JPH0539337A - New allylic oligomer - Google Patents

Abstract

PURPOSE:To obtain an allylic oligomer improved in heat resistance by forming an oligomer represented by a specified formula and having an allyl ester group at each of its terminals and an organic residue derived from a dicarboxylic acid and an organic residue derived from a diol in its inside. CONSTITUTION:A diallyl ester such as diallyl phthalate is mixed with diols of formulas I and/or II (wherein (m) is 1-3, and (y) is 0-3) such as tricyclo[5,2,1,0<2>,<6>]-decanedimethanol in a carboxyl/hydroxyl ratio of 20/19 to 5/1, and the mixture is heated at 100-300 deg.C in the presence of a catalyst such as dibutyltin oxide in a nitrogen stream. The allyl alcohol formed by the reaction is distilled off, and the pressure is further decreased to promote distillation after a specified amount of the distillate is formed. By cooling after the reaction, the objective allylic oligomer of formula III (wherein A is an organic residue derived from a dicarboxylic acid, (n) is 1-10, and Rs are organic residues of formulas IV and/or V) is obtained. This oligomer is cured to obtain a product excellent in heat resistance and hydrolysis resistance.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel allylic oligomer which gives a cured product having high heat resistance and excellent hydrolysis resistance.

[0002]

2. Description of the Related Art Artificial marble composed of a thermosetting resin and an inorganic filler such as aluminum hydroxide or a glass filler has been used in a bathtub. However, in Japan, since water is heated in a bathtub before use, it is required that the boiling resistance of artificial marble be very strict. Recently, many attempts have been made to directly obtain an artificial marble molded product without attaching a gel coat, but in this case, artificial marble using an unsaturated polyester resin that could be used in the past was used for blistering resistance test. However, it causes a whitening phenomenon and is insufficient as a base material for bathtubs.

Also known is an allyl ester resin having an allyl ester group at the terminal and having the following structure derived from a polyvalent saturated carboxylic acid and a polyvalent saturated alcohol inside (Japanese Patent Laid-Open No. 2-251509). Bulletin). _{CH 2 = CHCH 2 O (COR} 'COOBO) n CORCOOCH 2 CH = CH 2 where, ^R' is a divalent or trivalent organic residue derived from a saturated carboxylic acid, B is a divalent or polyvalent polyols Derived organic residue, n represents an integer of 1 to 20.

Although a cured product having excellent heat resistance and impact resistance is obtained, when an artificial marble molded article using this resin is subjected to a boiling resistance test, no blistering phenomenon occurs, but the surface treatment of the filler is unsatisfactory. If it is sufficient, there is a drawback in that water easily penetrates into the interface between the resin and the inorganic filler to cause a whitening phenomenon.

[0005]

[Problems to be Solved by the Invention] As a resin for artificial marble, an artificial marble molded product which has improved heat resistance and boiling water absorption of allyl ester resin and does not cause blistering and whitening phenomenon found in existing materials in a boiling resistance test. Develop a new thermosetting resin that gives

[0006]

Means for Solving the Problems As a result of intensive studies for achieving the above object, the present inventors have found that the compound has an allyl ester group at the terminal and is internally composed of a polyvalent saturated carboxylic acid and a polyvalent saturated alcohol. By using the diol represented by the general formula 3 and / or the general formula 4 as a raw material when synthesizing the derived allyl ester oligomer, heat resistance,
They have found that the boiling resistance can be improved, and have completed the present invention.

[0007]

[Chemical 5]

[0008]

[Chemical 6]

The invention according to claim 1 of the present invention is an oligomer having the following structure. _{CH 2 = CHCH 2 O (COACOORO} ) n COACOOCH 2 CH = CH 2 However, A is an organic residue derived from a divalent carboxylic acid, n represents a number from 1 to 20. R represents an organic residue represented by the general formula 1 and / or general formula 2, m represents an integer of 1 to 3, and y represents an integer of 0 to 3.

[0010]

[Chemical 7]

[0011]

[Chemical 8]

The invention according to claim 2 of the present invention is an oligomer having an allyl ester group at the terminal and having the following repeating units:-(COACOORO)-Structure -A-(COACOO) _X -ZO-COArCOO- Structure-B where x is an integer of 1 to 5, Z represents an organic residue derived from a polyol having x + 1 hydroxyl groups, and A represents an organic residue derived from a divalent carboxylic acid. R is an organic residue represented by general formula 1 and / or general formula 2, m
Represents an integer of 1 to 3, and y represents an integer of 0 to 3. Of the composition of the oligomer excluding the terminal allyl group, the mole fraction of structure-A is in the range of 10 to 100%, the rest is structure-B, and GPC (gel permeation chromatography ) The polystyrene-equivalent number average molecular weight (Mn) is 500 to 15,000 and the weight average molecular weight (Mw) is 1,000 to 70,000, and Mw is
It is an allyl oligomer characterized in that the ratio of / Mn is 1.2 to 20.0.

[0013]

[Chemical 9]

[0014]

[Chemical 10]

Such an allylic oligomer is obtained by reacting a corresponding diallyl ester of a dicarboxylic acid with a compound represented by the general formula 3 and / or
Alternatively, it can be obtained by reacting a diol represented by the general formula 4 and, if necessary, a divalent or higher valent polyol in the presence of a transesterification reaction catalyst while distilling off allyl alcohol.

As a more industrially useful method, instead of the diallyl ester of dicarboxylic acid, a diester of a corresponding dicarboxylic acid with a lower aliphatic alcohol having 1 to 3 carbon atoms and allyl alcohol are used as raw materials. It can be obtained by reacting while distilling off the lower aliphatic alcohol.

Specific examples of the diol represented by the general formulas 3 and 4 include tricyclo [5,2,1,0].
^2.6 ] Decanedimethanol, norbornane-2,3-dimethanol, perhydro-1,4; 5,8-dimethanonaphthalene-2,3-dimethanol are mentioned. Examples of the diol represented by the general formula 4 are described in JP-A-3-56429.

As the divalent saturated carboxylic acid which gives A, 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-phenylenediacetic acid, p-carboxyphenylacetic acid, methylterephthalic acid, tetrachlorophthalic acid and the like. Of these, divalent saturated carboxylic acids containing a benzene ring, such as terephthalic acid and isophthalic acid, are particularly preferable for improving heat resistance and boiling resistance.

Examples of the divalent saturated alcohol which gives Z include ethylene glycol, propylene glycol,
1,3-propanediol, 1,4-butanediol,
1,3-butanediol, neopentyl glycol,
1,5-pentadiol, 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 -Saturated glycol consisting of only carbon such as ethyl-2,5-pentanediol, 2-ethyl-1,3-hexanediol and styrene glycol, and diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol and bisphenol-A. Ethylene oxide adduct,
Also included are divalent saturated alcohols containing ether groups such as propylene oxide adducts of bisphenol-A, and glycols containing bromine such as dibromoneopentyl glycol. Among these, propylene glycol and 1,3-
When a glycol such as butanediol or dipropylene glycol is used, the compatibility with other copolymerizable monomers is good, and the transparency of the cured product is excellent.

Examples of trivalent or higher polyvalent saturated alcohols that give Z include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, and alkyl oxide adducts of isocyanuric acid. The use of these is preferable from the viewpoint of heat resistance, but since the viscosity of the produced allyl ester oligomer is remarkably increased, it is preferable to use only a small amount.

In order to obtain an allyl ester oligomer having an allyl ester at the end, the ratio of these compounds used in the general formula 3 and / or the general formula 4 is more than that in the carboxyl group of the divalent saturated carboxylic acid. It is necessary to use less of the hydroxyl groups of the represented diol and other polyhydric alcohols. Further, if the usage ratio of this functional group is too close, the molecular weight of the produced allyl ester oligomer will increase remarkably. Therefore, these ratios are such that the ratio of carboxyl group / hydroxyl group is 2
It is desirable to fall within the range of 0/19 to 5/1, more preferably 6/5 to 3/1.

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.
oxides, hydroxides of r, Pb, Ti, Co and Sn,
Examples thereof include 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, 0.0001 wt% to 1 w based on diallyl or dialkyl ester
t%, particularly preferably 0.001 wt% to 0.1 wt%
It is preferred to use degrees.

As an embodiment of the reaction, when a diallyl ester is used, it is heated above the boiling point of allyl alcohol, and when a dialkyl ester of a lower alcohol is used, it is heated above the boiling point of a lower alcohol for transesterification. The allyl alcohol or lower alcohol which is produced in a favorable manner for the production of is removed from the reactor out of the system by reactive distillation. Generally, the reaction is carried out under normal pressure or under pressure, but it is also effective to use a method in which the reaction system conversion rate is increased and the reaction system is depressurized to rapidly distill off allyl alcohol or lower alcohol.

As mentioned above, when the diallyl ester is used, the reaction temperature is not higher than the boiling point of allyl alcohol, so that the distillation of allyl alcohol cannot be effectively carried out. Since there are problems such as
Generally between 100 ° C and 300 ° C, more preferably 1
It is selected from between 30 ° C and 250 ° C.

When a dialkyl ester of a lower alcohol is used, since the boiling point of the allyl alcohol to be reacted with the lower alcohol produced is close, heating at an excessively high temperature from the initial stage of the reaction causes allyl alcohol to be distilled out together with the lower alcohol. There is a fear. Therefore, an efficient rectification column is attached, and the reaction temperature is generally 80 ° C to 150 ° C, more preferably 90 ° C to 130 ° C in the initial stage of the reaction, and most of the lower alcohol is distilled. After that, it is better to select between 100 ° C. and 300 ° C., more preferably between 130 ° C. and 250 ° C.

The amount of allyl alcohol used in this case is at least 0.2 with respect to the dialkyl ester.
A molar equivalent is necessary, and usually 0.5 molar equivalent or more, preferably 1 molar equivalent or more should be used. However, if used in an excessively large amount, excess allyl alcohol must be removed, and the reaction rate does not necessarily increase, so it should be kept at 20 molar equivalents or less. A polymerization inhibitor such as hydroquinone may be allowed to coexist in the reaction solution depending on the reaction temperature.

Various methods can be used to take out the oligomer after the reaction. For example, it is possible to purify the produced allyl ester oligomer by removing the monomer by distillation or reprecipitation, but usually it can be used even in the coexistence of the diallyl ester monomer used as a by-product during the reaction or used as a raw material. This is possible and industrially advantageous. Also, for the purpose of adjusting the viscosity,
It is also possible to positively add a diallyl or triallyl type monomer, and examples of such a diallyl or triallyl type monomer include diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl adipate, triallyl isocyanurate, triallyl trimellitate. There are tate, diallyl 2,6-naphthalenedicarboxylic acid, diallyl endic acid and the like.

The structure of the oligomer described here was confirmed in the following experiments. A) Method for measuring and determining iodine value Oligomer was precisely weighed in the range of 0.25 to 0.35 g and 2
Place in a 00 ml iodine flask and add 30 ml of chloroform to completely dissolve the sample. To this, wijs
Reagents (7.9 g iodine trichloride and 8.2 g iodine,
After dissolving in 200-300 ml of glacial acetic acid,
Accurately add 20 ml using a whole pipette to mix both solutions to make 1 l, and then add 2.5% mercuric acetate glacial acetic acid solution 1
After adding 0 ml, the reaction is completed by leaving it in the dark for 20 minutes. To this, 5 ml of a newly prepared 20% KI solution was added, and using 1% starch solution as an indicator, 0.1 NNa ₂
Titrate with S ₂ O ₃ standard solution. At the same time, perform a blank test. a: Number of ml of 0.1N-Na ₂ S ₂ O ₃ solution required for blank test b: ml of 0.1N-Na ₂ S ₂ O ₃ solution required for main test
Number f: titer of 0.1 N-Na ₂ S ₂ O ₃ solution s: g number of sample

B) Method for determining Mn and Mw by GPC method Mn and Mw in terms of polystyrene are measured by GPC. S
HODEX column AC-80P, 802, 804, 80
6 Each one is connected in series in this order, and chloroform is used as a solvent, and the measurement is performed at a temperature of 25 ° C. and a flow rate of 1.0 ml / min. First, at least 10 kinds of commercially available standard polystyrenes having known average molecular weights were used, and the retention time of each was measured together with the diallyl terephthalate (DATP) monomer. The relationship between the average molecular weight and the retention time is a cubic curve,
Alternatively, a calibration curve was created by approximating with a polygonal line. 20 mg of a sample is dissolved in 20 ml of chloroform, and 0.5 ml is injected into a column through a line filter using a loop injector. Shimadzu CR-3A based on the calibration curve prepared in
Mn and Mw are calculated automatically in a data processor such as 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.

Since the oligomer thus obtained has a cross-linked alicyclic structure in the molecule, its heat resistance and boiling resistance are remarkably higher than those of ordinary allyl ester oligomers. The novel oligomer can be used as it is or after being dissolved in another polymerizable monomer to reduce the viscosity, if desired. As such a polymerizable monomer, for example, an aromatic vinyl compound,
(Meth) acrylic acid and its ester, unsaturated dibasic acid and its derivative, saturated aliphatic or aromatic carboxylic acid vinyl ester and its derivative, vinyl cyanide compound such as (meth) acrylonitrile, unsaturated hydrocarbon, halogen And unsaturated hydrocarbons.

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

Examples of (meth) acrylic acid and its esters include acrylic acid, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate.

As the unsaturated dibasic acid and its derivative,
Examples 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.

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

As the unsaturated hydrocarbon, 1-hexene,
Examples include 1-octene and 4-vinylcyclohexene.

Examples of halogenated unsaturated hydrocarbons include vinyl chloride and vinyl bromide.

Further, a crosslinkable polyfunctional monomer can also be used,
As such, for example, diallyl carbonate, diethylene glycol diallyl carbonate, divinyl benzene, neopentyl glycol (meth) acrylate, difunctional adipate divinyl crosslinkable monomers such as divinyl trimethylolpropane tri (meth) acrylate, Examples thereof include trifunctional or higher functional crosslinkable monomers such as pentaerythritol tetra (meth) acrylate, diallylmaleate 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.

For applications other than resins for artificial marble, fillers, polymerization accelerators, polymerization inhibitors, internal mold release agents, coupling agents, pigments and other additives are blended to the extent that physical properties are not impaired. Can also be used as a molding material. Further, since this oligomer has a double bond appropriately, it can be used as a mixture with unsaturated polyester resin, diallyl phthalate resin or the like, or as a cross-linking agent for EPR, chlorinated polyethylene, synthetic rubber or the like. Can be used. The present invention will be described in more detail below.

[0041]

【Example】

Example-1 A 2-liter three-neck separable flask equipped with a distillation apparatus was charged with 130 parts of diallyl terephthalate (hereinafter abbreviated as DATP).
0 g, tricyclo [5,2,1,0 ^2.6 ] decane dimethanol (hereinafter abbreviated as TCD) 637.6 g, and dibutyltin oxide 0.65 g were charged, and then 18 under a nitrogen stream.
The mixture was heated to 0 ° C., and the produced allyl alcohol was distilled off. When about 250 g of allyl alcohol was distilled, the pressure inside the reaction system was reduced to about 50 torr to accelerate the distillation rate of allyl alcohol. After distilling the theoretical amount of allyl alcohol, heating was continued 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 5 and Comparative Examples 1 to 2 Allyl ester oligomers were synthesized in substantially the same manner as in Example 1 except that raw materials and charged molar ratios were different. The results are also shown in Table 1. Further, as a comparative example, an allyl ester oligomer synthesized by using propylene glycol instead of tricyclo [5,2,1,0 ^2.6 ] decanedimethanol is also shown.

In addition to these allyl ester oligomers, dicumyl peroxide 2 is further used as a radical polymerization initiator.
phr was mixed. The obtained composition was placed on a heating plate at 160 ° C., and the time until no stringing was determined was examined and the gel time was taken. Also, a predetermined amount of the composition obtained above was used and cast polymerization was performed at 130 ° C. by using a cellophane-tensioned glass plate.
After curing for 1 hr, 160 ° C./5 hr after curing was performed for curing. The physical properties of the obtained molded product are measured according to JIS K-691.
It was measured according to 1. These results are also shown in Table 1.

[0044]

[Table 1]

Example 6 In a 3 liter three-necked flask equipped with a rectification device, 946.3 g of dimethyl terephthalate and tricyclo [5,2,2] were used.
1,0 ^2.6 ] decane dimethanol 637.7 g, allyl alcohol 566.0 g, dibutyltin oxide 0.5
g was charged and heated to 150 ° C. under a nitrogen stream to distill off the produced methanol. In addition, allyl alcohol accompanied with methanol was charged into the reactor by the amount of the distillate. Theoretical amount of methanol (312
When g) was distilled, the reaction temperature was raised to 180 ° C. and allyl alcohol was distilled off. When about 300 g of allyl alcohol was distilled, the reaction system was heated to 50 mmH.
The pressure was reduced to g to accelerate the distillation rate of allyl alcohol. After the distillate was almost gone, the pressure was reduced with a vacuum pump and kept for another hour to distill off the residual allyl alcohol, and the reaction product was cooled to obtain a polymerizable oligomer similar to that in Example-1.

[0046]

INDUSTRIAL APPLICABILITY The present invention provides a novel allylic oligomer which gives a cured product having high heat resistance and excellent hydrolysis resistance, and was found in conventional allyl ester resins in a boiling resistance test. Since it does not cause blistering or whitening,
It can be used in the fields of artificial marble and various molding materials where heat resistance and hydrolysis resistance are important, and its industrial utility value is enormous.

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Claims (2)

[Claims] 1. An oligomer having the following structure. _{CH 2 = CHCH 2 O (COACOORO} ) n COACOOCH 2 CH = CH 2 However, A is an organic residue derived from a divalent carboxylic acid, n represents a number from 1 to 20. R represents an organic residue represented by the general formula 1 and / or general formula 2, m represents an integer of 1 to 3, and y represents an integer of 0 to 3. [Chemical 1] [Chemical 2] 2. An allyl ester group is attached to the terminal,
An oligomer having the following repeating unit:-(COACOORO) -Structure -A-(COACOO) _X -ZO-COArCOO-Structure -B where x is an integer of 1 to 5 and Z is x + 1 hydroxyl groups. The organic residue derived from the polyol having A, A represents the organic residue derived from the divalent carboxylic acid. R is an organic residue represented by general formula 1 and / or general formula 2, m
Represents an integer of 1 to 3, and y represents an integer of 0 to 3. Of the composition of the oligomer excluding the terminal allyl group, the mole fraction of structure-A is in the range of 10 to 100%, the rest is structure-B, and GPC (gel permeation chromatography ) The polystyrene-equivalent number average molecular weight (Mn) is 500 to 15,000 and the weight average molecular weight (Mw) is 1,000 to 70,000, and Mw is
The ratio of / Mn is 1.2-20.0, Allyl-type oligomer characterized by the above-mentioned. [Chemical 3] [Chemical 4]