JPS6011732B2 - Method for producing unsaturated polyester resin - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing unsaturated polyester resin suitable for various uses such as paints, adhesives, columns, and fiber-reinforced plastics. The present invention relates to a method for producing an unsaturated polyester resin. Currently, unsaturated polyester resins are used for a variety of purposes, and their use is expected to continue to grow. However, ordinary unsaturated polyester resins use 30 to 5% by weight of styrene in order to adjust the viscosity of the resin, and the strong odor of styrene that evaporates during curing not only harms the working environment. It is also viewed as a problem as a cause of air pollution. In order to solve the problem of such unsaturated polyester resins, for example, other pinyl monomers or allyl monomers can be used instead of styrene monomers, but these monomers are not necessarily satisfactory in terms of polymerizability, curability, etc. Not yet reached. The present inventors have also conducted various studies in order to reduce the amount of styrene monomer used, but they have yet to achieve satisfactory results regarding unsaturated polyesters with Q-8 unsaturated polybasic acid residues as crosslinking points. has not yet been reached. There is also a method of directly esterifying Q-8 unsaturated monobasic acid, polyhydric alcohol, and polybasic acid using a large amount of strong acid such as sulfuric acid as a catalyst. However, it has some drawbacks and has not been widely implemented. The present inventors have repeatedly studied a method for producing an unsaturated polyester resin that is easy to work with and can be cured at room temperature without using a crosslinking agent, and has found that Q- 8
An unsaturated hydroxyl polyamide in which one end group is an unsaturated bond and the other is a hydroxyl group is obtained by reacting a mixed system of an unsaturated monobasic acid and a polybasic acid anhydride with a saturated or unsaturated monoepoxy compound. By reacting the hydroxyl group of the ester with an unsaturated cycloacetal compound obtained by a condensation reaction of an unsaturated aldehyde and a polyhydric alcohol, an unsaturated polyester resin having one or more unsaturated bonds at the end of the molecule is obtained. They discovered a method and completed the present invention. A model chemical formula is shown below to help understand the present invention. Methacrylic acid anhydride Phthalic acid propylene oxide Unsaturated polyester (1) Diarylidene bentaerythri, sotho (unsaturated cycloacetal) Unsaturated polyester resin of the present invention As shown in the above examples, the reaction in the method of the present invention is Since this is an addition reaction, it does not require steps such as catalyst removal or purification, and has the characteristic that the reaction product can be used immediately. The thus obtained unsaturated polyester resin having one or more unsaturated bonds at the end of the molecule generally has a low viscosity, depending on the type and amount of the polybasic acid, and can be directly or 20%
It can be cured by using a small amount of crosslinking agent within the range below. The reaction in the method of the present invention uses a catalyst selected from acids, bases, amines, organometallic compounds, etc.
It will be held from 70:00 to 150:00. The Q-3 unsaturated monobasic acid used in the synthesis of unsaturated polyester '1} in the method of the present invention is most commonly acrylic acid or methacrylic acid, which is sufficient for the purpose of the present invention. In addition, for example, crotonic acid, fumaric acid monoester, itaconic acid monoester, maleic acid monoester, etc. can also be used in combination. Polybasic acid anhydrides used in the synthesis of unsaturated polyester tl include, for example, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, maleic anhydride, itaconic anhydride, succinic anhydride, dodecenylsuccinic anhydride,
Trimellitic anhydride, bag oil or drying oil fatty acid and maleic anhydride adduct, rosin maleic anhydride adduct, anthraceso-maleic anhydride adduct, terbene maleic anhydride adduct, tetrachlorophthalic anhydride, tetrabrom anhydride such as phthalic acid. Further, a part of the polybasic acid anhydride can be replaced with a polybasic acid. The monoepoxy compound used in the synthesis of unsaturated polyester (1-) has the advantage that since the reaction is an addition reaction, there are no by-products, the reaction is at a lower temperature than a condensation reaction, and the reaction is rapid. Monoepoxy compound Examples include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, epichlorohydrin, cyclohexane vinyl monoxide, dibenthene monoxide,
These are saturated or unsaturated compounds such as cresyl glycidyl ether, Q-pinene oxide, and glycidyl methacrylate, and they can also be used in combination. The method of the present invention includes
Unsaturated polyester obtained by reaction of the above compounds
The hydroxyl group of 1- is reacted with an unsaturated cycloacetal to link the polyesters together. The unsaturated cycloacetals having two or more unsaturated bonds in the molecule used in the present invention are diarylidene bentaerythrite and triarylidene sorbitol. Unsaturated polyester in the method of the invention

The ratio of [1} and unsaturated cycloacetal {2) can be changed depending on the purpose, but the ratio of unsaturated bonds in unsaturated cycloacetal to 1 mole of hydroxyl groups in unsaturated polyester '11 is 0.1 to 0. It is effective in the range of 1 mole. It goes without saying that the proportion of Q-B unsaturated monobasic acid and polybasic acid anhydride varies depending on the required molecular weight, but in general, the proportion of -3 unsaturated monobasic acid used is the proportion of the total acid. 0 of
．． When the amount is less than 1 mole, the viscosity of the unsaturated polyester resin obtained increases, the curing properties are delayed, and the heat resistance of the cured resin decreases. The unsaturated polyester resin having one or more unsaturated bonds at the molecular terminal obtained by the method of the present invention can be used alone or in combination with polymerizable monomers, thermoplastic polymers, rubbers, and oligomers as necessary. . It goes without saying that inorganic or organic reinforcing materials, fillers, dyes, shaping agents, curing agents, accelerators, etc. can also be used as desired. Next, examples will be shown below to help understand the present invention. Example 1 Into a four-walled flask equipped with a key extractor, reflux condenser, thermometer, and dropping funnel, methacrylic acid 1722 was added.
, Phthalic anhydride 148%, Boron trifluoride ether solution 0
．． The mixture was heated to 120-130° C., and 200 portions of propylene oxide, which tends to be heated vigorously, was added dropwise. After finishing dropping, 1. The reaction continued at the same temperature for an hour and the acid value reached 4.
9, a hydroxyl unsaturated polyester having a hydroxyl value of 118 was obtained. Then, the temperature was lowered to 9,000 ℃, 212 ml of diarylidenebentaerythritol was added, and the reaction was continued for an additional 3 hours. As a result of infrared analysis, about 90% of the hydroxyl groups disappeared. Further, 0.3 ml of triethylamine and 0.3 ml of dimedone were added and cooled to obtain a pale reddish brown, syrup-like unsaturated polyester resin. Its molecular structure is estimated as shown in the following formula. To a solution with a viscosity of about 20 poise obtained by adding 10 parts by weight of styrene to 10 parts by weight of unsaturated polyester resin ■, 3 parts by weight of cyclohexanone peroxide and cobalt naphthenate (styrene solution of 6% Co) were added.
Mix 1 part of talc, 15 parts of talc, and 3 parts of Erosyl, and apply it to a paint steel plate to a thickness of 5 ribs, then add 80 qo.
When heated for 30 minutes, it gelled, and after 10 minutes it became possible to polish. The final hardness was pencil hardness, and it passed the bending test of 90 qo without peeling. Example 2 Into a two-four flask equipped with a rope strainer, a thermometer, a gas inlet tube, and a reflux condenser, 144 g of acrylic acid, 332 g of endomethylenetetrahydrophthalic anhydride, 2.5 g of phosphoric acid, and triphenyl phosph were added. In 2.5 evenings, hydroquinone 02
The mixture was heated to 130 to 140 °C, and a mixed solution of 228 °C of allyl glycidyl ether and 130 °C of propylene oxide was added dropwise while stirring. After the dropwise addition was completed, the reaction was carried out at the same temperature for 2 hours, and the acid value was 5 or less and the hydroxyl value was about 140. The temperature was lowered to 90q0, and 296 g of triarylidene sorbitol, 116 g of 2-hydroxylethyl acrylate, and 3.5 g of paratoluenesulfonic acid were added, and the reaction was continued at the same temperature for an additional 5 hours. As a result of infrared analysis, about 80% of the free hydroxyl groups disappeared. After the reaction was completed, 2.5 nights of dimedone and 1 night of triethylamine were added, and the stirring was continued for an additional 30 minutes. After removing the amine under reduced pressure, it was dissolved in a mixture of 300 g of bentaeri stridate triacrylate and 100 g of hexanediol diacrylate to obtain a light reddish brown unsaturated polyester resin 'B' with a viscosity of about 60 poise. 3 parts by weight of unsaturated polyester resin ■10 parts by weight of penzoyisobutyl ether
Parts by weight were added and coated onto a glass plate using knife caulk to a thickness of 0.15. When irradiated with a high-pressure mercury lamp with an output of 200 W/ln at 0°C, it gelated in 1 second and hardened in 3 seconds. Its surface strength is 3 days on a pencil hardness, and it is useful as a vehicle for photocurable inks or paint resins. Example
3. Dripping machine, reflux condenser, dripping. In a four-walled flask equipped with a thermometer, add 172 g of methacrylic acid, 154 g of hexahydrophthalic anhydride,
Prepare 0.1 night of benzoquinone and 1 night of phosphorous acid, 150 ~
Propylene oxide 19 was heated at 155°C while being heated violently.
0 evening was injected. After 4 hours, the acid value became 10 or less, and a hydroxyl unsaturated polyester with a hydroxyl value of about 200 was obtained. Next, the temperature was lowered to 9,020 ℃, 160 mol of diarylidene bentaerythritide and 0.6 mol of paratoluenesulfonic acid were added, and the reaction was continued for a further 3 hours. As a result of infrared analysis, 68% of the hydroxyl groups disappeared. After the reaction was completed, 1 night of dimedone and 0.5 night of triethylamine were added, and 160 nights of cyclohexyl methacrylate were added to obtain a pale yellow liquid unsaturated polyester resin having a viscosity of about 14 poise. After adding 15 parts by weight of Waterstriped Alumina to 15 parts by weight of 'log' to the unsaturated polyester resin and rolling milling, 3 parts by weight of cumene hydroperoxide and 0.5 parts by weight of cobalt octylate (8% Co) were added. , 0.1 part of dimethylaniline was added, and the mixture was poured into a glass slope coated with a mold release agent so as to obtain a casting plate with a thickness of two feet. Defoaming at room temperature.
After gelling and curing by heating at 80q0 for 2 hours,
Further, it was post-cured at 120 oo for 1 hour to obtain a cast plate. The tracking resistance of this columnar plate was very shallow at 600V and 51 drops (according to the mC test method) at an erosion depth of 0.07. A similarly molded cast plate using a cycloaliphatic epoxy resin made from hydrogenated bisphenol diglycidyl ether and hydrogenated diaminodiphenylmethane had an erosion depth of 0.21 in the same tracking test. Example 4 To 10 parts by weight of the unsaturated polyester resin of Example 1,
3 parts by weight of cyclohexyl methacrylate, 2 parts by weight of diethylene glycol dimethacrylate, 2 parts by weight, respectively.
- 5 parts of hydroxyethyl methacrylate, 3 parts of cumene hydroperoxide, 0.3 parts of dimethyl paratoludine,
The composition obtained by adding 0.5 part of phthalimide and 0.0 part of benzoquinone and dissolving it uniformly has excellent properties as an anaerobic adhesive, and is used for bonding 3/8" bolts and nuts. However, after 30 minutes, I was unable to move it with my hands.
The escape torque after the second special period was 350k9. Example 5 Methacrylic acid 172 was placed in a stainless steel flask equipped with a rope strainer, a reflux condenser, a thermometer, and a gas inlet tube.
0 evening, methyltetrahydrophthalic anhydride 840 evening, parabenzoquinone 0.1 evening, triphenylphosphine 7.5 evening
After the mixture was heated to 130 to 135 qo, 880 qo of ethylene oxide was blown into the flask. When the reaction was continued for another hour at the same temperature, a hydroxy unsaturated polyester having an acid value of 10.4 and a hydroxyl value of about 130 was obtained. The temperature was lowered to 90° C., 9 mols of paratoluenesulfonic acid and 1500 ml of diarylidenebentaerythritol were added, and the reaction was continued for 3 hours. As a result of infrared analysis, about 80% of the hydroxyl groups disappeared. After the reaction was completed, triethylamine and dimedone were added to obtain an unsaturated polyester resin plate with a light yellowish brown color and a viscosity of about 30 poise. 3 parts of peroxide and 1 part of cobalt naphthenate (6% Co) were added, and a test piece with a thickness of 3 legs was layered at room temperature using plain woven glass cloth. The surface in contact with the laminate was non-adhesive.The properties of the obtained laminate are shown in Table 1.It was comparable to those using conventional resins.Table 1

Claims (1)

[Claims] 1 An unsaturated compound having a hydroxyl group and a polymerizable unsaturated bond in the molecule obtained by adding a saturated or unsaturated monoepoxy compound to a mixed system containing an α-β unsaturated monobasic acid and a polybasic acid anhydride and reacting the mixture. An unsaturated compound having two or more unsaturated bonds in the molecule obtained by a condensation reaction between polyester (1) and an unsaturated aldehyde polyhydric alcohol that is reactive with the hydroxyl group of the unsaturated polyester (1). A method for producing an unsaturated polyester resin, which comprises reacting the resin with cycloacetal (2).