JPH0113485B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a cyclized diene resin. In particular, the present invention relates to a method for producing a cyclized diene chloride resin suitable for obtaining coating materials such as printing inks and paints, adhesive layers, etc., which have excellent adhesion to polyolefins and metal plates. . Salt oxides of natural rubber have been known for a long time, but
This conventional chloride oxide rubber has poor solubility in solvents, and its usage conditions are extremely limited in the fields of inks, paints, and adhesives that are used in a solution state. On the other hand, the inks, paints, and adhesives that can be used for polyolefins are limited due to the nonpolar nature of polyolefins, and cyclized rubbers, low-chlorinated polyolefins, and the like are used. However, all of these resins have the disadvantage that the dried film is hard, brittle, and lacks texture, and they are used only because there is no alternative. Furthermore, if the degree of chlorination is increased to a chlorine content of 40% or more, the stability deteriorates and, moreover, the adhesiveness of the polyolefin is lost. The present inventors have discovered that polyolefin has excellent solubility in solvents, has flexibility, softness, impact resistance, cold resistance, good texture, and has low gas permeability when applied to the surface of polyolefin. As a result of various studies in order to provide a chlorinated diene resin that can provide a coating or an adhesive layer, we found that 100 parts by weight of a diene resin containing 50% or more of non-butadiene diene monomer units and having a molecular weight of 5,000 to 100,000; By mixing 3 to 50 parts by weight of polybutadiene with a molecular weight of 300 to 100,000, cyclizing it, and then oxidizing 50 to 100% of the existing double bonds with hydrochloric acid, it adheres to a soft polyolefin film and has flexibility. It has flexibility, impact resistance, cold resistance, and a good texture, and surprisingly, it also adheres to hard metal plates such as tin, mortar, glass plates, etc., making it flexible and impact resistant. The result is a chlorinated diene resin that can provide a durable and weather-resistant coating or adhesive layer. The molecular weight of the diene resin other than polybutadiene used in the present invention is 5,000 to 100,000, preferably 8,000.
It is preferably about 65,000; if it is less than 5,000, drying properties are poor, and if it is greater than 100,000, solubility is poor. The diene resin is isoprene, 2-ethylbutadiene-1,3,2-isopropylbutadiene-
1,3,2-amylbutadiene-1,3, methylpentadiene-1,3, pentadiene-1,3,
Non-butadiene diene polymers such as hexadiene-1,3 and hexadiene-2,4, or copolymers of these dienes and copolymer components such as styrene, acrylonitrile, butadiene, etc. can be used, but preferably 50 moles of isoprene units are used. % or more, and particularly preferred is polyisoprene. The polybutadiene to be co-cyclized may be any polybutadiene subjected to radical polymerization, anionic polymerization, cationic polymerization, coordination anionic polymerization, or living anionic polymerization, but it is preferably liquid in view of the viscosity after cyclization, etc. 300～
A value of about 10,000 is preferable. The combined mixing ratio of diene resin and polybutadiene resin is 100 parts of diene resin (based on weight, the same applies below)
The amount is 3 to 50 parts, preferably 5 to 35 parts, of the polybutadiene resin. If it is less than 3 parts, the resin oxidized with hydrochloride after cyclization will have less softness and poor texture, and if it is more than 50 parts, it will tend to gel during cyclization, or there will be partial insoluble matter during the subsequent salt oxidation. This is because a uniform resin cannot be obtained, or even if a uniform resin is obtained, the adhesion to metal plates etc. is deteriorated. The cyclization method may be carried out in accordance with a conventionally known method, using a solvent in which the raw material diene resin and polybutadiene are dissolved, and in which the product cyclized product and chloride oxide are soluble, such as aromatic hydrocarbons such as benzene, toluene, and xylene; Aliphatic halogenated low hydrocarbon solvents such as chloroform, carbon tetrachloride, trichloroethylene, tetrachloroethylene, and dichloroethane are used, and particularly preferred are benzene, toluene, and the like. Reaction temperature is 50℃~150℃
However, by performing the process at a temperature of about 60℃ to 110℃,
A cyclized product can be obtained without producing a gelled product or the like. Friedel-Crafts type catalysts such as boron trifluoride, tin tetrachloride, aluminum chloride, titanium tetrachloride, and zinc chloride can be used as catalysts for the cyclization reaction, but the catalyst must be deactivated after the reaction. From the viewpoint of removal operations, boron trifluoride is preferred, but tin tetrachloride, which is also effective in the next step of the hydrochloric oxidation reaction, is also preferred. The amount of catalyst used correlates with the desired degree of cyclization, but
0.001-5% based on the resin used, preferably 0.05
~2.0% is good. If the degree of cyclization is too high, the amount of chlorine added in the next step of salt oxidation will decrease and the adhesion to non-polar films such as polyolefin will decrease, so the degree of cyclization is preferably 65% or less. The method of salt oxidation after cyclization is not particularly limited, and it may be sufficient to react the hydrochloric acid by blowing hydrogen chloride gas into the solvent while stirring and heating at room temperature or if necessary, as described above. Alternatively, a method may be used in which a specified hydrochloric acid is dissolved in a solvent, a cyclized diene resin is separately dissolved in a solvent, and the cyclized diene resin is added to the dissolved system and mixed. The reaction may be carried out by the following method. If necessary, azobisisobutyronitrile, perbenzoic acid, aluminum trichloride, tin tetrachloride, etc. may be used as a catalyst. After reacting to a predetermined ratio, remove remaining hydrogen chloride gas with nitrogen gas or air, add a stabilizer such as an epoxy resin to produce a product, or precipitate a chloride oxide such as methanol, It may be separated and dried to produce a product. The degree of oxidation is 50% of the double bonds present in the polymer.
% or more. The invention will be explained in more detail with reference to Examples below. Production example 1 Polyisoprene with a molecular weight of 50,000 (Clareprene)
LIR-50, manufactured by Kuraray Soprene Co., Ltd.) 108g
and liquid polybutadiene (Hu¨ls polyoil P-
110, molecular weight approximately 1600, manufactured by Hu¨ls) in 320 g of toluene under a nitrogen stream, the temperature was raised to 100-105°C, and while stirring, the catalyst BF ₃ · Et ₂ O (trifluoride) was dissolved. 100g of boron ether complex) 0.1wt% (based on resin)
Dissolve in toluene and drip in 30 minutes. After stirring for 5 hours under the same conditions, the catalyst was inactivated with Ca(OH) ₂ and filtered. Next, while stirring hydrogen chloride gas at room temperature,
Feed and perform salt oxidation, sample over time and perform salt oxidation, and after reaching the appropriate degree of salt oxidation, drive out hydrogen chloride gas with nitrogen gas, and add epoxy resin equivalent to 2% of the resin amount. After adding the stabilizer, the mixture was stirred for 30 minutes to obtain a sample in a solution state. The resin part of the obtained product has a degree of cyclization of 21% (calculated from the iodine value before and after cyclization), and a residual double bond of 95%.
% was oxidized with salt, and the chlorine concentration was 32.0%. Production example 2 LIR-50; 108g, P-110; 17.5g, BF ₃ .
When the reaction was carried out in exactly the same manner as in Production Example 1 except that 0.2wt% of Et ₂ O was used, the degree of cyclization was 38% and the remaining double bonds were 82%.
was oxidized, and the chlorine concentration was 26.7%. Production Example 3 The reaction was carried out in the same manner as in Production Example 1, except that 108 g of LIR-50, 36 g of P-110, 480 g of toluene for dissolution, and 0.20 wt% of BF ₃ Et ₂ O were used.
A resin with a degree of cyclization of 49%, a degree of chloride oxidation of 72.5%, and a chlorine concentration of 16.4% was obtained. Production example 4 Polyisoprene with a molecular weight of 30,000 (Clareprene)
LIR-30, manufactured by Clarei Soprene Co., Ltd.) 108g, P
-110 4.0g and 0.1wt% BF ₃ · Et ₂ O were used, but when the reaction was carried out in exactly the same manner as in Production Example 1, the degree of cyclization was 15.
%, a degree of salt oxidation of 96%, and a chlorine concentration of 33.2 wt%. Production Example 5 A cyclization reaction was carried out in the same manner as in Production Example 1 using 108 g of LIR-50; 17.5 g of polybutadiene PB-1000 (molecular weight 1000, manufactured by Nippon Soda Co., Ltd.) and 0.5 g of tin tetrachloride. After cooling and adding an additional 0.5 g of tin tetrachloride at room temperature, salt oxidation is performed. The degree of cyclization is 25%, the degree of salt oxidation is 90%, and the chlorine concentration is 28.6.
% resin was obtained. Production example 6 LIR-50 108g, polybutadiene (Hu¨ls
polyoil P-160, molecular weight 6000, manufactured by Hu¨ls)
Except for using 8.25g and 0.1wt% of BF ₃ · Et ₂ O.
When reacted in exactly the same manner as in Production Example 1, the degree of cyclization was 18.0.
%, a degree of salt oxidation of 97%, and a chlorine concentration of 24.2%. Comparative production example 1 Dissolve 108 g of LIR-50 in 320 g of toluene, feed it while stirring with hydrogen chloride gas at room temperature, perform salt oxidation to reach a predetermined amount, and then oxidize the hydrogen chloride gas with nitrogen gas. Drive out, stabilizer
When 2wt% is added and mixed, the degree of salt oxidation is 85% and the chlorine concentration is
28.9wt% resin was obtained. Comparative production example 2 LIR-50; 108g was added to 320g of toluene,
The temperature was raised to 105°C under a N ₂ stream, and while stirring, BF ₃ .
A solution of 0.1wt% Et ₂ O in 100g of toluene is added dropwise over 30 minutes. After reacting for 5 hours under the same conditions to carry out the cyclization reaction, the catalyst was deactivated with Ca(OH) ₂ to carry out the reaction. When salt oxidation was carried out using a conventional method, a resin with a cyclization rate of 9.5%, a degree of salt oxidation of 80%, and a chlorine concentration of 24.6 wt% was obtained. Comparative production example 3 LIR-50; 108g, P-110 72g toluene
Dissolve in 560g, heat to 85℃, BF ₃・Et ₂ O0.2wt
% dissolved in 100g of toluene was added over 30 minutes, then the temperature was raised to 105℃, and after reacting for 5 hours, Ca
Add filtrate (OH) ₂ . When the obtained product is oxidized with salt according to a conventional method, the degree of cyclization is 45% and the degree of salt oxidation is 92.
%, and a resin with a chlorine concentration of 23% was obtained. Comparative production example 4 LIR-50; 54g, P-110 54g to toluene
Dissolve in 320g, heat to 105℃, and add 100g of toluene.
When BF ₃ ·Et ₂ O dissolved in was added dropwise, gel insoluble matter was gradually formed, and the entire product became a gel within 1 hour after the dropwise addition. Comparative Production Example 5 Same as Comparative Production Example 4, LIR-50; 54g, P-
When 54 g of 110 was dissolved in 320 g of toluene and hydrochloric acid was fed at room temperature, insoluble gel was partially formed. Comparative Production Example 6 200 g of toluene was placed in a 4-necked flask against 20 g of cis-1,4-polybutadiene, and after blowing chlorine gas into it for about 10 minutes, 1 wt% of tin tetrachloride was added to the polybutadiene. Thereafter, hydrogen chloride gas was blown into the solution to oxidize the solution. Then, hydrogen chloride gas was removed by nitrogen feed and filtration was performed. The chlorine content of the obtained product is
It was 27.8%. Example 1 The cyclized hydrochloride diene resin obtained in Production Examples 1 to 6 and Comparative Production Examples 1 to 3 was adjusted to a 20 wt% toluene solution, and coated on an untreated polypropylene film and a tin plate using a No. 18 bar coater. It was applied and evaluated as a clear paint. Table 1 shows the results.
Shown below.

[Table] The resin obtained by the method of the present invention has excellent adhesive properties equivalent to conventional coating materials for polyolefins, and at the same time has flexibility and resistance to hand rubbing. Needless to say, at the same time, results were obtained in which the physical properties of the coating film on tinplate plates were excellent even when the composition was used alone. Example 2 In order to test as a gravure ink, 27.6 g of the resin (solid content equivalent) obtained in the production example and comparative production example, 100 g of toluene, and Adekasizer-O were used.
-130 (manufactured by Asahi Denka Co., Ltd.), Taipei, R-550
(Rutile type titanium white, Ishihara Sangyo Co., Ltd.)
30.0 g was mixed overnight in a ball mill, adjusted to 30 seconds using a Zahn cup #3, thoroughly mixed, and coated on various substrates using a bar coater No. 18 to evaluate performance. The results are shown in Table 2.

【table】

[Table] Cyclization of isoprene/butadiene mixture obtained by the method of the present invention from the results of printing coating.
The salt-oxidized product has good fir strength, Scotch tape peeling test, blocking resistance, and light resistance, and also shows good alkali resistance and acid resistance as a propylene film, but with the same composition, it has good resistance to hard substrates such as tin plate. It can be seen that it exhibits sufficient adhesion to materials. Example 3 The solubility in toluene, which is a typical solvent for chlorinated polyisoprene rubber, was evaluated for chlorinated rubber obtained by chlorinating natural rubber having an isoprene structure and the cyclized chlorinated rubber of the present invention. Table 3 shows the results.
Shown below. As is clear from Table 3, the cyclized hydrochloride oxide rubber of the present invention exhibits excellent solubility.

【table】

Claims (1)

[Claims] 1 After mixing 100 parts by weight of a diene resin excluding polybutadiene with a molecular weight of 5,000 to 100,000 and in which 50% or more of the monomer units are derived from diene monomers and 3 to 50 parts by weight of a polybutadiene resin with a molecular weight of 300 to 100,000 and cyclizing the mixture, 1. A method for producing a cyclized hydrochloride diene resin, characterized by carrying out salt oxidation until 50% or more of the double bonds are oxidized.