JPS5818945B2 - Compound materials for polymer resins - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a compounding material for polymer resins obtained by refining cracked distillate oil.

More specifically, the present invention provides a method for polymer resins obtained by refining cracked distillate distilled when thermal cracking or oxidative dehydrogenation is carried out on petroleum aromatic extracts and petroleum heavy residues. Regarding compound materials.

In order to effectively utilize aromatic extracts and heavy petroleum residues extracted from petroleum fractions with furfural, phenol, etc., we perform pyrolysis polycondensation reactions or oxidative dehydrogenation using oxidizing agents such as oxygen or air. By performing polycondensation reactions, we produce binders for coke production, resin compounds for paints,
Our company is conducting research on methods for obtaining paving agents or rubber additives, and has already filed several patent applications (for example, JP-A-48-31204, JP-A-53-10602, JP-A-55).
-139407).

When the above-mentioned aromatic extract or petroleum heavy residue is subjected to thermal cracking or oxidative dehydrogenation, oil (hereinafter referred to as cracked distillate) is distilled out, but the amount of cracked distillate is Over 50% during decomposition reaction, 2 during oxidative dehydrogenation polycondensation reaction
It reaches about 5%.

Conventionally, this cracked distillate has had a low reputation and has only been used as a fuel oil as a C heavy oil blending material, so it is important from an economic standpoint to utilize it with increased added value.

Therefore, an object of the present invention is to utilize cracked distillate oil effectively.

The present inventors focused on the fact that cracked distillate oil contains a large amount of highly aromatic fractions, and in particular, the distillate oil obtained during oxidation treatment is highly polar and contains chemically stable oxygen-containing compounds. Then, when aromatic fractions and oxygen-containing compounds were selectively extracted using furfural, phenol, or similar solvents, this refined oil was extracted from epoxy resins, urethane resins, acrylic resins, chlorinated rubber, vinyl chloride resins, The present invention was completed by discovering that it has good compatibility with polymer resins such as alkyd resins and can be used as a compounding material for polymer resins.

The polymer resins targeted by the compound of the present invention have different polarities.

There are various properties required for polymer resin compounding materials, but particularly good compatibility with the resin is important.

That is, the compatibility between the polymer resin and the compounding agent is extremely important in that the compounding material does not ooze out from the resin plasticized with the compounding material.

Flory, P. J. (J. Chem. Phys.
s, 9 660 (1940), ibid., 10 51 (194
2), 12 '425 (1944)) and Hugqi
nslM, L, (Anale N, Y, Acad.

Sci, 43 1 (1942), from the thermodynamic theory of polymer solutions, it is known that compatibility is regulated by the volume concentration and the interaction constant μ.

Also, the solubility index (Solubility Parameter)
er, hereinafter referred to as S, P, value.

) are also constants related to compatibility, but they are deeply related to the molecular weight and cohesive energy (molecular polarity) used in s, p, value calculations.

) is related to the volume concentration of molecules and the interaction constant μ, and the compounding material needs to have an appropriate molecular weight and cohesive energy for the corresponding resin, that is, an appropriate volume concentration and interaction constant μ.

In other words, the compounded material is required to have a narrow molecular weight distribution and to have an average molecular weight and polarity appropriate to the resin.

Ordinary petroleum products have a wide molecular weight distribution, so it is assumed that there is a considerable distribution of their volumetric concentrations.
That is, it is clear that since it contains a saturated hydrocarbon with a large interaction constant μ with the resin, it is not compatible with the resin and cannot be used as a compounding material.

The cracked distillate oil, which is the raw material for the resin compounding material of the present invention, is subjected to some degree of distillation during the reaction, so the molecular weight distribution is narrow except for a small amount of light fraction, and the distillate oil is distilled out by the cracking reaction. Since it is a fruit oil, it is expected that the fraction will be more aromatic (higher aromaticity index fa).

Furthermore, the distillate oil when oxidized with an oxidizing agent such as oxygen or air contains highly polar and chemically stable oxygen-containing compounds.

However, since cracked distillate oil also contains a considerable amount of saturated hydrocarbons, it does not exhibit compatibility with resins as it is.

Therefore, the present inventors extracted cracked distillate oil with furfural, phenol, or similar solvents, and selectively obtained highly aromatic fractions and oxygen-containing compounds. Rich in fractions with small interaction constant μ,
It has been found that it has good compatibility with resins and can be used as a compounding material for epoxy urethane resins, acrylic resins, chlorinated rubber, vinyl chloride resins, alkyd resins, etc.

The resin compounding materials according to the present invention will be sequentially explained below.

(1) Raw material cracked distillate oil Distillation of cracked distillate oil distilled when air was blown into an aromatic extract with an average molecular weight of 320 extracted with furfural at a reaction temperature of 290°C to perform an oxidative dehydrogenation polycondensation reaction. Data (Table I) - Membrane properties and gel-chromatic analysis results (Table ■) are shown.

* Nippon Rubber, association magazine, 50th Volume, No. 1O, p669 According to the method.

The distillation data in Table I shows that this distillate has a fairly narrow boiling point range (and narrow molecular weight distribution), except for a small amount of light fraction.

Furthermore, the gel chromatography analysis results shown in Table 3 indicate that the oil contains a considerable amount of aromatic fraction, which indicates that it is desirable as a raw material oil for the present invention.

Furthermore, since the acid value is low, it is inferred that the oxygen-containing compound mainly has ether or ester bonds.

This oxygen-containing compound having an ether or ester bond is expected to have high polarity and good compatibility with the resin.

Regarding cracked distillate oil other than this example, for example, those obtained from thermal cracking reactions do not contain oxygen-containing compounds, and those made from petroleum heavy residues may contain somewhat less aromatic fractions. Although there were some differences, it had almost the same properties as the distillate oil shown above, and was sufficient as a raw material oil for obtaining the compounded material of the present invention.

By the way, this distillate oil cannot be obtained as a refined oil that can be used as a compounding material of the present invention under conventional lubricating oil refining conditions.

In other words, in the conventional extraction conditions for lubricating oil refining, the main focus is on refining the lubricating oil, which is the extraction residue, so the extraction temperature is raised (and a low aromatic residue with a large interaction constant μ) is used. Since the oil is dissolved and extracted in a solvent such as furfural or phenol, the resulting extracted oil lacks compatibility with the resin as a whole.

Therefore, extraction conditions (particularly extraction temperature) using solvents such as furfural and phenol become a problem.

) is the most important requirement for obtaining refined oil as a compounding material for resins.

(2) Purification of cracked distillate oil and compatibility with resin Using the cracked distillate oil shown in (1) as a raw material, an extraction and purification experiment was conducted using furfural.

The extraction conditions, the yield of the refined oil obtained, and the results of a compatibility test using a bisphenol-epichlorohydrin type epoxy resin with an epoxy equivalent of 190 as the resin are shown in Table 2.

The epoxy resin used here is a condensation product of epichlorohydrin and bisphenol, and the commercially available epoxy resin has the following general formula, where n=2 to 12, but is not particularly limited by n.

After the compounding agent of the present invention is compounded in the form of a prepolymer,
It is used after being polymerized (cured) with a curing agent such as amine.

*Equal weight parts of refined oil and resin were stirred and mixed at 150°C for 10 minutes, cooled, and then observed under a 400x microscope.S: Completely dissolved;
■: Insoluble table The refined oil obtained from the results of ■ is soluble in resin under the extraction conditions of No. , extraction temperature 5
0.0°C) is desirable.

Various extraction conditions were investigated for cracked distillate oils other than the distillate oil shown in (1), but the results were almost the same, with the yield of refined oil varying depending on the conditions.

In addition, compatibility tests with thermoplastic acrylic resin, oil-modified urethane resin, and vinyl chloride resin were conducted.

The results are shown in the following table ■. The acrylic resin used here is generally obtained by polymerizing an acrylic monomer represented by the following formula.

In the above formula, R1-R4 are H, an alkyl group, an active group (-NH
2, COOH, -OH, etc.), and in this case, we investigated compounding agents for a typical styrene/acrylamide/ethyl acrylate copolymer system.

Urethane resin has a urethane bond (-0CONH-) consisting of an incyanate group (-NGO) and a hydroxyl group (-oir).
Typical examples include polyurethane resins formed from polyurethane resin, but in this case, TDI (ruene diisocyanate) is used in
A prepolymer of the following formula linked with a dihydric alcohol was used.

□Such a prepolymer is called a moisture-curing polyurethane resin because NCO reacts with moisture in the air to form urea bonds and becomes a polymer.

Also, prepolymers such as oil-modified polyurethane resins in which TDI is bonded with oil are cured by a different mechanism.

In this case, oil-modified polyurethane resin was used as the target resin.

Vinyl chloride resin is a typical plastic and is manufactured from acetylene and hydrochloric acid or ethylene.

In this case, we investigated its use as a plasticizer for soft PVC (polyvinyl chloride).

*In the case of acrylic and urethane resins, equal parts by weight of the refined oil in the present invention, and in the case of vinyl chloride resin, 20 parts by weight of the refined oil in the present invention for 80 parts by weight of the vinyl chloride resin. The mixture was stirred and mixed at 150°C for 10 minutes, cooled, and observed under a 400x microscope.

S: completely dissolved, PS: partially dissolved, ■: insoluble The results are exactly the same as in the case of the epoxy resin shown in the previous table ■, and the compatibility is the most important requirement for a polymer resin compound material explained below. It can be seen that the refined oil in the present invention is very useful as a compounding material for polymer resins.

(3) General properties of refined oil Table V shows the general properties of the refined oils obtained under the first to second extraction conditions shown in (2).

* Based on JIS-2540 turbine oil thermal stability test (170°C x 12 hours).

(4) Gel-chromatic analysis, elemental analysis, and aromaticity index of refined oil and raw materials Gel-chromatic analysis, elemental analysis, and aromaticity index fa of each refined oil shown in (3), and the average for comparison. Molecular weight 320
Similar analysis results for aromatic extracts are shown in Table 3.

In the present invention, the target resins are generally high viscosity liquids or solids, and therefore, when these resins are used, they are used to improve workability, improve moldability, or when used as adhesives. In order to sufficiently wet the surface of the adherend,
It is necessary to reduce the viscosity of the resin.

In the case of the bisphenol-epichlorohydrin type epoxy resin mentioned in (2), amines are added as a curing agent during use, which lowers its viscosity, but since the mixing ratio of this curing agent is fixed, It is not possible to freely adjust the viscosity of the resin.

Therefore, methods for reducing the viscosity of this type of epoxy resin include adding a solvent or increasing the temperature.

However, the solvent addition method has problems such as vaporization and foaming if the solvent is not completely expelled after use, resulting in a decrease in mechanical strength, and the temperature increase method shortens the usable time of the resin and makes on-site work easier. make it difficult

The method of using refined oil as a blending material according to the present invention is very useful since it compensates for the drawbacks of the above three methods.

(5) Compatibility with various resins The refined oil obtained under the extraction conditions No. 1 shown in (3) was distilled under reduced pressure and divided into five fractions.

The results of examining the general properties and compatibility with epoxy resins for each fraction are shown in Table 3.

From Table ■, it can be seen that since the raw material oil itself is originally an oil with a narrow molecular weight distribution, there is no big difference in the properties of each fraction obtained.
The compatibility with the epoxy resin is good (it can be seen that it can be used as a compounding material).

Similarly, compatibility tests with thermoplastic acrylic resins, oil-modified urethane resins, and vinyl chloride resins were conducted on the five fractions mentioned above.

The results are shown in the following table ■.

The compatibility test method and the meaning of the symbol S are the same as in Example 3.

The results show that each fraction has sufficient compatibility with each resin.

Plasticizers such as DEP (diethyl phthalate) and DOP (dioctyl phthalate), which are generally used in polymer resins such as acrylic resins, have a constant interaction constant μ with respect to the resin and a constant volume concentration, so they are compatible. However, in the case of the mineral oil-based compounding material used in the present invention, refined oil has a molecular weight distribution within a certain range, so even if temporary compatibility is shown as a whole, there is no problem with compatibility. When there is no compatibility across the molecular weight distribution, that is, some molecular weights and light fractions are often incompatible with the resin, which often results in the blooming phenomenon.

The above test results show that the refined oil in the present invention has sufficient compatibility with the resin over the entire molecular weight distribution, and also proves that phenomena such as blooming do not occur.

(6) Adjusting the viscosity of epoxy resin The refined oil obtained under the extraction conditions described in (3) and the epoxy resin with an epoxy equivalent of 190 were dissolved at different mixing ratios, and the viscosity change of each mixture was measured. The results are shown in Table 3 and Figure 1.

*Measurement temperature was 25.0°C. The linearity of the viscosity measurement of the mixture of refined oil and epoxy resin according to the present invention shown in Figure 1 shows the compatibility and sufficient plasticizing effect of the two.

(7) Adjusting the viscosity of thermoplastic acrylic resin in the same way as in (6). and shown in FIG.

*The measurement temperature was 25.0°C. As with the epoxy resin (6), it is clear that the two are compatible and have a sufficient plasticizing effect.

(8) Adjustment of viscosity of oil-modified urethane resin Similarly to (6) and (7), adjust the viscosity of oil-modified urethane resin using the refined oil obtained under the condition No. 1 described in (3). The results are shown in Table M and FIG.

*The measurement temperature was 25.0°C. Similar to (6) and (7), the compatibility and sufficient plasticizing effect of both can be seen.

The above results show that the refined oil according to the present invention is very useful as a compounding material for polymer resins.

(9) An epoxy resin having an epoxy equivalent of 190 was mixed with the refined oil according to the present invention [obtained under the extraction conditions shown in (2) under No. The results of measuring the tensile speed of a test piece prepared with an amine curing agent using the extract and the results of observing the appearance oozing (B looming) are shown (Tables ■ and X■).

For reference, similar test results are also shown for tar epoxy, which has been conventionally known as an epoxy resin compound (Table xiv).

*1 The amount of compounding material added is 100% of the epoxy resin, which is the main ingredient.
against the department.

*2 Tensile test is based on JIS K6911.

When the aromatic extract was used as a compounding agent, the test piece was opaque, cloudy, and oozed, indicating that they were not mutually dissolved.

Therefore, when 10 parts of the additive was added, the tensile strength was close to that of the case without the additive, and no plasticizing effect was exhibited.If the amount added was large, fractures occurred in the non-uniform parts, and the strength suddenly decreased. Ta.

However, when the refined oil according to the present invention is used as a compounding material, it has good compatibility with the epoxy resin, so the test piece is transparent and homogeneous, and a small amount of addition has a sufficient plasticizing effect. It was found that the tensile strength did not decrease as the amount increased, and the results were good.

This tendency is the same for conventionally used tar epoxy, and the compounded material in the present invention is good as a compounded material for polymer resins, and it is also effective against carcinogenic substances such as coal tar (for example, 3,4-pentupyrene). ), it can be seen that it is very useful as a substitute.

As described above, the present invention selectively converts cracked distillate oil, which has conventionally been evaluated only as an inexpensive C heavy oil blending material, into a highly aromatic fuel oil using furfural, phenol, or similar solvents. oil or highly polar,
Furthermore, by extracting and purifying chemically stable oxygen-containing compounds, we have provided a compounding material for polymer resins that is inexpensive and has good compatibility.

[Brief explanation of drawings]

FIG. 1 is a graph showing the relationship between the mixing ratio of the compounding material according to the present invention and its viscosity for an epoxy resin, FIG. 2 for an acrylic resin, and FIG. 3 for a urethane resin.

Claims (1)

[Claims] 1. Petroleum-based heavy residue or average molecular weight 150-8500
Aromatic fractions extracted from petroleum fractions with furfural, phenol, or similar solvents are
Obtained by extracting cracked distillate, which is distilled out during thermal decomposition polycondensation reaction or oxidation treatment with an oxidizing agent such as oxygen or air, at a temperature of 500°C using furfural, phenol, or a similar solvent. Compound material for polymer resin. 2. The compounding agent for a polymer resin according to claim 1, wherein the polymer resin is an epoxy resin. 3. The compounding agent for a polymer resin according to claim 1, wherein the polymer resin is a urethane resin. 4. The compounding agent for a polymer resin according to claim 1, wherein the polymer resin is an acrylic resin. 5. The compounding agent for a polymer resin according to claim 1, wherein the polymer resin is a vinyl chloride resin.