JPS5936137A - Graftpolymer with its main chain constituted by chlorinated polyolefin - Google Patents

Abstract

PURPOSE:To provide a water-absorptive graft polymer capable of curing and molding, constituted by a specific chlorinated polyolefinic main chain and polyoxyalkylene graft chain connected to said main chain through sulfonamide bond. CONSTITUTION:The objective graft polymer can be obtained by first dissolving a chlorosulfonated polyolefin and primary amino group-terminated polyalkylene oxide in a solvent (e.g., an aromatic hydrocarbon) followed by carrying out a reaction pref. at 40-80 deg.C. This graft polymer is constituted by a chlorinated polyolefinic main chain and polyoxyalkylene graft chain connected to said main chain through the sulfonamide bond. USE:For membrane and medical materials, molding compounds, coating composition, elastic fibers, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the main chain of a chlorinated polyolefin produced by the reaction of a chlorosulfonated polyolefin and a polyalkylene oxide having a primary 7-mino end group, and a polyester bonded to the main chain by a sulfonamide bond. This invention relates to a graft polymer composed of oxyalkylene graft chains and a method for producing the same.

The present inventor first produced a novel graft polymer characterized by reacting a chlorosulfonated polyolefin dissolved in an inert organic solvent that is incompatible with water with a polyalkylene oxide having a hydroxyl group at at least one end. I found a way. (Japanese Unexamined Patent Publication No. 118422, September 17, 1981) The new graft polymer obtained by this method has unique properties as a nylon tor with water absorption, and its solution has excellent film formation properties. It is possible to provide transparent films and filaments that exhibit high elasticity and high stringability, and have remarkable elasticity. In view of these properties, it has been recognized that this graft polymer may be used for various special purposes.

As shown in Q above, this method is characterized by carrying out the reaction in a heterogeneous system consisting of two phases: an organic phase containing a 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 a raw material become sulfonate groups during the reaction, and only a portion of them are bonded to the main chain through sulfonic acid ester bonds. The thing is (1'W is held).

The reason why this graft polymer exhibits excellent rubber elasticity and tensile properties similar to ordinary vulcanized rubber even without vulcanization is due to the presence of strongly ionic agglomerated regions.
It 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. In addition, when processing as a solution, the usable solvents (d) are limited to aprotic polar solvents. Therefore, by having a polyoxyalkylene graft chain, it maintains the unique properties of a water-absorbing elastomer as described above. However, on the other hand, it would be of great practical significance to find a material that can be easily processed and molded in the same way as ordinary chlorosulfonated polyolefins, and that can be dissolved in ordinary solvents to form a solution. I think that the.

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 No. 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 (such graft polymers are also included within the scope of the present invention). Therefore, this graft polymer exhibits interesting properties as a water-absorbing nidistomer similar to the above-mentioned sulfonate group-containing graft polymer, and when it does not contain sulfonate groups, it can be used as a normal chlorosulfonated polyolefin. 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 polymer 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. , synthesized by reacting with 802-012 or sulfuryl chloride in a solution according to a known method, but in this case, the product always has hydrogen substituted in addition to the sulfonyl chloride group, and a certain amount of chlorine. The chlorine and sulfur contents (which naturally correspond to the content of sulfonyl chloride groups) can be varied widely by changing the reaction conditions. In particular, chlorosulfonated polyethylene is an elastomer material with excellent weather resistance, with a chlorine content of 20 to 40% and a sulfur content of fi: 1.
Various brands of about 1.5% to 1.5% are industrially manufactured and commercially available, and it is advantageous to use these commercially available products in the present invention. However, in the case of the present invention, the chlorine content is 10-60% and the sulfur content is 02-2%.
It is possible to use high molecular weight chlorosulfonated polyolefins with a sulfonyl chloride group content in the zero coefficient range.

Polyalkylene oxide having a primary amino group at the end (hereinafter referred to as aminated PAO) is another reaction raw material.
can be synthesized by known methods from polyalkylene glycols produced by ring-opening polymerization or copolymerization of alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide, and some of them are available as ready-made products. (For example, P, EO-amine manufactured by Yoken Fine Chemical Co., Ltd.). In particular, polyethylene glycol is industrially produced in a wide range of molecular weights, from several hundred to several thousand. -C can be used using aminated PA, O as a raw material. However, sufficient modification effect by grafting reaction on chlorosulfonated olefin polymer,
In particular, in order to achieve hydrophilicity, it is preferable to use aminated polyethylene oxide and aminated ethylene oxide/propylene oxide copolymers having a molecular weight of several thousand or more.

The reaction is carried out by dissolving both reactants in a solvent and stirring for a suitable period of time, preferably under heat. Therefore, the amount of solvent used must be such that sufficient agitation of the reaction mixture is possible under the reaction conditions. Further, it is preferable to use the aminated PAOid in an amount such that the amount of amine groups present is approximately equal to or more than the -SO2Cl group present in the chlorosulfonated polyolefin 1 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. 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 the reaction is carried out as a heterogeneous system, use chlorine.

The sulfonated polyolefin is dissolved in an organic solvent that is incompatible with water, while the aminated PAO is dissolved in water or a dilute alkaline aqueous solution, the sub-solution is mixed and sufficiently stirred to form a well-dispersed emulsified state, and the mixture is heated. Alternatively, stirring may be continued for an appropriate period of time without heating. Although the amount of water used is arbitrary, it is usually used to completely dissolve the polyalkylene oxide used and to form a homogeneous emulsion of the reaction mixture in the acid. corresponds to the sum of the molecular weights of phosphorus and aminated PAO when washed with water. The molecular weight of the product can therefore vary widely depending on the molecular weight of the polymer used as a 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 its film-forming ability. It is preferable that

The grafting ratio, expressed as a weight percentage of the polyoxyalkylene graft chain to the chlorinated polyolefin main chain as the backbone polymer, depends on the molecular weight of the chlorosulfonated polyolefin used and, in particular, the sulfonyl chloride group content;
In addition, by changing the molecular weight of the aminated P A O, the ratio of both reaction components used, reaction conditions, etc.
Although it can be varied within a wide range of ~100%,
In terms of physical properties of the product, especially mechanical properties, 50%
It is desirable that it is not yet 1ti7j.

In homogeneous reactions using only organic solvents and heterogeneous organic solvent-water reactions, in many cases, only a portion of the sulfonyl chloride groups in the chlorosulfonated polyolefin as a raw material are converted into aminated P A O. It reacts with the terminal amino group to form a polyoxyalkylene graft chain based on sulfonamide bonds, and many of the sulfonyl chloride groups remain unreacted, so as mentioned above, as in normal chlorosulfonated polyolefins, Vulcanization using oxides, polyamines, etc. is possible. However, the grafted product is generally a raw material before reaction, even without such vulcanization treatment. 'Mums differ and exhibit elastic properties similar to vulcanized rubber.

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 exhibits excellent properties comparable to ordinary vulcanized rubber even without vulcanization, just like the graft polymer of JP-A-118422.

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. In addition to its properties as a water-absorbing elastomer, it exhibits various interesting properties and has many useful applications as new membrane materials, medical materials, molding materials with special properties, coating compositions, elastic threads, etc. You can expect it.

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

Example 1 2 g of commercially available chlorosulfonated polyethylene () Inoclon 40 (Showa Neoprene Co., Ltd.), polyethylene oxide having primary amino groups at both ends (stirred in a constant temperature bath for 2 hours. The reaction solution was homogenized) The product was precipitated into a coarse powder by stirring with 3 times the amount of methanol in a homogenizer.Washing with methanol and water was repeated while stirring in a homogenizer to remove unreacted aminated polyethylene oxide, and vacuum drying was performed. After drying in a vessel at 40°C, 2.46 g of product was obtained.The infrared absorption spectrum of the film of this product showed a significant absorption of ether bonds at 1110 cm'. Based on -8O2Cl<
The absorption at 1370 cm' was lower in intensity than that of the raw polymer, and a new absorption appeared at 13501 that was attributed to the sulfonamide bond. The IH magnetic resonance spectrum of the product showed an absorption based on polyoxyethylene chains at 3.651) pm. 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. The film was immersed in water at 30°C and when it reached equilibrium it had absorbed 45 inches of its original weight of water. Moreover, the above solution showed extremely high invasiveness.

Example 2 2.38 g of a dry product 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%.

Oboro Example 3 The dry product 2.
27.9 was obtained. The grafting rate was 21.5%.

Example 4 2 g of chlorosulfonated polyethylene (Hypalon 40)
was dissolved in 1.5 ml of 1,2-dichloroethane, and on the other hand, aminated polyethylene oxide (1) E Oamine 6000) was dissolved in 15 ml of water. Both solutions were mixed and stirred at 60°C for 2.5 hours. Example 1
Working up as in gave 2.12 g of dry product. The graft rate was 168 cases.

Example 5 2 g of chlorosulfonated polyethylene (Hypalon 40)
20m of carbon tetrachloride and 12m of 1,2-dichloroethane
6. Dissolve aminated polyethylene oxide (PEO-Amine 6000) in 20 ml of water,
7 ml of INNa01-1 solution was added thereto. Both solutions were mixed and stirred at 60°C for 1 hour. The reaction was processed as in Example 1 to obtain dry product 2.32.9. Its infrared absorption spectrum was 1195 cTL'-1 and it was soluble in polar solvents such as oxane, dimethylformamide, and N-methyl-pyrrolidone.

Example 6 A commercially available ethylene, fluoropylene rubber (ethylene:propylene, approximately 50:50) was prepared with a sulfur content of 51% and a sulfur content of 22.9% by reacting with sulfuryl chloride in carbon tetrachloride.
A chlorosulfonated ethylene-propylene copolymer with a chlorine content of % was synthesized. Chlorosulfonated polymer】g and aminated polyethylene L/7 oxide (PE0
-Amine 6000) 1 j9 in chloroform 20rn
After stirring at 60° C. for 3 hours, the reaction solution was poured into a large amount of hexane to precipitate the reaction product. The precipitate was thoroughly washed with methanol and water in a homogenizer and then dried under vacuum to obtain 1.2 g of product.
obtained. The grafting rate determined from I HN M l (, 43.7%).

Claims (1)

[Claims] (I) A chlorinated polyolefin main chain obtained by reacting a chlorosulfonated polyolefin with a polyalkylene oxide having a primary amino group at least at one end in a solution, and a polyoxyalkylene bonded to the main chain through a sulfonamide bond. A graft polymer consisting of graft chains.