JPH06313033A - New allylic oligomer - Google Patents

Abstract

PURPOSE:To obtain a low shrinkage resin composition capable of providing a cured product excellent in surface smoothness without limiting the amount of styrene, etc., as a reactive diluent, and causing trouble, e.g. occurrence of unevenness or milky turbidity or lowering of strength due to occurrence of void in the cured resin. CONSTITUTION:This new allylic oligomer is obtained by reacting raw materials containing the following components (A) to (C) in the following molar ratio. (A) Triallyl trimellitate and/or tetraallyl pyromellitate, (B) a dialkyl ester of 4-20C divalent aromatic and/or aliphatic dicarboxylic acid and (C) a diol having two alcoholic hydroxy groups. [Molar ratio: 0.9<(A+B)/C<4 and 0<=B/A<3].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel allylic oligomer, more specifically, a novel allylic compound capable of obtaining a cured product having a fast curing rate and excellent surface hardness and heat resistance. The present invention relates to a system oligomer.

[0002]

2. Description of the Related Art DAP resins using diallyl phthalate (hereinafter abbreviated as DAP) as a monomer are molding materials,
It is widely used for decorative boards, laminated boards, etc., and has earned the trust that its electrical characteristics under high temperature and high humidity do not deteriorate over a long period of time. However, as machines and electric parts to be used have higher performance, there is an increasing demand for a resin having further improved heat resistance while maintaining the present excellent surface. Also,
DAP resin has two double bonds in the monomer, and if it is polymerized normally, it will gel at a low conversion rate, so the polymer obtained by temporarily stopping the polymerization before gelation is taken out as a prepolymer. , It is used by putting a polymerization initiator and a filler in the prepolymer for actual use. Therefore, how to efficiently produce a prepolymer is also an important issue, and it is not sufficient at present, and development of an efficient production method has been desired.

When diallyl terephthalate (hereinafter abbreviated as DAT) having excellent symmetry is used as a monomer, improvement in heat resistance can be expected, but at present, the secondary cured product of DAT has poor mechanical properties such as brittleness. It is known that it has not been put to practical use.

Heretofore, a method of bulk polymerization or a method of polymerizing into a prepolymer using various solvents has been known. However, in the case of bulk polymerization without using a solvent, the iodine value decreases only to about 80 even if the polymerization is carried out just before the gel conversion rate, and the Mw of the GPC method in that case becomes a very high value. I will end up. According to the study of the present inventors, when a secondary cured product is obtained by using a prepolymer having an iodine value and a high Mw which are too high, not only the drawback of being hard and brittle is not improved but also the viscosity at the time of molding is improved. It just rises mischievously and the physical properties are not improved.

Further, Japanese Patent Laid-Open No. 59-80409 discloses that
Described is a method for synthesizing a prepolymer capable of obtaining a cured product having excellent heat resistance and high mechanical strength by copolymerizing DAT and an aromatic hydrocarbon having at least one hydrogen atom at the benzyl position such as toluene and xylene. Has been done. However, in order to obtain such a copolymer, it is necessary to devise a polymerization method and a reaction device in which a monomer and an initiator-aromatic hydrocarbon must be blown out from a special nozzle under high speed stirring. Moreover, this method has a drawback that it requires a large amount of initiator and is difficult, if not impossible, to reuse the monomer because it is a radical copolymerization.

Besides, it is possible to carry out the polymerization by using a halogenated hydrocarbon having a relatively high chain transfer constant, an aldehyde derivative or the like, but in this case also, the radical generated from the solvent is added to the allyl group. That is, so-called telomerization occurs, and the performance as a polymer deteriorates. In addition, a diallyl isophthalate resin is also known as a resin having high heat resistance, but although it is industrially produced, the monomer price is very high and it is not practical.

A method using a special monomer such as naphthalenedicarboxylic acid diallyl ester has also been proposed in the patent, but this also has a high monomer price and has not been put to practical use. Moreover, it cannot be said that the productivity of the prepolymer is improved by any method. DAP
Attempts have also been made to copolymerize a monomer with another monomer having a double bond, and those having good physical properties such as a copolymer with ethylene are known. However, in this case as well, the DAP monomer has two double bonds, which causes gelation, so polymerization must be stopped in the middle, and even if physical properties are improved, monomer recycling, rather productivity, etc. Often disadvantageous in terms. Unsaturated polyesters based on terephthalic acid are also known, but in this case, maleic anhydride and fumaric acid must be added as unsaturated components, and the heat resistance of this part is not sufficient.
The g is not so high either.

In addition, having an allyl ester group at the terminal
Part derived from polyvalent saturated carboxylic acid and polyvalent saturated alcohol
Allyl ester resin having the following structure is also known
It CH₂= CHCH₂O (CORCOOBO)_nCORCOOCH₂CH = CH₂  [Wherein R is an organic residue derived from a divalent organic acid, B is
Is a polyvalent organic residue derived from polyol, n is 1 to
It is an integer of 20] When a terephthalic acid skeleton is used for R, heat resistance and impact resistance
It gives a cured product with excellent impact resistance,
It is hard to say that they have sufficient physical properties, and
The curing reaction is slow due to the curing reaction only by the allyl groups at the edges.
It also had the drawback of being bad.

[0009]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide an allyl type curable resin which has a high curing rate and which is excellent in surface hardness, heat resistance and curability. New thermosetting resin.

[0010]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that when an alkyl ester of a trivalent or higher polyvalent carboxylic acid was conventionally used in a transesterification reaction. , Gelation occurs in the polycondensation reaction process, it is difficult to take out the reaction product, on the other hand, if the amount of the polyvalent carboxylic acid used is limited, the entire reaction solution will not gel, Even in this case, insoluble matter that seems to be a partial gel may be generated, and there is a drawback that it is necessary to considerably reduce the amount of polyvalent carboxylic acid to be used in order to avoid it. When an allyl ester having a double bond is used as the ester at a specific molar ratio, the transesterification rate in the presence of a transesterification reaction catalyst is comparable to that of the corresponding saturated alkyl ester. It is not necessary to carry out the reaction at high temperature like usual polycondensation reaction, and the polyester having an allyl ester group in the side chain and the main chain skeleton derived from dicarboxylic acid and polyvalent saturated alcohol can be obtained. The inventors have found that a cured product excellent in surface hardness, heat resistance and curability can be obtained from this polyester, and thus completed the present invention.

The invention of claim 1 of the present invention comprises the following (A) to
A novel allylic oligomer obtained by reacting a raw material containing the component (C) in the following molar ratio in the presence of a transesterification reaction catalyst. (A) triallyl trimellitate and / or tetraallyl pyromellitic acid, (B) dialkyl ester of divalent aromatic and / or aliphatic dicarboxylic acid having 4 to 20 carbon atoms, and (C) two alcoholic hydroxyl groups. However, the alkyl group of the dialkyl ester (B) is an alkyl group derived from a saturated or unsaturated hydrocarbon having 3 or less carbon atoms. Molar ratio: 0.9 <(A + B) / C <40 0 ≦ B / A <3 where A, B and C are the component (A) and (B), respectively.
It represents the number of moles of the component and the component (C). Although low molecular weight raw material monomers such as allyl ester monomers remain in the synthesized oligomers, these residual monomers can be used as they are without separation,
In the present invention, an oligomer containing these residual monomers is also treated as an oligomer.

The invention according to claim 2 of the present invention is the novel allyl oligomer according to claim 1, characterized in that a diol (C) component containing a polyol having a valence of 3 or more is used.

The invention of claim 3 of the present invention is (A) to
3. A raw material containing a copolymerizable monomer in addition to the component (C) is used.
It is a novel allylic oligomer described.

The present invention will be described in detail below. As described above, when an allyl ester having a double bond is used as the alkyl ester of polyvalent carboxylic acid, the transesterification rate is considerably faster than that of the corresponding saturated alkyl ester, and the polycondensation reaction So you don't have to do it at high temperatures. When the polycondensation reaction is carried out at a relatively low temperature, in the case of a polyvalent carboxylic acid having a carboxylic acid at the 1- and 2-positions of the benzene ring, such as trimellitic acid and pyromellitic acid, one carboxylic acid is used. When the allyl ester participates in the transesterification reaction, the transesterification reaction of the other carboxylic acid allyl ester is significantly delayed. As a result, triallyl trimellitate and tetraallyl pyromelliticate behave as divalent carboxylic acid allyl esters. Moreover, the resulting polycondensate becomes a polymer having an allyl ester group on its side chain, and if this double bond is used to carry out radical polymerization, it becomes possible to use it as a thermosetting resin. As described above, the polycondensate can improve the curing speed, the surface hardness, and the heat resistance of the cured product, which have hitherto been defects of the terminal type allyl ester oligomer.

Regarding the molar ratio of the components (A), (B), and (C) used, unless the component (A) is used for a certain amount or more, the side chain allyl ester polycondensate described above is naturally used. In addition, the component (B) must be used under a limited use molar ratio. However, depending on the molding method, curing may be too fast or heat resistance may be sacrificed. It is a useful compound for improving strength and impact resistance.

The molar ratio of the components (A), (B) and (C) to be used can be selected from a wide range, but when the amount of the diol (C) used is too large, the unreacted diol is used. Remains, which is not preferable as a thermosetting resin, so it is necessary to purify the oligomer. When the amounts of the components (A) and (B) used are larger, the residual monomer derived from the raw material is often a compound containing an allyl group even if it is derived from the component (B). Although it can be used as a resin, excessive residual is not preferable because the cured product of the polycondensation product formed becomes brittle. Therefore, the molar ratio of these is preferably 0.9 <(A + B) / C <40 ≦ B / A <3, and more preferably 0.95 <(A + B) / C <30 ≦ B / A <3. It is more preferable to select from

Examples of the dialkyl ester of the divalent aromatic or aliphatic dicarboxylic acid as the component (B) 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,
Undecane dicarboxylic acid, dodecane dicarboxylic acid, fumaric acid, maleic acid, itaconic acid, citraconic 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
Examples thereof include dialkyl esters such as 4'-dicarboxylic acid, p-phenylenediacetic acid, p-carboxyphenylacetic acid, methylterephthalic acid, and tetrachlorophthalic acid.

As the alkyl group, it is preferable to use an allyl group or to give an alcohol having a boiling point lower than that of allyl alcohol. Examples of such an alkyl group include a methyl group, an ethyl group and an isopropyl group, particularly a methyl group. It is preferable in terms of boiling point and economical efficiency of the produced alcohol.

As the diol as the component (C), ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,5-pentane are used. Diol, hexamethylene glycol, heptamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, undecamethylene glycol, dodecamethylene glycol, tridecamethylene glycol, eicosamethylene glycol,
Hydrogenated bisphenol-A, 1,4-cyclohexanedimethanol, 2-ethyl-2,5-pentanediol,
Saturated glycol consisting of only carbon such as 2-ethyl-1,3-hexanediol, styrene glycol and tricyclodecane dimethanol, and ethylene oxide adduct of diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol and bisphenol-A. , A divalent saturated alcohol containing an ether group such as a propylene oxide adduct of bisphenol-A, and a glycol containing bromine such as dibromoneopentyl glycol.

If a very small amount of polyvalent saturated alcohol having a valence of 3 or more is used in the component (C), it can be used in place of the diol. The use of trihydric or higher polyhydric saturated alcohols is preferable from the viewpoint of heat resistance, but it is extremely easy to cause gelation, so it is better to use only a small amount, and in the case of trihydric polyols (A) + (B) component of 0.
5 times mol% or less, more preferably 0.33 times mol% or less, and in the case of a tetravalent or higher polyol, 0.33 times mol% or less of (A) + (B) components, more preferably 0.2 times mol% % Or less is preferable. Examples of trivalent or higher polyhydric saturated alcohols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, and isocyanuric acid alkyl oxide adducts.

The transesterification reaction catalyst used is
Although conventionally known transesterification catalysts can be used, particularly preferred are alkali metals, alkaline earth metals and their oxides, and weak acid salts, Mn, U, Zn, Cd, Z.
Examples thereof include oxides of r, Pb, Ti, Co and Sn, hydroxides, inorganic acid salts, alcoholates, organic acid salts, organic tin compounds such as dibutyltin oxide, dioctyltin oxide and dibutyltin dichloride.

The amount used should be such that allyl alcohol can be distilled at an appropriate rate, although it depends on the activity of the catalyst. Generally, it is preferable to use 0.0001 wt% to 1 wt%, particularly preferably 0.001 wt% to 0.1 wt% with respect to the components (A) and (C).

When the reaction temperature is lower than the boiling point of allyl alcohol, the distillation of allyl alcohol cannot be carried out effectively, and when the temperature is too high, the selectivity of the reaction does not appear, and not only thermal polymerization but also Since there is a risk of gelation even in the polycondensation reaction itself, it is generally preferable to select from 100 ° C to 200 ° C, more preferably from 130 ° C to 180 ° C.

When a dialkyl ester other than the allyl group is used, the corresponding alcohol is produced together with the allyl alcohol. In this case, if an efficient rectification column is attached and the lower alkanol other than allyl alcohol is first distilled off, the allyl group can be efficiently left.

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.
For example, it is possible to remove the monomer from the produced allyl ester oligomer by distillation or reprecipitation for purification, but usually it is also used as a by-product during the reaction or in a state in which the allyl ester monomer used as a raw material coexists. This is industrially advantageous. It is also possible to positively add another copolymerizable monomer for the purpose of adjusting the viscosity. The appropriate amount of the other copolymerizable monomer used varies depending on the other monomer to be combined, but from the viewpoint of the shrinkage ratio, it is preferably 60% by weight or less, and more preferably 40% by weight or less, based on the whole monomer.

Other copolymerizable monomers include, for example,
Cyanation of allylic monomers, 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, (meth) acrylonitrile, etc. Examples thereof include vinyl compounds, unsaturated hydrocarbons and halogenated unsaturated hydrocarbons.

The allyl monomers include allyl benzoate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, 1,4- or 1,3- or 1,2-cyclohexanedicarboxylic acid diallyl, diallyl adipate, triallyl isocyanurate. , Triallyl cyanurate, diallyl 2,6-naphthalenedicarboxylate, diallyl endic acid, diethylene glycol diallyl carbonate, triallyl trimellitate, tetraallyl pyromelliticate and the like.

As the aromatic vinyl compound, styrene or α-methylstyrene, α-ethylstyrene, α-
Α-Substituted styrene such as chlorostyrene, fluorostyrene, chlorostyrene, bromostyrene, chloromethylstyrene, nuclear-substituted styrene such as methoxystyrene and the like can be mentioned.

Examples of (meth) acrylic acid and its ester include acrylic acid, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, benzyl methacrylate, and methacrylic acid. Examples thereof include phenyl and isobornyl methacrylate.

As the unsaturated dibasic acid and its derivative,
Examples thereof include dialkyl esters of maleic acid such as dimethyl maleate and diethyl maleate, and dialkyl esters of fumaric acid such as dimethyl fumarate and diisopropyl fumarate.

Examples of vinyl esters of saturated aliphatic or aromatic carboxylic acids and their derivatives include vinyl acetate, vinyl propionate, vinyl benzoate and vinyl n-butyrate.

As the unsaturated hydrocarbon, 1-hexene,
1-octene, 4-vinyl cyclohexene, etc. can be mentioned.

Examples of halogenated unsaturated hydrocarbons include vinyl chloride and vinyl bromide. Further, a crosslinkable polyfunctional monomer can also be used, and as such, for example, a difunctional crosslinkable monomer such as diallyl carbonate, divinylbenzene, neopentyl glycol di (meth) acrylate, and divinyl adipate, trimethylol. Examples thereof include trifunctional or higher functional crosslinkable monomers such as propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, diallyl malate and diallyl fumarate.

Further, a polymer having a double bond such as unsaturated polyester can be used in the same manner as the reactive monomer.

The novel allylic oligomer of the present invention is added with a filler, a polymerization accelerator, a polymerization inhibitor, an internal mold release agent, a coupling agent, a pigment, and the like, like the conventional DAP resin and allyl ester resin. It is also possible to use it as a molding material by blending the agent in an amount that does not impair the physical properties.

Since the novel allyl oligomer of the present invention has an appropriate double bond, it can be used as a mixture with unsaturated polyester resin, diallyl phthalate resin, etc., EPR, chlorinated polyethylene. It can also be used as a crosslinking agent for synthetic rubber and the like. The present invention will be described in more detail below.

[0037]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. (Example 1) 1200 g of triallyl trimellitate was added to a 2 liter three-neck separable flask equipped with a distillation apparatus,
Propylene glycol 184.3 g, dibutyltin oxide 1.2 g, and Irganox 1076 [manufactured by Ciba-Geigy Co., Ltd.] 0.12 g were charged and then heated to 180 ° C. under a nitrogen stream to distill off the produced allyl alcohol. . When about 220 g of allyl alcohol was distilled, the pressure inside the reaction system was reduced to about 10 torr to accelerate the distillation rate of allyl alcohol. After the theoretical amount of allyl alcohol (twice the molar amount of propylene glycol) was distilled off,
Heating (180 ° C.) was continued under reduced pressure for another hour. Then, the system was placed in a nitrogen atmosphere at atmospheric pressure, cooled to 120 ° C., and the product was taken out at that temperature. The physical properties of the product are shown in Table 1.

(Examples 2 to 12) Side chain allyl ester oligomers were synthesized in substantially the same manner as in Example 1 except that the raw materials and the charged molar ratio were different. The results are also shown in Table 1 (Examples 2 to 7) and Table 2 (Examples 8 to 12).

(Examples 13 to 14) Side chain allyl ester oligomers were synthesized in substantially the same manner as in Example 1 except that the polyol was used together with the diol. The results are shown in Table 3.

(Examples 15 to 17) Side chain allyl ester oligomers were synthesized in substantially the same manner as in Example 3 except that the copolymerizable monomers shown in Table 3 were used together. The results are also shown in Table 3.

(Comparative Examples 1 and 2) As comparative examples, allyl ester oligomers synthesized by using diallyl terephthalate and diallyl isophthalate instead of triallyl trimellitate and tetraallyl pyromellitic acid were synthesized, and the physical properties of the products were measured. It is also shown in Table 2.

The monomer concentration remaining in the synthesized allyl ester oligomer was determined by analysis by the GC method. For the measurement of the molecular weight by the GPC method, Mn, Mw and Mz in terms of polystyrene were obtained. <Measurement of Mn and Mw by GPC method> Mn and Mw in terms of polystyrene are measured by GPC. SHO
One DEX column AC-80P, 802, 804, and 806 is connected in series in this order, and chloroform is used as a solvent at a temperature of 25 ° C. and a flow rate of 1.0 ml / min. First, using at least 10 kinds of commercially available standard polystyrenes having known average molecular weights, the relationship between the respective storage times together with the diallyl terephthalate (DATP) monomer was approximated by a cubic curve or a broken line to prepare a calibration curve. 20 mg of sample is dissolved in 20 ml of chloroform, and 0.5 ml is injected into the column through a line filter using a loop injector. Shimadzu CR based on the calibration curve prepared in
-Automatically calculated in a data processor such as -3A, M
Find n and Mw. Here, the peak was divided at intervals of 10 seconds, the molecular weight of each division point was Mi, and the height of the peak was Hi, and calculation was performed by the following formula.

[0043]

(Gel time) The allyl ester oligomers obtained in Examples 1 to 17 and Comparative Examples 1 to 2 were further supplemented with dicumyl peroxide 2ph as a radical polymerization initiator.
r mixed. The obtained composition was placed on a heating plate at 160 ° C., and the time until no stringing was observed was examined and the gel time was taken.

(Physical Properties of Cured Product) A predetermined amount of the composition obtained above is cured by cast polymerization using a cellophane-tensioned glass plate at 130 ° C./1 hr, and then cured by after-curing at 160 ° C./5 hr. (Depending on the viscosity of the sample, it was partially molded by pressing). The physical properties of the obtained molded product are JIS K-
Measured according to 6911. HDT represents heat distortion temperature. These results are also shown in Tables 1 to 3.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

It can be seen from Tables 1 to 3 that the oligomers of the examples can give cured products having a faster curing rate and excellent surface hardness and heat resistance as compared with the oligomers of the comparative examples.

[0050]

INDUSTRIAL APPLICABILITY As described above, the present invention relates to a novel allylic oligomer, and when an allyl ester having a double bond is used at a specific molar ratio as an alkyl ester of polycarboxylic acid, the ester is The exchange reaction rate is considerably faster than that of the corresponding saturated alkyl ester, and it does not need to be performed at high temperature like usual polycondensation reaction, and it has an allyl ester group in the side chain and the main chain skeleton is dicarboxylic acid and polycarboxylic acid. A polyester derived from a valent saturated alcohol is obtained, and a cured product excellent in surface hardness, heat resistance and curability can be obtained from this polyester. INDUSTRIAL APPLICABILITY The novel allyl oligomer of the present invention can be easily and economically molded into various molded products by using a known molding method as in the case of conventional thermosetting resins, and thus has high industrial utility value.

Continuation of front page (72) Inventor Yoji Tanaka Oita City, Oita Prefecture Nakanosu 2 Showa Denko Co., Ltd.

Claims (3)

[Claims] 1. A novel allylic oligomer obtained by reacting a raw material containing the following components (A) to (C) in the following molar ratio in the presence of a transesterification reaction catalyst. (A) triallyl trimellitate and / or tetraallyl pyromellitic acid, (B) dialkyl ester of divalent aromatic and / or aliphatic dicarboxylic acid having 4 to 20 carbon atoms, and (C) two alcoholic hydroxyl groups. However, the alkyl group of the dialkyl ester (B) is an alkyl group derived from a saturated or unsaturated hydrocarbon having 3 or less carbon atoms. Molar ratio: 0.9 <(A + B) / C <40 0 ≦ B / A <3 where A, B and C are the component (A) and (B), respectively.
It represents the number of moles of the component and the component (C). 2. The novel allylic oligomer according to claim 1, wherein a diol (C) component containing a polyol having a valence of 3 or more is used. 3. The novel allylic oligomer according to claim 1 or 2, wherein a raw material containing a copolymerizable monomer is used in addition to the components (A) to (C).