JPS61215667A - Production of chlorinated polyolefin containing carboxyl group - Google Patents

Abstract

PURPOSE:To obtain the titled chlorinated material having improved coatability, by chlorinating a carboxyl group-contg. polyolefin and polymerizing the residual unsaturated carboxylic acid and (meth)acrylic acid monomer. CONSTITUTION:A polyolefin having a melt viscosity of 30-3,000cPs at 200 deg.C is reacted with an unsaturated polycarboxylic acid or its anhydride to synthesize a carboxyl group-contg. polyolefin, which is then chlorinated. The residual carboxyl groups or anhydride groups thereof and (meth)acrylic acid monomer are polymerized to obtain the titled chlorinated polyolefin. When a polyolefin having a melt viscosity of below 30cPs is used as a binder, the cohesive force of the resulting coating film is low and hence, the required effect is not obtd., while when a polyolefin having a melt viscosity exceeding 3,000cPs is used as a binder, viscosity is too high and it is of no practical use in respect of workability.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing a carboxyl group-containing polyolefin chloride, specifically, a method for producing a carboxyl group-containing polycarboxylic acid or its acid anhydride (methacrylic acid monomer). This is a method for improving physical properties such as paint suitability of the chlorinated carboxyl group-containing polyolefin by polymerizing it with mfJ5.

[Conventional technology]

Poly-10-pyrene resin has excellent properties such as chemical resistance, ozone resistance, heat resistance, water resistance, and good electrical properties, and because it is lightweight and inexpensive, it is used in home appliances, automobile parts, etc. It is beginning to be widely used as an industrial material, and is one of the materials whose demand is most expected to grow in the future. However, despite having these characteristics, when it comes to automobile parts such as holes, various plastics are being used to reduce weight from the perspective of energy conservation, and the amount of plastic used is increasing year by year. The use of resins is limited to some parts. One of the reasons hindering its widespread use is that the 11-propylene resin is non-polar and crystalline, making it extremely difficult to paint or adhere. For these reasons, there is a strong desire to develop a coating composition that has good adhesion to polypropylene resins. Traditionally, when printing or adhering polypropylene resin, treatments such as corona discharge have been used to improve adhesion, but these methods cannot be applied uniformly to molded products with complex surfaces. There is a drawback that there is no

Therefore, as a method of painting without these pre-treatments,
(1) Various primer compositions that have good adhesion to propylene have been proposed. For example, Tokuko Sho 49-18089,
Examples include a primer composition comprising a cyclized rubber, an aromatic petroleum resin, an oil-soluble phenol resin, a coumaron indene resin and a chlorinated polyolefin, as disclosed in Japanese Patent Publication No. 49-5214. However, even though these have good adhesion to polypropylene, they have insufficient adhesion to the top coat, and even though they show good adhesion to both polypropylene and the top coat, It has the disadvantage of poor solvent resistance. Particularly in recent years, paints that are used outdoors, such as automobiles and motorcycles, have come to be required to have stronger adhesion, weather resistance, and gasoline resistance. Regarding these, please refer to JP-A-56-76
433, which is a combination of a chlorinated Bot-1 olefin, a basic nitrogen-containing acrylic copolymer, and an epoxy resin; A coating composition has been proposed in which an epoxy resin is blended with a nitrogen-containing acrylic monomer and other acrylic monomers copolymerized with gold, but in order to obtain satisfactory coating performance, , it is necessary to reduce the chlorinated polyolefin content in the coating resin, resulting in problems with adhesion to special polypropylene resins.

[Problem that the invention seeks to solve]

In order to solve the above-mentioned problems, the present inventors have developed a method for improving the saponification value of polyolefins modified with one or more compounds selected from the group consisting of unsaturated carboxylates or their acid anhydrides. is 6 to 60, which is t-10 to
A paint or coating composition containing a chlorinated Bo II olefin gold binder chlorinated in the range of 50 wt% was proposed in JP-A-59-75958, Japanese Patent Application No. 58-230614, and Japanese Patent Application No. 58-230615, and the results were met with great satisfaction. I was able to write all the compositions with the physical properties that are as good as they are. However, after modifying the polyolefin with one or more compounds selected from the group consisting of unsaturated polycarboxylic acids or their acid anhydrides, unreacted unsaturated polycarboxylic acids or their acid anhydrides become carboxyl. If it remains in the group-containing polyolefin, it will remain as it is until after the chlorination reaction and will be mixed into the final carboxyl group-containing Form II olefin salt complex.

Unreacted unsaturated carboxylic acid or its acid anhydride has low solubility in aromatic solvents such as toluene and xylene that are normally used in paints, coatings, or inks, resulting in a decrease in the transparency of the solution. . Furthermore, the paint, coating agent, or ink is affected by unreacted unsaturated polycarboxylic acid or its acid anhydride.
Physical properties such as moisture resistance and gun resistance (1) are drastically reduced.

Japanese Patent Publication No. 50-10916 describes methods for separating unreacted unsaturated polycarboxylic acids from the reaction mixture, such as purging with an inert gas while maintaining the temperature of the melt between 200 and 300°C, and steam strike I+. Methods have been described for further purifying modified polyolefins by methods such as tupping, solvent extraction, or dissolution in an aqueous medium and release by removal of solvent or water, but purging alone with an inert gas does not It is impossible to completely remove unreacted unsaturated boron II carboxylic acid, and all of the above-mentioned purification methods require complicated operations and are not practical.

[Means for solving problems]

Therefore, the present inventors investigated the problem of reducing the transparency of toluene solutions of carboxyl group-containing polyolefins due to unreacted unsaturated polycarphonic acids or their acid anhydrides, and of reducing the moisture resistance and resistance of paints, coatings, or inks using carboxyl group-containing polyolefins. As a result of intensive studies aimed at improving the deterioration of physical properties such as gasoline properties, the present invention has been completed.

That is, the melt viscosity at 200°C is 30-3+OOO
CPS polyolefin is reacted with unsaturated phospho-11 carboxylic acid or its acid anhydride to synthesize carboxyl group-containing polyolefin, followed by conventional method 5, for example, purging with inert gas in molten state, or suction under reduced pressure. In this method, residual unreacted unsaturated carboxylic acid or its acid anhydride is removed to some extent. Then, after fully chlorinating the produced t-carboxyl group-containing polyolefin,
By polymerizing the unsaturated polycarboxylic acid or its acid anhydride that has not been completely removed with a (meth)acrylic acid monomer in the presence of a catalyst, it can be added to aromatic solvents such as toluene and xylene. Paints caused by residual sulfur in the 7-mer state by imparting solubility and completely capturing unsaturated polycarboxylic acids or their acid anhydrides which are free in the monomer state;
It has been found that deterioration of physical properties such as moisture resistance 5 gas resistance 11 of coating agents or inks can be improved, and 7'
C0 Unsaturated bo-11 carboxylic acid or the like according to the present invention.

A chlorinated polyolefin modified with one aid or two or more compounds selected from the group consisting of acid anhydrides can be produced by a known method.

An example of its production method and [7] include crystalline bo-11 propylene, amorphous bo-11 propylene, bo-11 butene-1, polypentene-1,4-methylpentene-1, polypentene-1,4-methylpentene-1, ＠ degree or a
- A molten polyolefin resin is modified with an unsaturated polycarboxylic acid or its acid anhydride in the presence of a radical generator in a batch or continuous manner, and then dissolved in an aqueous medium or a chlorinated solvent. , in the presence of a catalyst or under irradiation with ultraviolet rays, by blowing chlorine gas into the reaction at a temperature of 50 to 120° C. under increased pressure or normal pressure.

Examples of radical generators used in the modification reaction include peroxides such as di-tert-butyl peroxide, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxide benzoate, and methyl ethyl ketone peroxide. There are azonitriles such as azobisisobutyronitrile and azobisisoprobionitrile.

Examples of unsaturated polycarboxylic acids and acid anhydrides include maleic acid, maleic anhydride, citraconic acid, citraconic anhydride, fumaric acid, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, and aconitic anhydride. be.

When the Bo II olefin H according to the present invention has a melt viscosity of 30e p 8 or less at 1200° C. and is used as a binder for paints, coatings, or inks, the cohesive force of the film is weak and the required performance cannot be obtained. Also, 200℃
If the melt viscosity in
When used in other applications, it becomes highly viscous and impractical in terms of workability.

After the chlorination reaction of the carboxyl group-containing olefin, the reaction product is dissolved in an aromatic solvent such as toluene or xylene, and a solution polymerization reaction is carried out with the unsaturated polycarboxylic acid or its acid anhydride remaining in the reaction product. Examples of commonly used (meth)acrylic acid monomers include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl acrylate.
methacrylic acid, methacrylic acid, ethyl methacrylate, butyl methacrylate, methacrylic acid 2
A (meth)acrylic acid monomer such as ethylhexyl can be used. As this solution polymerization reaction initiator,
It can be selected from the group of radical generators used in FCF reactions as described above.

〔Example〕

EXAMPLES Next, the present invention will be specifically explained using Examples, but the present invention is not limited thereto.

In order to further clarify the effects of the present invention, all comparative examples are also listed.

Comparative Example-1 Isotactic polypropylene 500fTh with a melt viscosity of approximately 2.000 CF8 at 200°C was placed in a three-neck flask equipped with a stirrer, a dropping funnel, and a cooling tube for refluxing the monomer, and kept at a constant temperature of 200°C. completely melted in an oil bath kept at . After purging the flask with nitrogen for 10 minutes, add 20f of maleic anhydride while stirring. The mixture was added over a period of about 5 minutes, and then 2 ft-101 Rt of sheet tert-butyl peroxide was dissolved in hebutane and added through a dropping funnel over a period of about 30 minutes.

The temperature inside the system was maintained at 200°C, and the reaction was continued for about 1 hour. After that, the pressure inside the flask was reduced using an aspirator for about 30 minutes to remove unreacted anhydrous malein. ' was removed. The saponification value of this adult organism was 26.

Next, this raw material was placed in a glass-lined reaction pot for 30 minutes.
After charging 5L of carbon tetrachloride and thoroughly dissolving it at 110℃ under a pressure of 2Kf/-, gaseous chlorine was blown from the bottom of the reaction vessel to a concentration of 24wt% while irradiating it with ultraviolet rays. . After completion of the reaction, carbon tetrachloride as a solvent was distilled off using an evaporator and replaced with toluene to obtain a 20 wt % toluene solution of chlorinated poly-10-pyrene modified with maleic anhydride.

Example-1 A 2Qwt% toluene bath solution of the maleic acid-modified chlorinated polypropylene produced in Comparative Example-1 was placed in a Mitsuro flask equipped with a 50-orv stirrer and a reflux condenser, and heated to 80°C in a hot water bath. Increase temperature. After replacing the inside of the flask with nitrogen for about 10 minutes, benzoylperoxyl was added while stirring. After 30 minutes, dissolve the methacrylic powder in 5 ft-5 f of toluene and add 30
A friend who took time to accompany me. During this time, the inside of the system was maintained at 80°C, and the reaction was continued for about 3 hours. After cooling, the reaction solution was concentrated under reduced pressure.
Adjust the solid content concentration to 2Qwt.

Comparative Example-2 Used in Comparative Example-1, nine isotactic polypropylene 5oot and maleic anhydride [30f and
Anhydrous maleic modified Bo II propylene with a saponification value of 37 was obtained in the same manner as in Comparative Example 1 using 2 ft of -butyl peroxide. Next, a chlorination reaction was carried out according to Comparative Example-1, and a 20 wt% toluene solution of maleic anhydride-modified chlorinated poly-10-pyrene with a degree of chlorination of 24 wt. was prepared in Chlorine Example-2. Using 2-ethylhexyl methacrylate instead of methacrylic acid in Example-1, a 20 wt% toluene solution of maleic anhydride-modified chlorinated polypropylene with a chlorination degree of 24 wt% captured and unreacted maleic anhydride rI11 was prepared in the same manner. Obtained.

Comparative Example-3 Ethylene having a melt viscosity of about 2,500 CF2 at 200°C and an ethylene content of 4.2 wt%
10 pyrene copolymer, 3 l of maleic anhydride, and 3 ff of di-tert-butyl peroxide, maleic anhydride and di-tert-butyl peroxide were used at a reaction temperature of 200°C.
Add butyl peroxide at the same time for about 30 minutes. Other than that, the method is the same as Comparison-1. The saponification value of the maleic anhydride-modified ethylene-propylene copolymer at this time was 32. Next, a chlorination reaction was carried out according to Comparative Example-1 to produce a maleic anhydride-modified chlorinated ethylene-propylene copolymer with a degree of chlorination of 24 wt% (2Qwt%).
A toluene solution was obtained.

Example-3 Maleic anhydride-modified chlorinated ethylene-10-pyrene copolymer with a degree of chlorination of 24 wt% produced in Comparative Example-3 [7]
Using a wt% toluene solution and using methyl methacrylate in place of methacrylic acid in Example-1, unreacted maleic anhydride was captured by the same operation to obtain a chlorination degree of 24 wt%.
A 20 wt % toluene solution of maleic anhydride-modified chlorinated ethylene-propylene copolymer was obtained.

〔Effect of the invention〕

Comparative Examples-1, 2, 3 and Examples-1, 2゜2Qwt% t-luene bath solution of maleic anhydride-modified chlorinated polypropylene and ethylene-propylene copolymer f 10 mφ glass cell The transmittance of the solution was measured at a wavelength of 525 μm using toluene as a standard using a Takasago Posilom spectrophotometer model 5 PECTRONIC 20 [7t0 results are shown in Table 1].

Table 15 Transparency of M solution (a blockage) Example-4 Comparative Examples-1, 2, 3 and Examples 1, 2. 2Qwt% toluene solution 2002 and titanium oxide 4? , carbon black 0.1 and Epicoat 828
(Made by Shell Chemical ■) 1.6? Mix and mix in a sand mill for 1 hour, dilute with toluene to an appropriate viscosity, and wash with toluene L7? :Po1+70 pirene plate f2X50X8
Through-coating was applied to the area (0 m) to a film thickness of 5 to 10 μm.

After 5 minutes, a two-component hardening urethane paint (manufactured by NOF ■) was spray-painted to a film thickness of 30 to 40μ, air-dried for 15 minutes at room temperature, forced dry at 80℃ for 30 minutes, and then left at room temperature for another 24 hours. After standing still, all physical property tests of the coating film were carried out.

The complete results are shown in Table 2.

Table 2 Results of physical property test of paint film Test method/Adhesion: 100 goblets are made on the coated surface at 1m intervals, and Sellotape is stuck on top of it, and it is peeled off in a 180° direction, and the goblets that remain. I checked the number of

・Gun resistance: Scratches that reach the substrate on the painted surface (
Marked with X) The gold case was immersed in a regular gun for 2 hours and 4 hours at 25°C, and the state of the coating film was examined.

-Bending resistance: ■The state of the coating film was examined by bending it 180° using a φ inch mandrel.

・Impact resistance: Using a DuPont impact tester with a striking core of Aφ inch and a load of 500 f, the product was dropped from a height of 50 cIn in the case of facing, and was dropped from a height of f125α in the case of backing.

-Water resistance: The condition of the coating film was examined by immersing it in warm water at 50°C for 120 hours and 240 hours.

・Moisture resistance = 120% in an atmosphere of 98% relative humidity at 50°C
The condition of the coating film was examined after being left for 240 hours.

Claims (1)

[Claims] A carboxyl group-containing polyolefin is synthesized by reacting a polyolefin with a melt viscosity of 30 to 3,000 cps at 200°C with an unsaturated polycarboxylic acid or its acid anhydride, and then, after chlorinating the carboxyl group-containing polyolefin, residual A method for producing a chlorinated carboxyl group-containing polyolefin, which comprises polymerizing a saturated polycarboxylic acid or its acid anhydride with a (meth)acrylic acid monomer.