JPS6017412B2 - Method for producing odorless or low odor crosslinkable compound - Google Patents

Description

Detailed Description of the Invention The present invention relates to a method for producing an odorless or low odor crosslinking compound, more specifically, an odorless or low odor compound obtained by reacting an aromatic hydrocarbon, formaldehyde, and an unsaturated monocarboxylic acid. This invention relates to a method for producing a crosslinkable compound.

Unsaturated polyester resins have excellent workability and various properties after curing, and are inexpensive, so they are used in large quantities.

This unsaturated polyester resin usually contains 40 to 6% by weight of styrene monomer as a crosslinkable monomer, and 10 to 3% by weight of the styrene monomer based on the total amount of the varnish is volatilized and lost during the heat curing process. However, since this styrene monomer has a unique pungent odor and is harmful, it has come to be legally regulated under the Offensive Odor Prevention Law or local ordinances. For example, the Osaka Prefectural Ordinance defines styrene as a harmful gas and its concentration is regulated at 1 ppm or less at the property line, and the Tokyo Metropolitan Ordinance regulates the concentration at the exhaust outlet to 5 ppm or less. Along with the tightening of these laws and regulations, it has become urgent to reduce the odor and brightness of unsaturated polyester resins, both from the standpoint of working environments and resource conservation. In response to this situation, manufacturers are developing and commercializing various low-odor unsaturated polyester resins.

Their feature is that they all use diallyl phthalate instead of styrene as a monomer. However, when this is used as a monomer, there are problems such as poor copolymerizability with polyester, poor electrical properties at high temperatures, and high cost. The present invention has been made in view of the above circumstances, and its purpose is to provide a method for producing an odorless or low-odor crosslinkable compound with good copolymerizability, which solves the above-mentioned problems.

In order to achieve the above object, the present inventors conducted various studies and found that aromatic hydrocarbons, formaldehyde and Q,
The crosslinkable compound obtained by the reaction of P-unsaturated monocarboxylic acid cures itself, has good copolymerizability with polyester, etc., and the cured product has good electrical properties at high temperatures and is odorless. The present inventors have discovered that it has low odor and have completed the present invention.

That is, the present invention relates to a method for producing a crosslinkable compound having a low or bad odor by reacting an aromatic hydrocarbon, formaldehyde, and Q,8 monounsaturated monocarboxylic acid.

Examples of aromatic hydrocarbons used as raw material components in the present invention include m-xylene, toluene, mesitylene, durene, and naphthalene.

Further, typical examples of Q,8-unsaturated monocarboxylic acids include methacrylic acid and acrylic acid. Further, examples of formaldehyde include paraformaldehyde, Q-polyoxymethylene, and a 37.5% by weight formalin aqueous solution. The above reaction of the aromatic hydrocarbon, formaldehyde and Q,3-unsaturated monocarboxylic acid is carried out under heating while blowing air, using an acidic catalyst and a polymerization inhibitor as necessary.

During the reaction, the type and blending ratio of raw materials, the amount of acidic catalyst,
By varying the reaction temperature, reaction time, etc., the viscosity of the product crosslinkable compound and the amount of unsaturated monocarboxymethyl group introduced can be adjusted as desired, allowing the creation of various crosslinkable compounds suitable for the application. It is possible to obtain. 1 to 5 formaldehyde per mole of aromatic hydrocarbon
It is preferable to use the Q,8-unsaturated monocarboxylic acid in an amount of 1 to 50 moles.

The reaction temperature is preferably 80 to 150°C, and the reaction time is preferably 5 to 3 feeding hours. Further, N-methylpyrrolidone, dimethylsulfoxide, benzene, etc. may be used as a solvent. Examples of acidic catalysts used as necessary in the reaction include sulfuric acid, perchloric acid, phosphoric acid, acetyl perchloric acid, trifluoromethanesulfonic acid, polyphosphoric acid, chlorosulfonic acid, toluenesulfonic acid, xylene sulfonic acid, Examples include poly(styrene sulfonic acid) resin, silica gel, and phosphoric acid supported on activated carbon.

The obtained crosslinkable compound is confirmed to have a Q,B-unsaturated monocarboxymethyl group by its infrared absorption spectrum and nuclear magnetic resonance absorption spectrum.

This compound has the feature of being odorless or having low odor. Moreover, it can undergo radical polymerization at low temperatures, forms a cured product by itself, and the obtained cured product has excellent electrical properties at high temperatures. Curing temperature ranges from room temperature to 200C○
Preferably, the curing time from room temperature to 150 qo is in the range of 1 minute to 5 field hours, preferably 1 to 1 patch time.

During curing, a curing agent described below and, if necessary, a curing accelerator described below are used. Furthermore, this crosslinking compound can be used as a crosslinking agent for unsaturated polyester, acrylic acid- or methacrylic acid-modified polybutadiene resin, etc., and the resulting cured product has electrical properties at high temperatures that are better than those using conventional crosslinking monomers. is also excellent.

Examples of the unsaturated polyester crosslinked with the crosslinkable compound of the present invention include various general-purpose unsaturated polyesters obtained from the following alcohol component, acid component, and modifier (optional component). '1' Alcohol component ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,3-pro/gundiol, 1,2-pro/gundiol, 1,2-butanediol, 1,3-butanediol , 1,4-butanediol, 1,2-bentanediol, 1,3-pentanediol, 1,2-hexanediol, 1,4-hexanediol, 2,3-hexanediol, dipropylene glycol, etc. Group glycols; cycloaliphatic diols such as cyclobentanediol and cyclohexanediol; xylene glycol,
Aromatic diols such as dimethylxylene glycol and 2,2-pis(4-hydroxyphenyl)propane; Ethers such as bisethylene glycol ether, pispropylene glycol ether, and bisbutylene glycol ether; glycerin, trimethylolethane, and trimethylolethane. - Polyhydric alcohols such as lupropane and bentaerystol: or mixtures thereof.

The above-mentioned alcohols are generally produced industrially and used in the production of unsaturated polyesters. '2' Acid component unsaturated carboxylic acids such as maleic acid, maic anhydride, fumaric acid, itaconic acid, citraconic acid, endomethylenetetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, linseed oil, soybean oil , vegetable oil fatty acids such as tall oil, coconut oil, and castor oil;
these inductions or mixtures thereof.

Phthalic acid, phthalic anhydride, isophthalic acid, as necessary.
Saturated acids such as terephthalic acid, adipic acid, etc. can be used with the above components. '3} Modifier (optional component) Cyclobentadiene, dicyclobentadiene, etc. are used.

The acrylic acid- or methacrylic acid-modified polybutadiene resin that is crosslinked with the crosslinkable compound produced by the present invention is a resin in which an active group is introduced at the end of polyptadiene, and this active group is reacted with the carpoxyl group of acrylic acid or methacrylic acid. Resins having reactive double bonds at the ends, such as TE-2000 (methacrylic acid-modified polybutadiene resin, manufactured by Nippon Soda), VTB200
0 × 164, VTBN1300 × 22,
Examples include VTBNX1300×23 (acrylic acid-modified polybutadiene resin, manufactured by Ube Industries K.K.).

20 to 5 parts by weight of a crosslinkable compound obtained by reacting an aromatic hydrocarbon, formaldehyde, and Q,8-unsaturated monocarboxylic acid to 100 parts by weight of unsaturated polyester or acrylic acid- or methacrylic acid-modified polybutadiene resin.
It is preferable to use 00 parts by weight.

The odorless or low odor resin composition obtained using the crosslinkable compound produced by the present invention contains, in addition to the above essential components, a curing agent, a curing accelerator, a crosslinkable monomer, a polymerization inhibitor,
It can contain fillers and the like.

As curing agents, acyl peroxides such as penzoyl peroxide and acetyl peroxide; hydroperoxides such as tert-butyl peroxide and kyumene hydroperoxide; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; Dialkyl peroxides such as tertiary-butyl peroxide and dicumyl peroxide; oxyperoxides such as tertiary-butyl perbenzoate and tertiary-butyl peroxyacetate can be used.

The amount used is generally from 0.5 to 0.5 based on the resin composition.
5% by weight, preferably in the range 1-3% by weight. As hardening accelerators, commonly used naphthenic or octenoic acid metal salts (e.g. cobalt, manganese, iron,
(lead, nickel, tin, zinc salts, etc.) can be used, and the amount added is 0 to 2. % by weight.

Styrene, various high-boiling point acrylic esters or methacrylic esters, high-boiling point allyl ethers or allyl esters, etc. are used as the soba monomer, for example, trimethylolpropane triallyl ether, glycerin triallyl, etc. Allyl ether, diallyl phthalate, diallyl isophthalate, etc.
Allyl esters such as triallyl isocyanurate and trifuryl cyanurate are used.

As a polymerization inhibitor, hydroquinone, paratasia 1'
-Butylcatechol, quinones such as pyrogallol, and other commonly used quinones can be used.

The amount added is 0 to 0.5% by weight based on the resin composition. As fillers, silica, talc, calcium acid, asbestos, glass fiber, wood flour, coloring agents, etc. added to polyester resins are used as necessary.

The present invention will be further explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 1 with air inlet tube, thermometer, reflux condenser and condenser
Into the four-necked flask, m-xylene 2129 (2.0
mole), paraformaldehyde (Wako Pure Chemical Reagent Grade 1)
180 mol (HCHO equivalent 6.0 mol), methacrylic acid 3
44 y (4.0 mol), t-butylcatechol 0.5 y
and 60% chloric acid for 20 hours per week, and vigorously koji worshiped at 10,000 ℃ while blowing air for 8 hours.

The reaction product was washed with water, an approximately 1% by weight aqueous sodium carbonate solution, and then water. Dehydrate the organic layer and
A crosslinkable compound (2) with a strength of 3 poise at room temperature was obtained. This compound■
was almost odorless. When the infrared absorption spectrum of this substance (1) was measured, strong absorption was observed at a ratio of 172 to -1 based on the carbonyl group of the methacryloylmethyl group. In addition, when we measured the nuclear magnetic resonance spectrum of this substance (2), we found that strong absorption based on methylene of the methacryloylmethyl group was observed at 8=5.1 pm; It was found that 0.8 mol of was present. Example 2 3 equipped with an air inlet tube, a thermometer, a reflux condenser and a syringe
Into the four-necked flask, add 212 g of m-xylene (2.0
180 moles of paraformaldehyde (6.0 moles in terms of HCHO), 1720 moles of methacrylic acid (20 moles),
1.0 ml of t-butylcatechol and 20 ml of concentrated sulfuric acid were added, and the mixture was heated under reflux for 8 hours while blowing air.

Next, after removing unreacted methacrylic acid, the product was washed repeatedly with warm water until it became neutral. Furthermore, after dehydration, an almost odorless crosslinkable compound {B) was obtained. This compound [B}' was a poise liquid at room temperature. Furthermore, when we measured the nuclear magnetic resonance absorption spectrum of this substance [B}, we found that
A strong absorption based on methylene of the methacryloylmethyl group was observed at 6=5.10 ppm, and it was found that 1.3 moles of the methacryloylmethyl group were present per mole of xylene nucleus. Example 3 Paraformaldehyde was added to 37.5% by weight formalin 4
The reaction was carried out under the same conditions as in Example 1, except that the reaction was changed, and an almost odorless crosslinkable compound {C' was obtained.

When the nuclear magnetic resonance spectrum of this compound [C' was measured, a strong absorption based on methylene of the methacryloylmethyl group was observed at 6 = 5.10 ppm, and the methacryloylmethyl group was 0.7% per mole of xylene nucleus. It was found that there are moles. Example 4 A reaction was carried out under the same conditions as in Example 1 except that paraformaldehyde was changed to Q-polyoxymethylene manufactured by Sumitomo Bakelite, and an almost odorless crosslinking compound was successfully obtained.

When the nuclear magnetic resonance vector of this compound blood was measured, strong absorption based on methylene of the methacryloylmethyl group was observed at 6 = 5.1 pm, indicating that the methacryloylmethyl group is It was found that 0.7 mol was present. Example 5 The amount of paraformaldehyde was 6
The reaction was carried out under the same conditions as in Example 1, except that the amount was changed to 0.0 (2 mol), to obtain an almost odorless compound [E}.

When the nuclear magnetic resonance spectrum of this compound leg was measured, strong absorption based on methylene of the methacryloylmethyl group was observed at 8 = 5.1 pm', and the methacryloylmethyl group was found to be 0.5% per mole of xylene nucleus. It was found that 4 moles were present. Example 6 A reaction was carried out under the same conditions as in Example 2, except that the amount of paraformaldehyde was changed to 600 mmol (2 moles), to obtain an almost odorless crosslinkable compound.

When the nuclear magnetic resonance spectrum of this compound {F} was measured, a strong absorption based on methylene of the methacryloylmethyl group was observed at 6=5.1 pm, and the ratio of 1 methacryloylmethyl group to 1 mole of xylene nucleus was observed. It was found that .0 mol was present. Example 7 A reaction was carried out under the same conditions as in Example 1, except that m-xylene was replaced with 1 mol of toluene (2.0 mol), to obtain an almost odorless crosslinkable compound (G).

When the infrared absorption spectrum of this compound (G) was measured, strong absorption based on carbonyl of the methacryloylmethyl group was observed at -1 of the 172 ratio. Further, when nuclear magnetic resonance spectrum was measured, strong absorption based on 6=5.10 ppm' was observed, and it was found that 0.8 mol of methacryloylmethyl group was present per 1 mol of toluene nucleus.

Example 8 A reaction was carried out under the same conditions as in Example 1, except that methacrylic acid was replaced with acrylic acid (4.0 mol), to obtain an almost odorless crosslinkable compound (H).

When the infrared absorption spectrum of this compound (H) was measured, strong absorption based on the carbonyl of the acroylmethyl group was observed at 1720 arc-1. In addition, when a nuclear magnetic resonance spectrum was measured, strong absorption based on 6=5.1 Pm was observed, and it was found that 0.8 mol of acryloylmethyl group was present per 1 mol of xylene nucleus. Reference Example 1 The crosslinkable compounds obtained in Examples 1 to 8 (PT-
28 (cobalt naphthenate solution, manufactured by Hitachi Chemical ■) and 1.5% by weight of CT-7 (tert-butyl perbenzoate, manufactured by Hitachi Chemical ■). % by weight was added, and the temperature was maintained at 12 mm for 5 hours to cure.

The state of the varnish and various properties of the cured product are shown in Table 1. 1st
Table (note),. ．． The odor was determined in the varnish state, and the odor during drying was determined using an SA type standard dryer (450 x 35
0 x 350 skin) at 130°C.''Put a tin container containing each varnish 309 (100 x 100 x 20 skin) into this, and judge the odor inside the dryer after 30 minutes.
Put 60 cm of metal Petri dish K varnish 109, 120 cm
The weight loss rate was measured when the sample was held at ℃ for 3 hours.

(Note 3)...Measured using a BL type rotational viscometer.

(Note 4).・．． 18 side ■ Varnish was placed in a test tube up to a height of 70 cm, and the gelation time was measured using a GE gel timer. (
Note 5)...The bending properties were measured using a Tensilon-type universal testing machine on a 5xloxloo skin slope with a bending speed of 3 skins/ml n' span 80 skins.

(Note 6),.・Silver tint was applied to the resin plate on the 2xlooxloo side, and measurements were made using a TR-2100 automatic material property measuring machine manufactured by Ando Electric KK. As is clear from Table 1, the posture-promoting compound legs of the present invention, [B},'C)
, plate, [E1, side, (G) and (H) have low odor to no odor when varnished or dry, and the amount of luminescence when held at 12000 for 3 hours is 2.8 to 4.4 weight. It was found that the percentage was low. Furthermore, it was confirmed that the electrical properties at high temperatures were also good. Reference Example 2 100% of the low-odor crosslinking compound obtained in Example 1 was added, and 100% of PS-57 body (unsaturated polyester manufactured by Hitachi Chemical) was added to 0.0% of the PT-28.
5% by weight and 1.5% by weight of CT-7. % by weight was added and cured.

Table 2 shows the properties of the varnished product and the cured product. Comparative Examples 1 and 2 The same procedure was used as in Reference Example 2, except that the low-odor crosslinking compound obtained in Example 1 was replaced with styrene or diallyl phthalate, and the results are shown in Table 2.

Reference Example 3 Low odor crosslinking compound W50, Diaryl phthalate 5 instead of low odor, figure-protecting compound K100
The procedure was the same as in Reference Example 2 except that 0.0% was used, and the results are shown in Table 2.

Table 2 (Note 1)...109 varnish on a metal petri dish with 60 skins
The weight loss rate was measured after holding at 130°C for 3 hours.

(Note 2)... Measured using a BL type rotational viscometer.

(Note 3) Varnish was placed in a 18-skin test tube to a height of 70 skins, and the gelation time was measured using a GE gel timer. (
Note 4). ...10 x 12.7 x 140 skin test pieces as AS
Measured according to TM-D648-45T(a) method.

(Note 5)...The bending properties of the resin plate on the 5xloxloo side were measured using a Tensilon type universal testing machine at a bending speed of 3 skins/min and a span of 8o. (Note 6)…2xlooo
The wood on the xloo side was temporarily coated with silver tint, and measured using an automatic material property measuring machine model TR-2100 manufactured by Ando Electric KK. (Note 7)...The resin plate on the 2 x 15 x 25 side was placed in an air circulation type air temperature tank at 160℃,
The critical reduction rate after 40 days was determined. As is clear from Table 2, the unsaturated polyester resin obtained by the production method of the present invention using a low-odor crosslinking compound as a monomer has a low odor and is maintained at 130°C for 3 hours, unlike the case where styrene is used as a monomer. The amount of luminescence when doing this is 2. It was confirmed that the weight percent was 1/10 of that in the case of using styrene, and that the electrical properties and heat deterioration resistance at high temperatures were also good.

Furthermore, compared to the case where the conventionally used diallyl phthalate is used as a monomer, the one using the low-odor crosslinking compound of the present invention as a monomer has good curability, and has excellent electrical properties and heat deterioration resistance at high temperatures. It turned out that there was.

Furthermore, when a mixture of the low-odor crosslinkable compound obtained by the production method of the present invention and other crosslinkable monomers such as diallylphthalate, styrene, triallyl isocyanurate, triallyl cyanurate, etc. is used as a monomer, It was found that the heat deformation temperature, bending strength, etc. were improved without impairing the above-mentioned advantages, and the properties were significantly improved compared to those using only diallyl phthalate as a monomer.

Reference Example 4 Low odor crosslinking compound obtained in Example 1 ■100 minutes, TE
-2000 (methacrylic acid modified polybutadiene resin, manufactured by Nippon Soda ■) 509, PT-28 (cobalt naphthenate solution, manufactured by Hitachi Chemical ■) 0.75 and CT-7 (tertiary butyl perbenzoate, manufactured by Hitachi Chemical ■) Varnish (1) was obtained by mixing for 1.5 nights.

Reference Example 5 Low odor crosslinking compound obtained in Example 1 100 days, TE
1200060 minutes, B-1000 (polybutadiene resin, number average molecular weight 1000, manufactured by Nippon Soda ■) 60 days, methacrylic acid laur 150 times, PT-280.7 times and CT-7 1.5 times were mixed; (J) was obtained.

Reference Example 6 Low odor crosslinkable compound sail obtained in Example 1 10
0. Evening, VTBN 2000 x 164 (acrylic acid modified POIJ butadiene resin, manufactured by Ube Industries ■) 50 Evening, PT
-280.759 and CT-7 1.5 days were mixed to obtain varnish (K). Varnishes obtained in Reference Examples 4 to 6 (1)
-(K) and the general properties of the cured products thereof are shown in Table 3.

Table 3 (Note 1)...The odor was determined in the varnish state, and the odor during drying was determined using the SA type standard dryer (450
x 350
Willow) was placed in the dryer, and the odor inside the dryer was determined 30 minutes later.

(Note 2) Varnish 109 was placed in a metal petri dish on the 60 side (■), and the weight loss rate was measured when the varnish was held at 120° C. for 3 hours. (Note 3)... Measured using a BL type rotational viscometer.

(Note 4)... Varnish was poured into a test tube with 18 ribs up to a height of 70, and the gel-hataterama was measured using a GE gel timer.
(Note 5) The bending properties of a 5xlo x 100 resin plate were measured using a Tensilon type universal testing machine at a bending speed of 3 min and a span of 80.

(Note 6)... 2xloo x 100 skin resin board was coated with silver tint and measured using a TR-2100 model automatic material property measurement made by Ando Denki KK.As is clear from Table 3. It has been confirmed that the resin composition obtained using the odorless or low-odor crosslinkable compound obtained by the production method of the present invention has low odor and low dispersion, and also has good electrical properties at high temperatures. As stated, according to the present invention,
Provided is an odorless or low-odor crosslinkable compound that satisfies the requirements for pollution prevention and resource conservation and produces a resin composition suitable for insulating materials.

Claims (1)

[Scope of Claims] 1. A method for producing an odorless or low-odor crosslinkable compound, which comprises reacting an aromatic hydrocarbon, formaldehyde, and an α,β-unsaturated monocarboxylic acid. 2. The method for producing an odorless or low-odor crosslinkable compound according to claim 1, wherein the aromatic hydrocarbon is m-xylene or toluene. 3. The method for producing an odorless or low-odor crosslinkable compound according to claim 1 or 2, wherein the formaldehyde is paraformaldehyde, α-polyoxymethylene, or a 37.5% by weight formalin aqueous solution. 4. The method for producing an odorless to low odor crosslinkable compound according to claim 1, 2 or 3, wherein the α,β-unsaturated monocarboxylic acid is methacrylic acid or acrylic acid.