JPS6088019A - Production of modified hydrocarbon resin - Google Patents

Abstract

PURPOSE:To obtain a low-MW resin low in odor and excellent in trasparency and compatibility with a synthetic resin, by reacting a specified polymer prepared by polymerizing a residual oil formed as a by-product in the synthesis of a phenol with a formaldehyde. CONSTITUTION:Of a residual oil formed as a by-product in the synthesis of a phenol via a hydroperoxide, a fraction having a b.p. of 180-210 deg.C is polymerized by using a catalyst to form a polymer comprising 50% or more unsaturated dimer and 30% or less saturated dimer and trimmer (stage 1). This polymer is reacted with a formaldehyde by using a catalyst (stage 2). From the necessity of forming as much dimer as possible, a catalyst having a low catalytic activity is used in stage 1, or it is used in conjunction with a substance having a lone pair in the molecule and serving as a compound for regulating the reaction. It is preferable to use a catalyst more active than that used in stage 1 as the catalyst used in stage 2.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a method for producing modified hydrocarbon resins.

More specifically, 180 to 21% of the residual oil produced as a by-product during the synthesis of phenols via hydroperoxide
Using by-product oil having a boiling point of 0°C as a starting material, a polymer containing a large amount of unsaturated dimers is produced in the first step, and then, in the second step, the polymer is reacted with formaldehyde. Concerning a method for producing modified hydrocarbon rosin.

(Purpose of Prior Art No. 1) Hydrocarbon resins such as petroleum resin acid phase and coal-based aromatic oils have traditionally been produced by adding a catalyst to the raw material oil and heating and stirring to form a liquid or solid ( ☆1 We manufacture fat.

However, when producing liquid carbonaceous resins.

V cannot be achieved unless the increase in the degree of polymerization is suppressed as much as possible.

However, there are many unreacted components in the rice, causing a bad odor, and if there are some highly reactive components in the raw oil, first, those components are VIF-coated to form a polymer for 1115 minutes. Since other components are delayed and offshore, high-molecular and low-molecular components are mixed, and the fIi[
It is well known that the molecular weight of coalescence becomes wider and the transparency of the resin deteriorates.

The present inventors have developed a low-molecular compound that does not have such drawbacks,
Moreover, it has excellent transparency and has little odor.

Furthermore, the present invention was completed as a result of research aimed at producing a 4M4 fat that has excellent compatibility with synthetic 4AV fats.

(Component 1 of the invention) In other words, the present invention deals with the treatment of 180 to
Polymerizing a by-product oil with a boiling point of 210°C using a catalyst to produce a polymer containing at least 50% unsaturated dimer and 30% or more saturated dimer and trimer. A method for producing a modified hydrocarbon resin, the 18th step being the 18th step, and the 2nd step being reacting the polymer with formaldehyde using a catalyst.

It is.

Next, the present invention will be explained in detail.

The raw material oil used in the present invention is hydroveroxa f)
The residual oil that is produced as a by-product during the synthesis of phenols via '' is used.

The residual oil contains acetophenone, methylacetophenone, inglovirphenol, inglovirhenzyl alcohol, etc., and has a unique odor. In the present invention, these components are removed.

In the present invention, in order to further improve the performance of the resin, the first
In step 1, the raw material oil is polymerized to produce a polymer containing a large amount of unsaturated oxidized compound, and then in step 1 and step 2, formaldehyde is mixed in a 1:1 addition reaction to make it transparent. To produce a liquid hydrocarbon resin with excellent properties, low odor, and excellent compatibility with synthetic resins such as epoxy resins made of polymers.

Because it is necessary to form as many unsaturated dimers as possible in the catalyst used in this first step, it is preferable to use one catalyst with weak catalytic activity, or to Substances that create lone pairs of electrons 1 e.g. water, alcohol + no zk f
fp it-thiophene, sulfolane, and oxidized oxygen are used as active compounds (Jl).Subsequently, the second stage reaction is carried out, and one is used as a catalyst for this reaction. 1. It is preferable to use a catalyst that is more active than the catalyst used in the first stage.

Catalysts with weak activity include -CU: +For example, solid catalysts supporting oxidized pentoxide, or cation exchange resins that improve specific properties. Examples of carriers that support phosphorus pentoxide include 7 oxide, alumina, silica-alumina, and silica.
It is preferable to use titania or the like which has been subjected to high-temperature firing treatment at 500° C. or higher to reduce its surface area.

Among these, single acid ratios such as silica or alumina are preferred over composite acid ratios such as silica-alumina and silica-titania in that they do not increase the catalytic activity. Another 1%
As a cation exchange resin having certain properties, for example, a strongly acidic cation exchange resin having a pore diameter in the range of 102 to 103X and a pore volume of 005 to 0.3 me/f is used. This is desirable.

As an example of a catalyst with strong catalytic activity used in the second stage (j
l, activity-enhancing boron trifluoride-complex.

Examples include para-toluenesulfonic acid, phosphoric acid, sulfuric acid, and mixtures thereof.

In the first step of the reaction of the present invention, raw material oil is polymerized, and one polymer contains at least 50 or more, preferably 60 or more, unsaturated polymers, and one polymer has at least 50 polymers or 3 polymers, and 1 polymer has at least 60 polymers or 3 polymers. The amount of the above polymer is 30%, preferably 15% or less. Then, in the second step, the formaldehyde compound 1 is reacted with the unsaturated compound 1 produced in the first step to form a trimer.

Formaldehydes include paraformaldehyde,
Polmarin, trioxa/etc. can be used. The second stage reaction is carried out by adding 5 to 90 parts of formaldehyde to 100 parts of the product produced by the reaction in the tr, +: -x++ stage. I could do it v11
To carry out the reaction in an anhydrous state, it is sufficient to use anhydrous formaldehyde such as il, i:, -to IJ Ogizan.

In addition, in an anhydrous reaction system, the above-mentioned phosphorus pentoxide't J:
It does not use solid catalysts such as catalytic catalytic agents or JJ cation exchange resins, and there is no release of acid into the coalescence during the initial reaction, so there is no need to wash with neutralizing water to remove the catalyst after the reaction. , 4 on the instep
It can be removed with only 4 passes, and the water usage public '7ji' 7
・This is preferable as a J-measure.

In the first stage reaction, the number of unsaturated polymers (6) of 49 units was 50 and 6!71, and the number of saturated dimers and trimers or higher polymers was 30.
If the temperature exceeds 100.degree. C., the modification with formaldehyde cannot be sufficiently carried out in the second stage reaction, resulting in poor compatibility with synthetic resins such as epoxy resins.

In the first step reaction of the present invention, low molecular weight unsaturated)
In this case, a normal polymerization method is carried out in which the J-2 aphrodisiac is produced and then modified with formaldehyde in the second step reaction, but without going through such a step, the raw material oil is directly modified with formaldehyde. .

Since a large amount of low-molecular weight substances are produced by reacting formaldehyde with the monomers in the raw material oil, a bad odor may be emitted, which is not preferable.t, J: None. Gas chromatography can be used to confirm the form of the substance produced by the reaction.

In the first stage reaction of the present invention, 0.1 to 10 parts of catalyst is used per 100 parts of feedstock oil, depending on the catalyst (4:1), and 0.5 to 10 parts are used at 60 to 150°C with stirring. The reaction is carried out for ~3 hours. When a reaction regulating compound is used in combination, the amount used is 05 to 200 with respect to the amount of the catalyst used.

Next, all the formaldehyde is added to carry out the second stage reaction, and the amount used is 5 to 90 parts per 100 parts of the product obtained by the reaction in the first stage. The catalyst used at that time is 0 to 10 parts per 00 parts of the product γ(]-00, and the reaction is carried out at 60 to 150°C for 05 to 3 hours.

After the reaction is complete, proceed to step A11. After removing the catalyst by water washing or i-1 filtration, unreacted components are removed by distillation to obtain a resin.

Tree h i,! XJ by II! ! 1 fat of crushed 41' is immediately transparent and weather resistant. Synthesis of epoxy resin, urethane resin, etc. with no odor and strong polymer fabric (η
1: Compatible with fat 1: It becomes very thick.

(Example) Next, the present invention will be explained using Example 11.

In the example, among the residual oils produced as by-products during the synthesis of cresol via hydroverogizide, the δ1) point range is 180 to 20.
A silica catalyst supporting phosphorus pentoxide (pentaacid f phosphorus containing <5 r+,
Add 2 parts of 4j) as a catalyst for the second stage anti-Li=,
After reacting for 1 hour with stirring at ()0 to .95'C, the catalyst was removed by -if' filtration. The product substance was analyzed by gas chromatography and the result was 73 rizu in Table 1.

Then, for 100 parts of the product, 151 parts of trioxane
41i and 2 parts of activity enhancer were added and reacted at -90 to 95°C for 1 hour. After the reaction was completed, the catalyst was removed by filtration, and the unreacted materials were removed at 3.50°C: l-50m
A resin was obtained by vacuum distillation at 11 mH. Resin (1 material) is shown in Table 2.

Example 2 To 100 parts of the same raw material as in Example 1, 2 parts of a silica-titania catalyst (containing phosphorus pentoxide 35.5%) supporting the pentate f-hydrine (phosphorus pentoxide content: 35.5%) was used as a catalyst for the first stage reaction. Then, 1 part of 1,4-dioxane was added as a reaction regulating compound, and the reaction was carried out at 90 to 95° C. for 1 hour with stirring, and then the catalyst was removed by -i:j filtration. The composition of raw 2Q material is shown in Table 1. Next, to 100 parts of the product, 15 parts of trioxane were added, and 2 parts of activated clay were added.
The reaction was carried out at 90 to 95°C for 1 hour. After the reaction is complete, l
All of the catalyst used was removed by filtration, and unreacted substances were then distilled off.The properties of the resulting resin are shown in Table 2.

Example 1 and 11 3 For 100 parts of the same raw material as in Example 1, the pore volume when the reaction catalyst in the second stage was 102 to 103 large was Q, 26 me/! A cation-exchanged Japanese fat (product name: Diaion HPK2!5-Mitsubishi Kasei G), which is
t4: After ion-substituting the Nα salt of the product (manufactured by ) with hydrochloric acid (10% aqueous solution) and adding sulfolane as a reaction regulating compound to oil, the mixture was reacted for 1 hour and 1 hour at 90 to 95°C with stirring. The composition of the horn material is shown in Table 1.

Then, for 100 parts of the product, Trioxa 715
After cooling, 72 parts of activated clay was added and the reaction was carried out at 90 to 95°C for 1 hour. After warping, the used catalyst was removed by Δ1 filtration, and unreacted substances were distilled off. I did h
The properties of j4 fat are shown in Table 2.

Comparative Example 1 1st step reaction IIFl: The reaction was carried out in the same manner as in Example 1, except that two pieces of Kikumejirogami were used as a medium ((11 fats were obtained. The graphite results are shown in Table 1, and the properties of the (1) fat obtained in the second stage reaction are shown in Table 2.

Comparison Example 2 The reaction was carried out in the same manner as i-1 and Example 1, except that 2 parts of a solid catalyst containing pyrophosphoric acid (diatomaceous earth diphosphoric acid ratio -1:2) was used as the reaction catalyst in the first stage. A resin was obtained. Table 1 shows the results of gas chromatography analysis of the product produced in the first stage reaction, and Table 2 shows the properties of the resin obtained in the second stage reaction.

Comparative Example 3 First and second stage reactions were carried out in the same manner as in Example 4, except that water was not used as the reaction compound) ☆1 fat was obtained.

Table i1 shows the composition of the product produced in the first stage reaction, and Table 2 shows the properties of Wa1 fat obtained in the second stage reaction.

Comparative Example 4 84 Chibara Formaldehyde 'i' OOpfll f was added to 1260 parts of the same raw wood 1 oil as in Fire Allocation 111, and 30 parts of catalytic paratoluenesulfonic acid was used.

After reacting at 100° C. for 2 hours, the catalyst was removed by washing with water. Next, vacuum distillation was performed at 150° C. + 150 nHg to remove unreacted components.

Table 2 shows the properties of raw 1+1';

Note 1 Epoxy Iη1 fat (bisphenol A QIJ EBOKI 7 JIa・+ fat, epoxy fi:l 60-=
200) Using a 40% solution (solvent: toluene: methyl ethyl ketone: methyl isobutyl ketone - 6:2:2), the resin produced according to the present invention and the epoxy equivalent were mixed in a solid content ratio of 1:1 or more, but no turbidity occurred. Those that did not cause this were considered to have good bathing properties.

Note 2 Tested in the same manner as Note 1 using an epoxy resin (bisphenol A epoxy resin, epoxy equivalent: 870-1ooo).

Claims (1)

[Claims] 1 Among the residual oils produced as by-products during the synthesis of phenols via hydroperoxides, by-product oils with a boiling point of 180 to 210°C are polymerized using a catalyst to remove at least 50 units of unsaturated dimers. In addition, the first step is to produce a saturated diploid and trimer or more or less than 30 polymer, and the second step is to react the polymer with formaldehyde using a catalyst. A process for producing modified hydrocarbon resins.