JPH01301703A - Novel chlorinated polyolefin containing hydroxyl group, production thereof and composition containing said polymer - Google Patents

Abstract

PURPOSE:To obtain a polyolefin capable of providing a cured material with rubbery elasticity excellent in heat and weather resistance and electrical characteristics by crosslinking and curing the polyolefin using various curing agents, by chlorinating and then reducing an oxidized type polyolefin. CONSTITUTION:An oxidized type polyolefin obtained, e.g. by thermal degradation of a polyolefin (preferably 10-10,000cP melting viscosity at 190 deg.C) using oxygen or ozone is chlorinated and then reduced to prepare a chlorinated polyolefin containing hydroxyl groups. The chlorination is carried out, preferably by dissolving the oxidized polyolefin in a chlorine-based solvent and blowing chlorine gas into the solution in the presence of a catalyst or under ultraviolet ray irradiation under the ordinary or a higher pressure at 0-130 deg.C. The resultant polyolefin is useful as a coating film composition for a paint, ink, binder, adhesive, etc.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a novel hydroxyl group-containing chlorinated polyolefin, and its production method and composition. A hydroxyl group-containing chlorinated polyolefin that can provide a cured product having rubber-like elasticity and excellent solvent resistance, heat resistance, weather resistance, and electrical properties, a method for producing the same, and a process using the same. The present invention relates to a composition.

(Prior Art and Problems to be Solved by the Invention) Polyolefins are non-polar and crystalline, so ordinary coating compositions do not adhere to them, making it difficult to paint, print, or adhere to polyolefins. The most commonly used methods include using a chlorinated polyolefin as the main component of the coating composition, and oxidizing the surface of the polyolefin in order to improve compatibility and surface wettability with the coating composition. However, is there a method of painting, printing, or adhering? These methods are difficult to apply depending on the type of coating composition and the surface condition of the boron olefin, and the adhesion is not completely satisfactory. In an attempt to obtain a coating composition with good adhesion to the surface of the
Proposed compositions include petroleum-based resins and cyclized rubber as shown in Japanese Patent Publication No. 49-5214, modified alkyd resins, acrylic resins, ethylene-vinyl acetate copolymer resins, etc., and chlorinated polyolefin resins. It was done. However, although these have good adhesion to polyolefins, the surface hardness of the coating is not sufficient, and they also have no oil or solvent resistance, so they have major practical limitations and are used in some cases as primer coatings for polyolefins. It's just being told.

In addition, in order to produce a coating composition that has adhesion to polyolefin and also has good coating film hardness, oil resistance, and solvent resistance, for example, as shown in JP-A No. 56-50971, Attempts have been made to impart oil resistance and solvent resistance to resin compositions mainly composed of chlorinated polyolefins and cyclized rubbers by blending crosslinking components into them, but generally polyisocyanate compounds, melamine resins or epoxy resins are used. Known compounds that act as crosslinking agents for resins have poor compatibility with chlorinated polyolefins and cyclized rubbers, and urethane bonds, amide bonds, etc. are not suitable because they significantly inhibit adhesion to the polyolefin surface.
In addition, oxidative polymerization type resin components such as oil-modified alkyd resins and boiled polybutadiene are compatible with chlorinated polyolefins and cyclized rubbers, but the temperature range that is commonly used for coating and adhesion without causing deformation of the polyolefins Therefore, a sufficient crosslinking effect cannot be expected.

Furthermore, polymers containing bitroxyl groups in the molecule, such as polybitroxypolyolefin produced by anionic polymerization as seen in JP-A-49-114692,
When it is chlorinated, the hydroxyl group cannot exist in a stable form, and even if this chlorinated product is used to form a paint, as shown in the comparative example of the present invention, it does not show sufficient curing behavior.

(Means for Solving the Problems) The present invention has been made to solve these problems, and it provides a hydroxyl group-containing chlorinated polyolefin, which is obtained by chlorinating an oxidized polyolefin and then reducing it. It is necessary to provide a method for producing the same and a coating composition using the same to meet the intended purpose.

= 5- The present invention will be described in detail below.

That is, the present invention relates to a novel chlorinated polyolefin having at least one hydroxyl group at both ends of the molecule, and its production and composition.
Polyolefin resins with a melt viscosity of 10 to 10,000 cps, such as crystalline polypropylene, amorphous polypropylene, polybutene-1,4-methylpentene-1° low density or high density polyethylene, ethylene-propylene, etc. A single polymer or a mixture of two or more of them is melted under heat or dissolved in an aliphatic hydrocarbon solvent, and thermal degradation is performed while introducing oxygen or ozone to introduce a carbonyl group into the molecule. For example, di-tert-butyl peroxide, 1er
t-Butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, methyl ethyl hemperoxide, 2゜5-dimethyl-2,5-di-tert-butylperoxyhexine- It is possible to increase the degradation rate by using peroxides such as No. 3 and azonitriles such as azobisisobutyroni-1-lyl and azobisisopropioni-1-helyl. If the polyolefin used in the present invention has a temperature of 190° C. (melt viscosity 10 C1) or less and is used as a paint, ink, binder or adhesive, the cohesive force of the film will be weak and the required performance will not be obtained. Also heated to 190°C (melt viscosity 10,000 cp)
If it is more than s, the viscosity will be high in these applications and the workability will be poor.

The oxidized polyolefin thermally degraded using oxygen or ozone as described above is dissolved in a chlorine-based solvent and heated to 130°C under pressure or normal pressure in the presence of a catalyst or under ultraviolet irradiation.
Chlorine is carried out by blowing chlorine residue at C(7) temperature.

Chlorinated polyolefins containing carbonyl groups can be dissolved in an aromatic solvent such as heluene or xylene, or an aliphatic solvent such as methyl ethyl ketone or tetrahydrofuran, and converted into a hydroxyl group using a reducing agent such as a metal hydride; . Commonly used reducing agents include, for example, lithium aluminum hydride, sodium aluminum hydride, sodium borohydride, diisobutylaluminum hydride, borohydride cum, and small orchid derivatives.

The novel hydroxyl group-containing chlorinated polyolefin of the present invention provides a resin composition with good color development, adhesiveness, and storage stability, and can be crosslinked and cured using isocyanate and other various curing agents to form two inks for coatings. It is possible to provide coating film compositions useful as applications, binders, adhesives, and the like.

(Examples) Next, the present invention will be specifically explained by examples, but the present invention is not limited thereto.

Example 1 190'C (melt viscosity approximately 2000 Ct)
Approximately 508 g of isotactic polypropylene is placed in a three-way flask equipped with a stirrer, an oxygen inlet, and a condenser, and completely dissolved in approximately 11 carbon tetrachloride at 80°C. 0.57 oxide was added and a degradation reaction was carried out for 5 hours while passing oxygen at 200 cc/min.The resulting carbon tetrachloride reaction solution was poured into hot water to obtain a solid oxidized polypropylene. .

Furthermore, this product 307 was charged into a chlorination reactor, and 1
After 10 carbon tetrachloride was added and dissolved at 80°C, gaseous chlorine was blown into the reactor from the bottom while irradiating it with ultraviolet rays until the degree of chlorination reached 15W1%.

After the reaction was completed, the solvent carbon tetrachloride was distilled off using an evaporator and replaced with tetrahydrofuran (hereinafter referred to as THF) to obtain a 20 wt % THF solution. This product (20w
Pour 100y of F solution >100y into a Mitsuro flask equipped with a stirrer, reducing agent inlet, and cooling tube, and lower HF8.
00!7 was added and the temperature was kept constant at 60°C, 0.19% of lithium aluminum hydride was added over a period of 10 minutes, and a distant reaction was carried out for about 1 hour. After the reaction, the resulting acid product was poured into a large amount of methanol, and the white precipitate was filtered.

−〇　− After drying, the filtrate was prepared into a 20% toluene solution.

Example 2 Example 1 was followed except that the degree of chlorination was 30 wt%.

Example 3 Except that the degree of chlorination was 55 wt% (J, according to Example month).

Comparative Example 1 Commercially available oxidized polypropylene with a number average molecular weight of 1000 to 2000 (manufactured by Sanyo Chemical Industries, trade name rTS-200J)
) 509 was put into a chlorination reactor, carbon tetrachloride of 11 was added and dissolved at 80 °C, and then gaseous chlorine was blown from the bottom of the reactor while irradiating it with ultraviolet rays until the degree of chlorination reached 15 wt%. . After the reaction was completed, the solvent carbon tetrachloride was distilled off using an evaporator and replaced with toluene.
% solution.

Comparative example 2 Comparative Example 1 was followed except that the degree of chlorination was 30 wt%.

Comparative Example 3 A polyhydroxypolyolefin with a number average molecular weight of 12,500 was synthesized by the method described in JP-A-49-114692,
The 507 was put into a chlorination reactor, carbon tetrachloride of 11 was added and dissolved at 80'C, and then chlorine in the form of scum was blown into the bottom of the reactor while irradiating it with ultraviolet rays until the degree of chlorination reached 15 wt%. is.

After the reaction was completed, carbon tetrachloride, which was a solvent, was replaced with toluene in a distillate using an evaporator to prepare a 20 wt % solution.

Example 4 2 owt of each of the hydroxyl group-containing chlorinated polyolefin copolymers or oxidized chlorinated polypropylene copolymers obtained in Examples 1 and 2.3 and Comparative Examples 1 and 2.3
% toluene solution 2007, titanium oxide 47, carbon black 0.19, and Epicoat 828 (manufactured by Shell Chemical ■) 1.67 were mixed, kneaded for 1 hour in a Xantmill, diluted with toluene to an appropriate viscosity, and mixed with toluene. A film thickness of 5 to 1
It was spray painted so that it had a thickness of 0μ.

After 5 minutes, a two-component curing type urethane paint (manufactured by NOF ■) was spray-painted to a film thickness of 30 to 40 μm, air-dried at a very hot stone for 15 minutes, then force-dried at 80°C for 30 minutes, and then dried for 24 minutes. After standing at room temperature for an hour, the physical properties of the coating film were tested. The results are shown in Table-1.

-12 One test method Adhesion: Place 100 goblets on the painted surface at 1# intervals and reach the substrate, and then stick cellophane adhesive tape on top of them.
It was peeled off in an 80° direction and judged based on the extent to which the coating film remained.

Accelerated weather resistance: A carbon arc sunshine weather meter was used. Glossiness was measured using 60° specular reflection, and whiteness was measured using a Hunter.

Hot water resistance: The coated board was immersed in hot water at 40°C for 120 hours and 240 hours, and the state of the coating film was examined.

Gasoline resistance: The coated surface soaked with natural gasoline on absorbent cotton was rubbed 50 times to examine the condition of the coated film.

Methanol resistance: Absorbent cotton was impregnated with methanol and the coated surface was rubbed 100 times to examine the condition of the coated film.

Evaluation criteria in the table ◎ Good ■ Very good △ Ya Poor 20w of each copolymer or oxidized chlorinated polypropylene copolymer
After dispersing 100 U of t% toluene solution and titanium dioxide 289 in a sand mill for 3 hours, isocyanate 1 to curing agent Coronate El-1 (manufactured by Nippon Polyurethane Industries Co., Ltd.) 7.99 and 10% zinc octylate solution as an accelerator were added. Add 2.79 of
The viscosity was adjusted with toluene so that it lasted for ~15 seconds, and spray painting was performed on a polypropylene plate EP-A2 (manufactured by Mitsui Toatsu Chemical Co., Ltd.). After leaving it in a warm and humid environment for about 15 minutes,
After being force-dried for 30 minutes at C, and left standing on campus for one week, the coating film was tested and the results are shown in Table 2. The test method and human evaluation criteria were the same as in Table-1.

(Effects of the Invention) The hydroxyl group-containing chlorinated polyolefin of the present invention is novel, and can be used for coatings by crosslinking and curing it using various curing agents.

The company is of great industrial value because it provides coating compositions useful for inks, binders, and adhesives.

Claims (6)

[Claims] (1) A hydroxyl group-containing chlorinated polyolefin, which is obtained by chlorinating and then reducing an oxidized polyolefin. (2) The hydroxyl group-containing chlorinated polyolefin according to claim 1, wherein the oxidized polyolefin is obtained by thermally degrading a polyolefin using oxygen or ozone. (3) Polyolefin has a melt viscosity of 1 at 190°C.
The hydroxyl group-containing chlorinated polyolefin according to claim 2, which has a hydroxyl group-containing chlorinated polyolefin of 0 to 10,000 cps. (4) Hydroxyl group-containing characterized by oxidizing a polyolefin to obtain a carbonyl-containing polyolefin, then chlorinating the carbonyl-containing polyolefin, and then reducing some or all of the carbonyl groups to hydroxyl groups using a reducing agent. Method for producing chlorinated polyolefin. (5) Coating compositions for paints, inks, binders, adhesives, etc. whose main ingredient is a hydroxyl group-containing chlorinated polyolefin obtained by chlorinating and then reducing an oxidized polyolefin. (6) Coatings for paints, inks, binders, adhesives, etc. obtained by crosslinking and curing hydroxyl group-containing chlorinated polyolefins obtained by chlorinating and then reducing oxidized polyolefins. Membrane composition.