JPS5933608B2 - Method for producing graft polymer with chlorinated polyolefin as main chain - Google Patents

Description

Detailed Description of the Invention The present invention is characterized by reacting a chlorosulfonated polyolefin with a polyalkylene oxide having a primary amino end group.The main chain is a chlorinated polyolefin, and the graft chain is a polyoxyalkylene. The present invention relates to a method for producing a graft polymer.

The present inventor first developed an inert organic solution that is incompatible with water.

We have discovered a new method for producing a graft polymer, which is characterized by reacting a chlorosulfonated polyolefin dissolved in a polyalkylene oxide with a polyalkylene oxide having a hydroxyl group at at least one end. (Unexamined Japanese Patent Publication No. 56-118422)
The new graft polymer obtained by this method has unique properties as a water-absorbing elastomer, and its solution exhibits excellent film-forming properties and great spinnability, and is transparent and has remarkable elasticity. It is possible to provide a film and a filament with a high quality.

In view of these properties, it has been recognized that this graft polymer may be used for various special purposes. As mentioned above, this method is characterized by carrying out the reaction in a heterogeneous system consisting of two phases: an organic phase containing the polymer and an alkaline aqueous solution phase. It is believed that this also results in the formation of sulfonate groups. In fact, many of the sulfonyl chloride groups present in the chlorosulfonated polyolefin used as the raw material become sulfonate groups during the reaction, and only some give polyoxyalkylene graft chains bonded to the main chain through sulfonic acid ester bonds. This has been confirmed. The reason why this graft polymer exhibits excellent rubber elasticity and tensile properties similar to ordinary vulcanized rubber even without the so-called vulcanization operation is due to the sulfonate group, which has a high cohesive ability as a strong ionic group. This is thought to be due to the formation of microphase-separated agglomerated regions, which function as crosslinking points.

However, on the other hand, the presence of such ionic aggregation regions is not necessarily advantageous in terms of processability.
For example, molding this material would require fairly high molding temperatures and the use of appropriate softeners. Further, when processing as a solution, usable solvents are limited to aprotic polar solvents. Therefore, by having a polyoxyalkylene graft chain, it maintains the above-mentioned unique properties as a water-absorbing elastomer, while also being easily processed and molded in the same way as ordinary chlorosulfonated polyolefins. It would be of great practical significance to find a material that can be dissolved in common solvents to give a solution. The novel graft copolymer according to the present invention was synthesized based on this viewpoint.

That is, the graft polymer according to the present invention differs from the graft polymer according to JP-A-56-118422, in that the sulfonyl chloride group in the chlorosulfonated polyolefin and the primary amino group present at the terminal of the polyalkylene oxide It has a polyoxyalkylene graft chain attached to the main chain by a sulfonamide bond based on the reaction between may contain sulfonate groups, and such graft polymers are also included within the scope of the present invention). Therefore, this graft polymer exhibits interesting properties as a water-absorbing elastomer similar to the sulfonate group-containing graft polymers described above, and when it does not contain sulfonate groups, it is comparable to ordinary chlorosulfonated polyolefins. Vulcanization and molding can be carried out under similar processing conditions, and solutions can be provided by dissolving in common organic solvents such as aromatic hydrocarbons, halogenated hydrocarbons, etc. The novel graft polymers according to the invention can be obtained by reacting a chlorosulfonated polyolefin with a polyalkylene oxide having a primary amino group at least at one end in a homogeneous or heterogeneous solution. The chlorosulfonated polyolefin used as a reaction raw material is an olefin such as polyethylene, polypropylene, or ethylene-propylene copolymer, which has a molecular weight sufficiently high to exhibit properties as a plastic or elastomer, usually 5,000 or more. The polymer is synthesized by reacting with SO2-Cl2 or sulfuryl chloride in a solution according to a known method, but the product in this case always contains a hydrogen-substituted group in addition to the sulfonyl chloride group. The chlorine content and the sulfur content (corresponding, of course, to the content of sulfonyl chloride groups) can be varied widely by varying the reaction conditions.

In particular, chlorosulfonated polyethylene is an elastomer material with excellent weather resistance, and various brands with a chlorine content of 20 to 40% and a sulfur content of 1 to 1.5% are industrially manufactured and commercially available. In the present invention, it is advantageous to use these commercially available products. However, in the case of the present invention it is possible to use high molecular weight chlorosulfonated polyolefins with a sulfonyl chloride group content in the range from 10 to 60% chlorine content and from 0.2 to 20% as sulfur content. Another reaction raw material, polyalkylene oxide having a primary amino group at the end (hereinafter referred to as aminated PAO), is produced by ring-opening polymerization or copolymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc. It can be synthesized from polyalkylene glycol by a known method, and some products can also be obtained as ready-made products (for example, PEO-amine manufactured by Kawaken Fine Chemicals).

In particular, polyethylene glycol is industrially produced in a wide range of molecular weights, from several hundred to several thousand. Aminated PAO can be used as a raw material. However, in order to achieve a sufficient modification effect, especially imparting hydrophilicity, to the chlorosulfonated olefin polymer by grafting, it is necessary to use aminated polyethylene oxide and aminated ethylene oxide/propylene oxide with a molecular weight of several thousand or more. Preference is given to using copolymers. The reaction is carried out by dissolving both reactants in a solvent and stirring for a suitable period of time, preferably under heating. Therefore, the amount of solvent used must be such that sufficient stirring of the reaction mixture is possible under the reaction conditions. Further, it is preferable to use the aminated PAO in an amount such that about the same mole or more of amino groups are present relative to the -SO2Cl groups present in the chlorosulfonated polyolefin used. When a reaction is carried out in a homogeneous system, it is common to dissolve both reactants in a common solvent. It can be anything as long as it is something.

It is usually advantageous to use aromatic hydrocarbons or halogenated hydrocarbons. The use of polar solvents is undesirable since it often reduces the grafting rate. The reaction temperature used is from room temperature to the boiling point of the solvent used, but a temperature of 40 to 80°C is usually convenient.

When carrying out the reaction as a heterogeneous system, the chlorosulfonated polyolefin is dissolved in an organic solvent that is incompatible with water.
On the other hand, dissolve aminated PAO in water or dilute aqueous alkaline solution, mix both solutions and stir thoroughly to obtain a well-dispersed emulsified state, and continue stirring for an appropriate period of time with or without heating. do it.

Although the amount of water used is arbitrary, it is usually used in such an amount that the polyalkylene oxide used is completely dissolved and the reaction mixture forms a homogeneous emulsion. Recovery of the reaction product from the reaction mixture can be carried out according to the usual method used for recovery of polymers from polymer solutions, and unreacted aminated PAO remaining in the reaction product can be washed with water. It can be easily removed by

Since the graft polymer of the present invention is produced based on a condensation-like addition reaction between polymers, its molecular weight is determined by the bonded chlorosulfonated polyolefin and aminated P.
This corresponds to the sum of the molecular weights of AO.

The molecular weight of the product can therefore vary widely depending on the molecular weight of the polymer used as raw material and the degree of grafting achieved, but for many applications it will be at least as high as the molecular weight representative of the film-forming ability. It is preferable that The grafting ratio, expressed as a weight percentage of the polyoxyalkylene graft chain to the chlorinated polyolefinic main chain as backbone polymer, depends on the molecular weight of the chlorosulfonated polyolefin used and, in particular, the sulfonyl chloride group content and the molecular weight of the aminated PAO. can be varied within a wide range of 5 to 100% by changing the ratio of both reaction components used, reaction conditions, etc. However, from the viewpoint of the physical properties of the product, especially mechanical properties, it is less than 50%. It is desirable that

In homogeneous reactions using only organic solvents and heterogeneous reactions using organic solvents and aqueous systems, in many cases, only a portion of the sulfonyl chloride groups in the chlorosulfonated polyolefin as a raw material are converted into terminal amino groups of the aminated PAO. It reacts with polyoxyalkylene graft chains based on sulfonamide bonds, and many sulfonyl chloride groups remain as they are without reacting. Vulcanization using , polyamine, etc. is possible.

However, even without such a vulcanization treatment, the grafted product generally exhibits elastic properties similar to vulcanized rubber, unlike the raw polymer before reaction. In the heterogeneous reaction carried out in the presence of an aqueous alkaline solution, it is possible to use alkali metal-based bases, especially aqueous solutions of alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, etc. preferable.

In this case, most of the sulfonyl chloride groups present in the chlorosulfonated polyolefin are hydrolyzed to become sulfonate groups, and some react with the terminal amino groups of the aminated PAO to give graft chains based on sulfonamide groups. . Therefore, the product in this case is
Just like the graft polymer No. 8422, it exhibits excellent properties comparable to ordinary vulcanized rubber even without vulcanization. In any case, the graft polymer of the present invention has a hydrophilic polyoxyalkylene chain grafted onto a hydrophobic main chain consisting of a chlorinated polyolefin, which itself has the essence of an elastomer. Then,
In addition to its properties as a water-absorbing elastomer, it exhibits a variety of interesting properties and is expected to have many useful applications as new membrane materials, medical materials, molding materials with special properties, coating compositions, elastic threads, etc. can.

Next, the present invention will be explained in more detail based on examples.

Example 1 Commercially available chlorosulfonated polyethylene (Hypalon 40, Showa Neoprene Co., Ltd.) 27 and polyethylene oxide having primary amino groups at both ends (PEO-Amine 6000, Kawakami Huain Chemical Co., Ltd.) 27 were cooled under reflux. The mixture was dissolved in 40 ml of chloroform in a Nituro flask equipped with a stirrer and a stirrer, and stirred for 2 hours in a constant temperature bath at 60°C.

The product was precipitated into a coarse powder by stirring the reaction solution in a homogenizer with three times the amount of methanol. Unreacted aminated polyethylene oxide was removed by repeated washing with methanol and water with stirring in a homogenizer and dried at 40° C. in a vacuum dryer to yield the product 2.467. The infrared absorption spectrum of the film of this product showed a significant absorption of ether bond at 1110cTn-1. -137 based on SO2Cl
The absorption strength of 0crrL-1 is lower than that of the raw material polymer, and 1350? -1, a new absorption appeared that was thought to be based on the sulfonamide bond. The 1H nuclear magnetic resonance spectrum of the product showed absorption at 3.65 ppm due to polyoxyethylene chains. The grafting ratio calculated from the strength was 25.0% based on the main chain polymer. A chloroform solution of the product was poured onto a glass plate, and the solvent was evaporated to obtain a colorless, transparent, tough film with rubber-like elasticity. This film was immersed in water at 30°C and when it reached equilibrium, it absorbed 45% of its original weight in water. Also, the above solution had extremely low spinnability. Sea Bream 2 A dry product of 2.387 was obtained in the same manner as in Example 1, except that 1,2-dichloroethane was used as the solvent and stirring was performed at 80°C for 6 hours.

The grafting rate was 21.6%. Example 3 A dry product of 2.277 g
I got it.

The grafting rate was 21.5%. Example 4 Chlorosulfonated polyethylene (Hypalon 40) 27
was dissolved in 15 ml of 1,2-dichloroethane, while aminated polyethylene oxide (the above PEO amine 6000
) was dissolved in 157 TL of water.

Both solutions were mixed and stirred at 60°C for 2.5 hours.
The reaction was worked up as in Example 1 to give the dry product 2.127. The grafting rate was 16.8%. Example 5 Chlorosulfonated polyethylene 27 (... Ipalon 40
) with 20 ml of carbon tetrachloride and 12 ml of 1,2-dichloroethane
It was dissolved in a mixture of m1.

Aminated polyethylene oxide (PEO-Amine 600
0) in 20ml of water, and add 1N NaOH solution 7 to it.
m1 was added. Both solutions were mixed and stirred at 60°C for 1 hour. The reaction was processed as in Example 1 to obtain a dry product of 2.327. Its infrared absorption vector is 119
5CT11-1 and 1050CTI1-1 - SO3Na
The absorption based on The grafting rate determined from 1H NMR was 23.2%.

This product was insoluble in aromatic hydrocarbons, logenated hydrocarbons, and soluble in polar solvents such as tetrahydrofuran, dioxane, dimethylformamide, and N-methylpyrrolidone. Example 6 Commercially available ethylene. Chlorosulfonated ethylene having a sulfur content of 5.1% and a chlorine content of 22.9% is produced by reacting propylene rubber (ethylene lipropylene, approximately 50:50) with sulfuryl chloride in carbon tetrachloride. A propylene copolymer was synthesized.

This chlorosulfonated polymer 17 and aminated polyethylene oxide (PEO-amine 6000) 17 were dissolved in 20 ml of chloroform, stirred at 60°C for 3 hours, and then the reaction solution was poured into a large amount of hexane to dissolve the reaction product. precipitated. The precipitate was thoroughly washed with methanol and water in a homogenizer and then dried under vacuum to obtain product 1.27. The grafting rate determined by 1H NMR was 43.7%.

Claims (1)

[Claims] 1. A method for producing a graft polymer having a chlorinated polyolefin main chain and a polyoxyalkylene graft chain, which comprises reacting a chlorosulfonated polyolefin with a polyalkylene oxide having a primary amino group at least at one end.