the presence of a transesterification catalyst, raw materials consisting of the following (a), (b), and optionally (c) are charged and reacted at a molar fraction expressed by the following relational formula (1). The polystyrene equivalent number average molecular weight (M
n) is 500 to 50,000, the weight average molecular weight (MW) is 1,000 to 1,000,000, and the degree of unsaturation expressed as an iodine value measured by the Wijs method is 10 to 180. An oligomer with an allyl ester at the end. Raw material (a) CH2=CHCH2OCOR'COOCH2CH
=CH2 (b) Nitrogen-containing polyol (c) HOZ-(OH)X However, R' is an organic residue derived from a divalent carboxylic acid having 2 to 12 carbon atoms, and Z is represents an organic residue having 2 to 20 carbon atoms derived from a polyol having hydroxyl groups of 1 or more and 8 or less. Relational expression (1) a /b = 50/1 ~ 4/3 However, a,
b represents the molar fraction of raw materials (a) and (b), respectively. [Claim 2] In the presence of a transesterification catalyst, raw materials consisting of the following (a'), (b), (d), and optionally (c) are mixed in moles expressed by the following relational formula (1)'. The polystyrene equivalent number average molecular weight (Mn) measured by the GPC (gel permeation chromatography) method is 500 to 50,000, and the weight average is obtained by reacting in fractions and distilling off ROH. Molecular weight (MW) is 1,000 to 1,000,000, and
An oligomer having an allyl ester at its terminal, characterized by having an unsaturation degree of 10 to 180 as expressed by an iodine number measured by the Wijs method. Raw material (a') ROCOR'COOR (b) Nitrogen-containing polyol (c) HOZ-(OH)X (d) Allyl alcohol where R is an organic residue derived from a lower alcohol having 3 or less carbon atoms, R' is an organic residue derived from a divalent carboxylic acid having 2 to 12 carbon atoms, and Z is x+1 (
x represents an organic residue having 2 to 20 carbon atoms derived from a polyol having a hydroxyl group (1 or more and 8 or less). Relational expression (1)' a '/b = 50/1 to 4/3 However,
a' and b represent the molar fractions of raw materials (a') and (b), respectively. 3. The nitrogen atom-containing polyol (b) of the raw material is at least one selected from the group consisting of ammonia, a primary amine, and an alkylene oxide adduct of isocyanuric acid. Allyl ester oligomer described in. 4. The allyl ester oligomer according to claim 3, wherein the alkylene oxide adduct of isocyanuric acid is tris(2-hydroxyethyl) isocyanurate [3 mole ethylene oxide adduct of isocyanuric acid].