JPH03234723A - Production of unsaturated polyester and unsaturated polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition reduced in the loss of styrene added thereto and curing shrinkage by reacting a specified reaction product with a polyisocyanate. CONSTITUTION:1 equivalent of tricyclo[5.2.1.0<2>,<6>]dec-3-en-8-yl maleate or tricyclo[5.2.1.0<2>,<6>]dec-3-en-9-yl maleate is made to react with 1.50-2.10 equivalents of a glycol (e.g. ethylene glycol) to obtain a reaction product (A). 1 equivalent of the hydroxy groups of component A is made to react with 0.06-1.00 equivalent of the isocyanate groups of a polyisocyanate (B) reactive with the hydroxyl groups of component A (e.g. tolylene diisocyanate) at 40-130 deg.C in the presence of a urethane formation catalyst to obtain an unsaturated polyester. This polyester is mixed with a crosslinking monomer (e.g. styrene), a reinforcement, a filler, a dye, a mold release, a curing agent, etc., to obtain an unsaturated polyester resin composition.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for producing unsaturated polyester and an unsaturated polyester resin composition, and more specifically, to a method suitable for use in paints, adhesives, casting, fiber-reinforced plastics, etc. The present invention relates to a method for producing unsaturated polyester and an unsaturated polyester resin composition to be used.

[Conventional technology]

tricyclo[5.2,1,02.6]dec-3-ene-
8-yl-maleate or tricyclo[5.2,1
,02-6) deca-3-en-9-yl-maleate (hereinafter referred to as tricyclo[5.2°1.02″6) deca-3
-en-8- or 9-yl-hydrogen=malate) and a polyol,
Unsaturated polyester resin set Ftfc' dissolved in vinyl monomer such as styrene! As shown in Japanese Patent Application No. 52-6935, etc., # has features such as low styrene dissipation, low curing shrinkage, and high heat resistance.

However, in recent years, the demand for low styrene dissipation properties has been increasing due to stricter regulations under the Industrial Safety Act, employment shortages due to strong odor and other working environments, and environmental issues related to air pollution. In order to meet this requirement, unsaturated polyester resin compositions in which the number average molecular weight of the unsaturated polyester is reduced and the styrene content is reduced have significantly inferior mechanical strength of the cured product.

On the other hand, an unsaturated polyester resin composition consisting of styrene and an unsaturated polyester obtained by condensation reaction of an α, β-unsaturated dibasic acid and a saturated dibasic acid used as necessary with glycol, In order to increase the mechanical strength of objects, a method has been adopted in which a polyfunctional isocyanate is mixed into an unsaturated polyester resin composition immediately before curing. However, in this case, there is a drawback that the number of steps required for curing the unsaturated polyester resin composition increases.

In addition, when the above unsaturated polyester and polyfunctional isocyanate are reacted in advance, the reactant has a high molecular weight,
In order to provide suitable workability, the styrene content must be increased, and styrene compatibility may be poor and phase separation may occur.Furthermore, if the amount of polyfunctional isocyanate reacted in advance is reduced, The mechanical strength of the cured product is not sufficiently improved.

[Problems to be Solved by the Invention] An object of the present invention is to solve the problems of the prior art described above, to obtain an unsaturated polyester resin composition with excellent low styrene dissipation properties, and to obtain an unsaturated polyester resin composition with excellent mechanical strength and boiling resistance. The purpose of the present invention is to provide a method for producing an unsaturated polyester and an unsaturated polyester resin composition that can produce a cured product having excellent properties such as hardness, low curing shrinkage, and adhesive properties.

[Means to solve the problem]

The present invention relates to tricyclo[5,2,1,0'') deca-
A reaction product (A) obtained by reacting 1 amount of 3-en-8 or 9-yl hydrogen = maleate with 1.50 to 2.10 equivalents of glycol, and a hydroxyl group of the reaction product (A). A method for producing an unsaturated polyester characterized by reacting the unsaturated polyester with a polyfunctional isocyanate (B) having reactivity with the polyester, and an unsaturated polyester resin comprising the unsaturated polyester obtained by the method and a crosslinkable monomer. Regarding the composition.

Tricyclol used in the present invention: 5.2.1゜02.
6] Dec-3-en-8 or 9-yl-hydrogen maleate is usually tricyclo[5,2°1.02”6]
Dec-3-en-8-yl-maleate and tricyclo[5,2,1,021)dec-3-en-9-yl-
Although mixtures with maleate are used, they may also be used as single compounds if they are available.

The tricyclo[5.2,1,0''°6]dec-3-en-8 or 9-yl-hydrogen-malaleate is, for example,
As shown in the chemical reaction formula below, (1) M Blaney (M
, Vrany) (Pracf, Nnasy Cen
ych Polyesterorgch Pryslc
Reaction of dicyclopentadiene and maleic acid by J.R. Richich, p. 79 (1960), (2) Tokuko Sho 5
Reaction of dicyclopentadiene, maleic anhydride and water according to Publication No. 5-2211, (3) Japanese Patent Publication No. 39-1875
Reaction of 5 or 6-hydroxy-3a, 4°5.6,7.7a-hexahydro-4,7-methanoindene with maleic anhydride according to Publication No. 3, (4) Two groups! The bottom can be achieved by a monoesterification reaction between an acid and an alcohol.

Below is the margin - Ma(J-()-〇1 U-(J-0 :!: II :!: ′''H Yu01 Tomono 11 , ) 1 solution) and Dinner + = II = 11- = 11- 0 :II + + Depending on the Barber synthesis method, dicyclopentadiene and water may be included in the product, but the
It is preferable to remove it by heating and reducing the pressure to 350 mIIHg.

In addition, with some specificization, tricyclo[5.2,1゜QL&
) deca-3-en-8-iluf malayate or tricyclo[5.2,1,0''b] deca-3-en-9
-Iruf Malay Art (hereinafter referred to as Tricyclo [5.2,
1,0”°6] deca-3-ene-8 or 9-yl-hydrogen = fumarate), but
It is preferable to use it as is from the viewpoint of curing reactivity and cost of the unsaturated polyester resin composition. This tricyclo [5
゜2, 1. 02°6] Dec-3-ene-8 or 9
In order to increase the production rate of yl-hydrogen = fumarate, after removing dicyclopentadiene etc.,
Heating to °C is also possible.

In addition, maleic acid and fumaric acid may remain or survive and be included in the product, but these compounds are used as raw materials for unsaturated polyester production in order to avoid a decrease in product yield and an increase in price due to increased man-hours. Although it is possible to use it as it is as it is, a reactant having two hydroxyl groups and a polymerizable unsaturated bond in the molecule grows and reacts with the polyfunctional isocyanate to form a high molecular weight unsaturated polyester resin or a gelled product. It is preferable to remove the styrene by filtration or the like from the viewpoint of low styrene dissipation.

Further, in producing the reaction product (A), it is also possible to use saturated dibasic acids such as phthalic anhydride and adipic acid, and unsaturated dibasic acids such as maleic acid and fumaric acid in combination.

The reactant (8) used in the present invention is the above tricyclo[
5.2,1,02°6]dec-3-ene-8 or 9-
It is obtained by a condensation reaction between yl-hydrogen-maleate and glycol.

The above glycols include ethylene glycol, propylene glycol, neopentyl glycol, 1.3-butanediol, 1.4-butanediol, 1.6-hexanediol, diethylene glycol, dipropylene glycol, hydrogenated bisphenol A1, bisphenol A, etc. Examples include propylene oxide adducts. Moreover, these glycols may be used in combination with polyhydric alcohols such as glycerin, trimethylolpropane, and pentalit.

The amount of glycol used is tricyclo[5,2°1.0
2=b) ranging from 1.50 to 2 DEG IO equivalents, preferably from 1.60 to 1.95 equivalents per equivalent of dec-3-en-8 or 9-yl-hydrogen-maleate. When the amount of glycol is less than 1.50 equivalents, the molecular weight of the reactant (A) becomes large, so the molecular weight of the unsaturated polyester obtained by reacting with the polyfunctional isocyanate also becomes large, and the low styrene dissipation property decreases. In addition, if the amount exceeds 2 or 10 equivalents, unreacted glycol increases, and this unreacted glycol reacts with the polyfunctional isocyanate, increasing the molecular weight of the unsaturated polyester, resulting in a decrease in low styrene dissipation and hardening. The boiling resistance of objects decreases.

The polyfunctional isocyanate (B) used in the present invention has reactivity with the hydroxyl group of the reactant (A), and includes, for example, tolylene diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate. , hexamethylene diisocyanate, polymethylene polyphenyl polyisocyanate, and the like. Two or more of these may be used in combination. The amount of the polyfunctional isocyanate to be used is preferably in the range of 0.06 to 1.00 equivalents of isocyanate groups relative to 1 equivalent of hydroxyl groups in the reactant (A) having an acid value of 20 or less. When the isocyanate group is less than 0.06 equivalent, the effect of the polyfunctional isocyanate is small, and when it exceeds 1°OO equivalent, it tends to gel during the reaction, and since the isocyanate group remains, it is easily affected by moisture in the air.

The unsaturated polyester according to the present invention can be produced as follows. An example of a chemical reaction formula for its production is shown below.

Margin below CH.

l! 1. HOH○ I CL -0-C-CH Reactant (A) First, the reaction between tricyclo[5.2,1,0''1)dec-3-en-8 or 9-yl-hydrogen-maleate and glycol Reactant (A) is obtained by a condensation reaction.This reaction can be carried out by heating, for example, to 140 to 230°C in an inert gas atmosphere and distilling the condensed water out of the system. It can be done with equal authority.

As shown in the above chemical formula, the main component of the reactant (A) resulting from the condensation reaction is one tricyclo[5.2°1.0t1
] It is a compound having a dec-3-en-8 or 9-hydrogen=yl group, one polymerizable unsaturated bond, and one hydroxyl group, but it is difficult to undergo thermal polymerization, addition of a hydroxyl group, etc. to the unsaturated bond, etc. Due to side reactions, compounds with higher molecular weight than the above compounds are also produced. In addition, two tricyclo[5.2,1,0''°6]dec-3-ene-8 or 9-yl-hydrogen maleates undergo a condensation reaction with one glycol, resulting in a condensation reaction with a polyfunctional isocyanate. Non-reactive compounds are also produced.

Therefore, the number average molecular weight of the obtained reactant (A) is several hundred. The acid value of the reactant (A) is preferably 20 or less, more preferably 10 or less. If the acid value is greater than 20, unreacted glycol will increase, and foaming will occur during the reaction with the polyfunctional isocyanate, which is undesirable.

Next, a polyfunctional isocyanate (
B) is added and an unsaturated polyester is obtained by addition reaction. This reaction is preferably carried out in an inert gas atmosphere at a temperature range of 40-130°C.

If the reaction temperature is less than 40°C, the reaction time will be longer and 13
If the temperature exceeds 0°C, gelation tends to occur. Although the urethanization reaction easily proceeds without a catalyst, a catalyst may be used to avoid gelation during the reaction. As the catalyst, tertiary amines, organometallic compounds, etc. that are widely used as urethanization catalysts can be used, and the amount used is in the range of 0.005 to 1.0% by weight based on the total amount charged. preferable.

It is also possible to proceed with the reaction at a low viscosity by adding and dissolving in advance a crosslinking monomer that is not reactive with a polyfunctional isocyanate such as styrene or vinyltoluene among the crosslinking monomers described below to the reactant (A). It is.

Although the unsaturated polyester obtained by the production method of the present invention has self-copolymerizability, it has poor reactivity at room temperature and needs to be used in combination with a crosslinking monomer.

Unsaturated polyester resin of the present invention! Examples of crosslinking monomers used in Jl Kaimono include styrene, vinyltoluene,
Divinylbenzene, methyl methacrylate, methyl acrylate, lauryl methacrylate, lauryl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, and the like. Two or more of these may be used in combination.

In the unsaturated polyester resin composition of the present invention, inorganic or organic reinforcing materials, fillers, dyes, pigments, mold release agents, curing agents, accelerators, and the like can be arbitrarily selected and used.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

tricyclo[5.2,1,0””)dec-3-ene-
Synthesis of 8- and 9-yl-hydrogen maleate (mixture of 8-yl-maleate and 9-yl-maleate).

Synthesis Example 1> 5 and 6-hydroxy-3a, 4,5,6°7.7a
-hexahydro-4,7-methanoindene (trade name, manufactured by Hitachi Chemical Co., Ltd., sidecanol: 5 hydroxy compound and 6
- 300 g of a mixture with a hydroxy compound) and 196 g of maleic anhydride were placed in 1J24 flasks, heated at 120°C in a nitrogen gas stream for 3 hours, and the acid value was reduced to 2.
23 tricyclo[5.2,1,0"・6]deca-3-
En-8 and 9-yl-hydrogen maleates were obtained.

Synthesis Example 2> Dicyclopentadiene 264 g, maleic anhydride 19
6 g and 36 g of water were placed in a 4-IJ2 flask, and this was heated at 140°C for 2 hours in a nitrogen gas stream.
A reaction solution with an acid value of 216 was obtained. In addition, maleic acid and fumaric acid were found to have precipitated at the bottom of the flask. This reaction solution was heated at 140°C for 15 minutes at CC120011IIH to distill off 1.8g of dicyclopentadiene and 2.3g of water. 9-yl-hydrogen maleate was obtained.

Example 1 In the same apparatus as in Synthesis Example 1, tricyclo [
5.2,1,0''''6] deca-3-en-8 and 9-
496 g of yl-hydrogen maleate, 191 g of diethylene glycol, and 0.1 g of hydroquinone were charged and reacted in a nitrogen gas stream at 140 to 200''C for 6 hours to obtain a reaction product (A) with an acid value of 5.8. To this was added 0.2 g of dibutyltin dilaure), and a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (trade name, Takenate 8, manufactured by Narita Pharmaceutical Co., Ltd.) was added.
0) 45g was added dropwise and reacted at 65°C for 3 hours to obtain an unsaturated polyester. Infrared analysis of this unsaturated polyester revealed that the absorption of isocyanate groups had almost disappeared. Moreover, its number average molecular weight was 746.

This unsaturated polyester is dissolved in styrene and has a viscosity of 3.
An unsaturated polyester resin composition (A) having a poise of 0 (25°C) was obtained.

Example 2 In the working example, tricyclo[5,2
,1,0”°6]dec-3-en-8 and 9-yl-
A reactant (A) having an acid value of 5.4 was obtained in the same manner as in Example 1, except that hydrogen=malate was used. This reactant (A
), an unsaturated polyester having a number average molecular weight of 768 was obtained in the same manner as in Example 1.

This unsaturated polyester is dissolved in styrene and has a viscosity of 3.
0 (25℃) poise unsaturated polyester resin composition (
B) was obtained.

Example 3 In Example 1, tricyclo[5.2
, 1,0!1) Dec-3-en-8 and 9-yl-hydrogen = Malayer) 496 g, neopentyl glycol 1
A reactant (A) having an acid value of 6.2 was obtained in the same manner as in Example 1 except that 98 g and 0.1 g of hydroquinone were charged. An unsaturated polyester resin having a number average molecular weight of 730 (calculated excluding the styrene peak) was obtained in the same manner as in Example 1, except that 120 g of styrene was added and dissolved in the reaction product (A).

Add styrene to this unsaturated polyester resin and dissolve it.
An unsaturated polyester resin composition (C) having a viscosity of 3.0 poise (25°C) was obtained.

Comparative Example 1 Tricyclo[
5.2,1,0''-' 3dec-3-ene-8 and 9
-yl-hydrogen = maleate 595g, phthalic anhydride 1
18g, maleic anhydride 78g, ethylene glycol 1
98 g and 0.15 g of hydroquinone were charged, and the temperature was gradually raised to 205°C over 3 hours under a nitrogen stream. The reaction was continued at this temperature for 5 hours, and the number average molecular weight was 973.
An unsaturated polyester was obtained.

This unsaturated polyester is dissolved in styrene and has a viscosity of 3.
An unsaturated polyester resin composition (D) of 0 poise (25°C) was obtained.

Comparative Example 2 An unsaturated polyester having a number average molecular weight of 738 was obtained in the same manner as in Comparative Example 1, except that 226 g of ethylene glycol was used.

This unsaturated polyester is dissolved in styrene and has a viscosity of 3.
An unsaturated polyester resin composition (E) having a poise of 0 (25°C) was obtained.

Comparative Example 3 Into the same apparatus as in Example 1, 333 g of phthalic anhydride, 221 g of maleic anhydride, 376 g of propylene glycol, and 0.1 g of hydroquinone were charged, and the temperature was gradually raised under a nitrogen stream to 210°C over 4 hours. I made it. The reaction was continued at this temperature for 6 hours to obtain an unsaturated polyester with a number average molecular weight of 1204.

This unsaturated polyester is dissolved in styrene and has a viscosity of 3.
0 poise (25°C) unsaturated polyester resin composition (
F) was obtained.

<Test Example> 0.5 parts by weight of cobalt naphthenate (cobalt content 6% by weight) was added to 100 parts by weight of each of the unsaturated polyester resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 above. , 1 part by weight of methyl ethyl ketone peroxide was added to obtain a curable composition, which was used to produce a cured product and FRP by the method described below.The properties of the resin composition, cured product, and FRP were also investigated, and the results were It is shown in Table 1.

(1) Preparation of cured product The curable composition was poured into a 300m x 300m x 3gm casting mold, cured at 25°C, and then heated at 50'C for 12 hours.
Time after cure.

(2) Preparation of FRP 304.5 g of curable composition was added to 300III1×3
Impregnated with 3 layers of chopped strand mat (FEM-0450 manufactured by Fuji Fiberglass Co., Ltd.) of 00-, defoamed,
After curing at 5°C, it was after-cured at 50″C for 12 hours.

(3> Measurement of heating residue Approximately 1 g of the unsaturated polyester resin composition obtained in Examples and Comparative Examples was weighed accurately in a Petri dish to the nearest 0.1
After leaving it in the dryer C for 2 hours, it was accurately weighed again and the ratio to the initial value was expressed as a percentage.

(4) Measurement of styrene dissipation amount Approximately log of unsaturated polyester resin composite soles obtained in Examples and Comparative Examples adjusted to 25°C ± 1°C were measured with a diameter of 60 mm.
The sample was accurately weighed to the nearest 0.1 square inch in a petri dish, left to stand for 30 minutes, and the weight loss during this period was measured.

(5) Measurement of styrene concentration Place a chopped strand mat (FEM-
0450) Place three layers, impregnate this with a curable composition using a roll, laminate FRP with a glass content of 30% by weight, and 20 minutes after lamination, at a position 3 m above the center of the upper edge surface. The styrene concentration was measured using a styrene gas detection tube (manufactured by Komei Rikagaku Kogyo Co., Ltd., Kitayo type N0158).

(6) Measurement of heat and boiling resistance A test piece cut out at 50w x 50m from the cured product obtained in (1) is immersed in hot water at 96±2°C, taken out at predetermined intervals and visually observed to determine whether cranks occur. Expressed in time.

(7) Measurement of bending strength Measured according to JIS K 6911.

(8) Linear shrinkage rate 90g of the curable composition was poured into a release-treated iron mold with the dimensions shown in Figure 1 (numbers are in units of units), cured at 25°C, and left for 24 hours. The length of the cured product was measured and calculated using the following formula.

(9) Boiling strength retention rate The test piece cut from the FRP obtained in (2) was
It was immersed in hot water of C for 100 hours, and the bending strength before and after immersion was determined as J.
It was measured according to IS K 6911, and the ratio from the initial value is expressed as a percentage.

From Table 1 below, the unsaturated polyester resins of the present invention (Examples 1 to 3) exhibit lower styrene dissipation, higher boiling resistance, lower curing shrinkage, and lower Unsaturated polyester resin of Comparative Example 12 which has styrene dissipation property and high boiling resistance %, it is possible to achieve better low styrene dissipation properties, and even when the styrene dissipation properties are the same, it is shown that the cured product is good without any decrease in mechanical strength or boiling resistance.

Further, the compositions of Examples 1 to 3 exhibit excellent low curing shrinkage even when the amount of styrene used is increased.

〔Effect of the invention〕

According to the production method of the present invention, since the condensation reaction and addition reaction during production basically use a compound with one reaction point as the main raw material, it is possible to lower the molecular weight and viscosity of the unsaturated polyester. The unsaturated polyester resin composition using this unsaturated polyester has excellent low styrene dissipation properties and low curing shrinkage, and the introduction of urethane bonds improves the mechanical strength and boiling resistance of the cured product due to the lower molecular weight. It is possible to suppress a decrease in adhesiveness and adhesiveness.

[Brief explanation of drawings]

FIG. 1a is a perspective view of the steel used for measuring linear shrinkage rates in Examples and Comparative Examples, and FIG. 1A is a cross-sectional view taken along line A-A' in FIG. 1a.

Claims (1)

[Claims] 1. Tricyclo[5.2.1.0^2^,^6]deca-
3-en-8-yl-malayate or tricyclo[
5.2.1.0^2^,6] 1 equivalent of dec-3-en-9-yl-malayate and 1.50 to 2.10 glycol
Production of an unsaturated polyester characterized by reacting a reactant (A) obtained by reacting an equivalent amount with a polyfunctional isocyanate (B) having reactivity with the hydroxyl group of the reactant (A). Law. 2. An unsaturated polyester resin composition comprising the unsaturated polyester according to claim 1 and a crosslinkable monomer.