JPS5817777B2 - Method for producing modified fatty acid pitch composition - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for producing a modified fatty acid pitch composition.

More specifically, the present invention relates to a method for producing a modified fatty acid pitch composition that does not contain harmful substances, has excellent compatibility with epoxy resins, and provides good water resistance, corrosion resistance, and oil resistance when used as a paint.

Coal tar epoxy paint is already known as one type of anti-corrosion paint.

However, since the paint has excellent physical properties such as water resistance, chemical resistance, and oil resistance, it can be applied to ship tanks, steel pipes, etc.
It is also widely used for various other corrosion prevention works.

That is, the paint is made of raw tar, collectively called coal tar,
It has the characteristic that the water resistance and chemical resistance of purified tar, tar pitch, swollen charcoal, etc., and the adhesion, hardness, and chemical resistance of epoxy resin are exhibited in harmony.

By the way, the coal tar contained in the paint has excellent physical properties.
Although it is a low-cost material with chemical properties, it contains more than 10,000 pP of 3,-4 benzupyrene, which is widely regarded as a carcinogen. Rules for handling specified chemical substances under the Safety and Health Act must be followed.

The present invention relates to a method for producing a modified fatty acid pitch composition that does not contain harmful substances, has excellent properties equivalent to those of coal tar, and can be produced at low cost.

That is, the present invention relates to a method for producing a modified fatty acid pitch composition, which comprises adding an epoxy group-containing compound to pitch-shaped natural oil fatty acid distillation residue (hereinafter referred to as fatty acid pitch).

The modified fatty acid pitch composition obtained by the method of the present invention does not contain any harmful substances as described above, has no acid value or has a low acid value due to the addition of an epoxy group-containing compound, has a high molecular weight, and has a high molecular weight and is compatible with epoxy resins. It has properties such as good compatibility, and when used in paints, provides excellent coating film performance.

The "fatty acid pitch" used in the present invention is a residue obtained by distilling crude tall oil.

For example, after dehydrating crude tall oil, it is passed through a heat exchanger to raise its temperature and led to a feed flasher, where the crude tall oil is vaporized by heat and reduced pressure and sent to a distillation column.
The vapor content is led to the fractionation column, and the heavy non-volatile substances remain in the distillation column and are taken out from the bottom of the distillation column.

This residue (fatty acid pitch) has hitherto only been discarded or has utility as a fuel substitute.

Therefore, there was a desire to develop new uses.

The above-mentioned [epoxy group-containing compound] used in the present invention.

As such, aliphatic, cycloaliphatic, and aromatic epoxy group-containing compounds can be used.

The epoxy group-containing compound has 2 to 3 epoxy groups in one molecule and has a molecular weight of about 1,500 or less.

In the above, if the compound has 2 to 3 epoxy groups in one molecule, an appropriate amount of epoxy groups can be introduced into the modified fatty acid pitch, thereby forming a flexible crosslinked and curable composition. I can do it.

On the other hand, if a compound having four or more epoxy groups in the molecule is used to modify fatty acid pitch, gelation may occur during the modification, and the crosslinked curable composition formed from the resulting modified fatty acid pitch may This is undesirable because it tends to cause problems such as poor flexibility.

Furthermore, if the molecular weight is greater than 1500, the viscosity of the modified fatty acid pitch increases and the solubility in solvents decreases, making it unsuitable for applications such as paints.

Particularly preferred are those having a molecular weight of about 200 to 950.

Examples of such epoxy group-containing compounds include C, phthyl glycidyl ether, phenyl glycidyl ether,
Allyl glycidyl ether, glycidyl methacrylate, glycerol diglycidyl ether, cresyl glycidyl ether, polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether,
Glycidyl ethers such as polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, butanediol diglycidyl ether, bisphenol A type, bisphenol A side chain type, epoxy novolak type, bisphenol A dimethyl glycidyl ether type, Epoxy resins such as ester ether type, resorcin glycidyl ether type, polyethylene glycol diglycidyl ether type, aliphatic diglycidyl ether type, and glycerin diglycidyl ether type can be used.

The reaction between the fatty acid pitch and the epoxy group-containing compound is a reaction between the acid groups, hydroxyl groups, etc. contained in the fatty acid pitch and the epoxy group of the compound, and is carried out at a temperature of 40 to 300°C, preferably 100 to 200°C.

In this case, an inorganic base, which is usually used as a catalyst for ring opening of an epoxy group, an organic base such as a tertiary amine, an organic acid,
An acid anhydride or the like may be used in combination.

The structure of the fatty acid pitch used in the present invention is very complex, and it is substantially difficult to determine its molecular formula.

Generally, many have an acid value of about 5 to 150.

The amount of the epoxy group-containing compound used is preferably about 5 to 120 parts by weight based on ioo parts by weight of fatty acid pitch.

Within the above range, if the amount of the epoxy group-containing compound used is less than 5 parts by weight, a sufficient modification effect cannot be obtained.

Furthermore, even if the amount exceeds 120 parts by weight, no further increase in the effect of modification is observed, and on the contrary, the characteristics of the fatty acid pitch itself, such as water resistance, chemical resistance, flexibility, and low cost, cannot be fully expressed. .

When using a fatty acid pitch with a particularly high acid value within the above range, it is recommended to set the amount of the epoxy group-containing compound such that the acid value of the modified fatty acid pitch is 90 or less in order to improve water resistance, corrosion resistance, etc. More preferable than point.

When using a compound containing two or more epoxy groups in the molecule as the epoxy group-containing compound, predetermined amounts of the epoxy group-containing compound and fatty acid pitch are mixed homogeneously in their respective amounts before the reaction, or Alternatively, it is preferable to cause both components to react by a method such as proceeding with the reaction while gradually adding fatty acid pitch to the total amount of the epoxy group-containing compound.

For example, first, the fatty acid pitch and the epoxy group-containing compound are stirred and mixed to form a homogeneous mixture at a temperature higher than the melting temperature of the fatty acid pitch and lower than the temperature at which the addition reaction occurs, and then the mixture is mixed at the temperature at which the reaction occurs. An effective method is to heat the

On the other hand, if the reaction proceeds while gradually adding an epoxy group-containing compound to the total amount of fatty acid pitch, a crosslinking reaction will occur in the early stage of the reaction. It becomes impossible to obtain a hardened modified fatty acid pitch.

The modified fatty acid pitch obtained as a result of carrying out the present invention has various properties ranging from black or dark brown, heat-melting, highly viscous and grease-like at room temperature to softening at about 60°C.

They are also soluble in common aromatic yet aliphatic solvents.

Furthermore, it is compatible with epoxy resins and has excellent water resistance, corrosion resistance, and oil resistance not found in unmodified or ester-modified products.

The modified fatty acid pitch of the present invention can be combined with an epoxy resin (with a solvent added if necessary) to produce a corrosion-resistant paint.

The paint is pollution-free, resource-saving, and has excellent coating properties such as adhesion, water resistance, oil resistance, and corrosion resistance.

The epoxy resin used in combination with the above-mentioned modified fatty acid pitch is one commonly used in paints, and may be a liquid epoxy resin, a solid epoxy resin, or a mixture thereof.

Specifically, epoxy resins exemplified as glycidyl compounds and epoxy group-containing compounds can be used.

Further, as a curing agent for the epoxy resin, commonly used resin family amine modified products, aromatic amine modified products, xylene diamine modified products, inphorone diamine modified products, etc. are used.

The anti-corrosion paint is generally dry at room temperature, and for example, modified fatty acid pitch is added to an epoxy resin in an amount of about 5 to 50*, stirred and mixed uniformly to produce a base agent, and when used, a curing agent of 0.5 It is blended in a proportion of ~1.5 equivalents.

Addition amount of modified fatty acid pitch to epoxy resin is 50
If the amount increases, sufficient crosslinking density will not be obtained and a practical corrosion-resistant coating film will not be formed.

On the other hand, if the amount added is less than 5, the effect of the combined use of modified fatty acid pitch will be lost, and the water resistance, chemical resistance and flexibility of the coating will decrease.

Furthermore, appropriate amounts of inorganic or organic coloring pigments, extender pigments, and other additives commonly used in paints may be added.

In addition, the modified fatty acid pitch obtained by the method of the present invention can be used alone or in combination with resins other than the above-mentioned epoxy resins as a color vehicle for paints, and has many other uses such as extenders for civil engineering adhesives and extenders for floors. It can be used.

When using the above-mentioned modified fatty acid pitch alone or in combination with other resins, it is preferable that the mixed resin composition has an acid value of 30 or less, particularly in terms of improving water resistance.

The present invention will be explained below with reference to Examples.

In addition, all parts and units in the examples are indicated by weight.

Example 1 100 parts of tall oil fatty acid pitch with an acid value of 70 and epoxy - a bisphenol A/epichlorohydrin type resin having two epoxy groups in the molecule (trade name Epicote 41)
-828, manufactured by Shell Chemical Co., Ltd., molecular weight 380, solid content 10
Place 22.8 parts of the mixture into a three-bottle flask equipped with a stirrer, thermometer, and condenser, heat and react at 200°C for 4 hours, then cool it to 100'C and add 31 parts of xylene to make a homogeneous solution. Composition A was obtained.

The acid value of this modified fatty acid pitch is 7, and the reduction rate of epoxy groups in the system (measured by infrared absorption analysis to measure the content of epoxy groups in the reaction system and production system, expressed as a reduction factor of 1, the same applies hereinafter) was in charge of 90.

Example 2 100 parts of tall oil fatty acid pitch with an acid value of 30 and 5.4 parts of glycerol diglycidyl ether (molecular weight 204) were placed in the same reaction vessel as in Example 1, and reacted at 150°C for 6 hours. Cool to 100℃ and add xylene 26
1 part was added to make a homogeneous solution, and Composition B was obtained.

The acid value of this modified fatty acid pitch was 2, and the amount of decrease in epoxy groups was 95.

Example 3 100 parts of tall oil fatty acid pitch with an acid value of 140 and epoxy - bisphenol A having two epoxy groups in the molecule
/Epichlorohydrin type resin (trade name Epicor t410
01 manufactured by Shell Chemical Co., Ltd., molecular weight approximately 900, solid content 100 parts) and 52 parts of xylene were placed in the same reaction vessel as in Example 1 and reacted at 180° C. for 2 hours to obtain Composition C.

The acid value of this modified fatty acid pitch was 30, and the reduction rate of epoxy groups was 80%.

Example 4 100 parts of tall oil fatty acid pitch with an acid value of 90 was mixed into a novolak type epoxy resin (with two epoxy groups in one molecule).
Product name: DOW D, E, N431 Manufactured by Dow Chemical Company,
20 parts (molecular weight: 370, solid content: 100%) were placed in the same reaction vessel as in Example 1, and reacted at 1300C for 3 hours.

Next, this was cooled to 100° C., and 30 parts of xylene was added to form a uniform solution to obtain a composition.

This modified fatty acid pitch had an acid value of 10 and a reduction rate of epoxy groups of 90.

Example 5 100 parts of tall oil fatty acid pitch with an acid value of 140 and 46 parts of an epoxy resin (trade name Epicote +823, manufactured by Shell Chemical Co., Ltd., molecular weight 380, solid content 100%) were charged into the same reaction vessel as in Example 1 and heated at 200°C. The reaction was allowed to proceed for 2 hours.

Next, this was cooled to 100° C., and 36.5 parts of xylene was added to form a uniform solution to obtain Composition E.

This modified fatty acid pitch had an acid value of 14 and a reduction in epoxy groups of 90%.

Example 6 Corrosion-resistant paints were prepared using the compositions A to E obtained in Examples 1 to 5, and property tests were conducted.

The results are shown in Table 1.

For comparison, the properties of paints containing commercially available non-tar extenders, unmodified tall oil fatty acid pitch, esterified tall oil pitch, and coal tar pitch were also tested at the same time in place of Examples 1 to 5.

Adjustment of each paint is based on the following formulation. 30 parts of epoxy resin (Epicor 4828), 30 parts of talc, and 159 parts of xylene were kneaded in a ball mill for 14 hours and uniformly kneaded and dispersed to prepare a main ingredient.

Paint A- was obtained by uniformly mixing the above-mentioned main ingredient, curing agent, and extender resin in the following formulations (parts by weight) immediately before use.

The above paint was applied to a sandblasting board to a thickness of 250 μm, dried at room temperature for 7 days, and subjected to property tests.

As shown in Table 1, the paints using the modified fatty acid pitch of the present invention have significantly superior properties compared to those using unmodified or esterified tall oil fatty acid pitch.

It can also be seen that it has better corrosion resistance and oil resistance than those using commercially available non-tar-based extender resins, and has performance equivalent to or better than those using coal tar pitch.

Example 7 Characteristic tests were carried out on the above composition A, a commercially available non-tar type extender resin using coumaron indene resin, and its content in the paint was varied, and a general tar epoxy paint (JIS Class 1 product). I did it.

The results are shown in Table 2.

Each paint was prepared by mixing each component in the following formulation (parts by weight) immediately before use and stirring uniformly.

As shown in Table 2, the products using the modified fatty acid pitch obtained as a result of implementing the present invention do not have a decrease in corrosion resistance even when the amount added to the paint is increased, and compared to commercially available non-tar-based extender resins, It was much better and had performance comparable to tar epoxy paint.

Claims (1)

[Claims] 1. A method characterized by adding an epoxy group-containing compound having 2 to 3 epoxy groups in one molecule and having a molecular weight of about 1500 or less to the fatty acid distillation residue of tall oil. A method for producing a modified fatty acid pitch composition. 2. The method for producing a modified fatty acid pitch composition according to claim 1, wherein the weight ratio of the fatty acid rectification residue to the epoxy group-containing compound is 10,015 to 120.