JPH0461883B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a water-soluble polymer having adhesive properties. More specifically, it is a method for producing a sticky polymer using an ultraviolet irradiation polymerization method, in which polymerization proceeds efficiently and the resulting polymer has significantly reduced adhesion or adhesion to polymerization equipment. Concerning the manufacturing method of coalescence. Traditionally, for example (meth)acrylamide;
(Meth)acrylate; N,N-dialkylaminoalkyl (meth)acrylate acid salt or 4
Ni-containing acrylic esters such as salts, acid salts or quaternary salts of N,N-dialkylaminohydroxyalkyl (meth)acrylates; diallylamine compounds such as diallylamine acid salts and diallyldialkylammonium salts; sulfoalkyl (meth)acrylates; Acrylates: (water-insoluble (meth)acrylic esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, etc. (meth)acrylamide derivatives such as acrylamide alkyl sulfonate and dialkyl (meth)acrylamide; acrylonitrile; when producing a water-soluble polymer using a vinyl group-containing monomer such as vinyl sulfonic acid or its salt; In general, polymers with a high degree of polymerization produce relatively hard gels, but they have remarkable adhesion and adhesion to the walls of the polymerization vessel.
It is not easy to peel off the polymer from the wall of the polymerization vessel. Moreover, even those with a low degree of polymerization have strong adhesion and adhesion to the wall surface, and once the produced polymer has adhered to the wall surface, it cannot be peeled off as a practical matter. The present inventors have previously proposed a method for producing an adhesive polymer using a polymerization apparatus in which the contact portion with the monomer solution is coated or equipped with a tetrafluoroethylene-ethylene copolymer resin. proposed. By the way, in the polymerization of vinyl group-containing monomers by ultraviolet irradiation polymerization, it has been found that the polymerization efficiency is generally better if a polymerization container is made of a material with high ultraviolet reflectance, such as mirror-finished stainless steel. There is. Furthermore, the present inventors have discovered that when a transparent tetrafluoroethylene-ethylene copolymer resin film is attached to the surface, the resulting sticky polymer can be easily peeled off. However, mirror-finished stainless steel is expensive and requires a large investment on an industrial scale. Furthermore, sticky polymers cannot be easily peeled off manually, even when stainless steel has a mirror finish. In particular, since the polymerization time required for polymerization by ultraviolet irradiation is extremely short, unless the polymer sheet can be easily peeled off from the polymerization apparatus, it will be of no industrial value at all, and improvement research is required. In view of the above-mentioned circumstances, the present inventors have developed an industrially valuable manufacturing method by irradiating adhesive polymers with ultraviolet rays, which uses an inexpensive polymerization vessel to obtain polymers with good polymerization state and peelability. As a result of further intensive research, we have developed a method for producing polymers or copolymers that inherently have adhesive or adhesive properties, with a method for producing polymers or copolymers that have an unsaturated double bond in contact with a polymerizable monomer solution. In the process of producing adhesive polymers, polymerization is carried out by irradiating ultraviolet rays using a polymerization device coated or equipped with a fluorine-containing copolymer resin on which a metal is vapor-deposited on the back side. When attached with a fluorinated ethylene-ethylene copolymer resin film, it is possible to obtain polymerization efficiency equal to or higher than that of the film and to reduce the adhesion or adhesion of the polymer. The inventors discovered that it is possible to use a polymerization reactor and completed the present invention. One of the features of the present invention is that continuous peeling is facilitated, and improvements have been made to the adhesive polymer so that it can be manufactured continuously, thereby further increasing its industrial value. Furthermore, since ultraviolet rays that exhibit polymerization activity can be effectively utilized, polymerization can be carried out efficiently. In the present invention, a fluorine-containing copolymer resin film is polymerized with fine metal particles of metal such as aluminum, chromium, nickel, or a mixture thereof deposited on one side of the film by a conventional vapor deposition method. It is attached to the part of the device that comes in contact with the monomer. As the fluorine-containing copolymer, a tetrafluoroethylene-ethylene copolymer is particularly preferred. The reasons why the tetrafluoroethylene-ethylene copolymer is preferable are as follows: (1) It has excellent resin moldability, good film moldability, is easy to heat seal, combine with rubber, and metal, and can be applied to polymerization containers. (2) It has excellent mechanical properties, especially tensile strength, and is highly applicable to polymerization vessels. (3) It has a very low gas permeability coefficient, has an excellent oxygen blocking effect, and has a high oxygen affinity on the film surface. Because it is small, polymerization inhibition on the film surface can be completely eliminated, and (4) it has excellent weather resistance, almost no UV deterioration, and has low UV transmittance at wavelengths of 300 to 400 mμ, which is necessary for UV irradiation polymerization. Because of its good properties, it is a suitable material for containers for ultraviolet polymerization. In the present invention, a conventional container such as a square or cylindrical container can be used as the polymerization container. Furthermore, a movable support such as an endless belt is coated with or attached to a fluorine-containing copolymer resin with a metal vapor-deposited on the back, and a monomer aqueous solution containing a photopolymerization initiator is applied in a thin layer. Continuously supplying, polymerizing by irradiating with ultraviolet rays from above, and continuously peeling the obtained polymer from the support,
In the method for producing a sticky polymer, which is characterized in that it obtains, continuous polymerization of monomers becomes possible. In the present invention, the adhesive polymer is produced by an ultraviolet irradiation polymerization method. The usable ultraviolet rays are 300~
500 mμ, preferably 350 to 400 mμ, and the ultraviolet intensity during polymerization is 2 to 100 W/m ² , preferably
It is 10-20W/ ^m2 . Examples of the polymerization initiator include benzoin, benzoin alkyl ether,
Known compounds such as benzophenone and anthraquinones can be used. The amount of such an initiator used is preferably about 0.001 to about 0.5% based on the weight of the monomer. In addition, the concentration of the monomer aqueous solution is about 15 to about 80% by weight,
Preferably, the polymerization is carried out at about 30 to about 70% by weight. If the amount of polymerization initiator used is less than about 0.001%, or if the aqueous solution concentration is less than about 15% by weight, sufficient polymerization will not occur. On the other hand, the initiator is about 0.5%,
Alternatively, if the concentration of the aqueous solution exceeds about 80% by weight, the degree of polymerization will decrease too much, which is not preferable. Polymerization is carried out using an aqueous monomer solution in which oxygen has been completely replaced with nitrogen or the like in a polymerization atmosphere that is deoxidized and filled with an inert gas such as nitrogen. Polymerization time is usually about 10 to about 60 minutes. If the above-mentioned time is too short, polymerization will not proceed sufficiently. On the other hand, if the time is too long, it is not only uneconomical, but also causes an undesirable crosslinking reaction to proceed, making it impossible to obtain the desired water-soluble polymer. When supplied onto a movable support, the aqueous solution has a thickness of about 3 to about 30 mm, preferably about 5 to about 15 mm. If the thickness is too thin, it is uneconomical, and if it is too thick, the polymerization heat generated during the polymerization stage cannot be completely removed, and the desired water-soluble polymer is not formed due to the translational crosslinking reaction. I can't. As described above, in the method of the present invention, materials that significantly inhibit the polymerization reaction caused by ultraviolet irradiation,
For example, stainless steel without mirror finish, SS material,
Adhesive polymers can be produced efficiently, uniformly, and even continuously using polymerization equipment made of colored or opaque resin materials, rubber materials, ceramics, etc., and the resulting polymer can be easily removed from the polymerization equipment. Can be easily peeled off. Next, the present invention will be explained based on examples.
Of course, the present invention is not limited to these embodiments. Examples 1 to 3 and Comparative Examples 1 to 3 Inner surface liquid part of a box-type polymerization apparatus (100 mm x 100 mm x 100 mm) equipped with a nitrogen blowing pipe, a thermometer, and a cooling jacket, and made of the materials shown in Table 1. To,
Tetrafluoroethylene-ethylene copolymer resin film with aluminum vapor-deposited on the back side (thickness 50μm)
Each was attached with adhesive and placed in a chamber filled with nitrogen gas. In this polymerization equipment, 100g of acrylamide and 25g of acrylic acid
and 14 g of sodium hydroxide were dissolved in 270 ml of distilled water, the prepared monomer aqueous solution was charged, and then nitrogen gas was blown in from the nitrogen blowing tube to remove dissolved oxygen contained in the aqueous solution. After adding 1.5 ml of benzoin methyl ether 1% acrylic acid solution and stirring uniformly, a light intensity of 50 W/m ² (as measured by an ultraviolet luminometer) was measured using an ultraviolet irradiation device installed at the top of the polymerization apparatus in the chamber. Polymerization was carried out for 30 minutes while water at 20°C was passed through the cooling jacket, and the polymerization state, polymerization rate, and peelability were measured and evaluated. The results are shown in Table 1. For comparison, Table 1 also shows the evaluation when polymerization was carried out in the same manner using a polymerization apparatus without an aluminum vapor-deposited resin film. The evaluation methods described above were as follows. Polymerization state: 〇 Uniform polymerization throughout the polymerization container x Large amount of unreacted liquid remaining near the wall of the polymerization container Polymerization rate: Cross the center of the produced polymer to a thickness of approximately 3 cm The meat was cut into pieces, homogenized using a meat grinder, and then measured using the KBrO ₃ method. Peelability: A: Peels off naturally when the container is turned upside down, or peels off by tapping the top of the upside down container B: Peels off with some manual effort, but
Items that do not peel off naturally even when the container is turned upside down Items C that cannot be peeled off manually Examples 4 to 6 and Comparative Examples 4 to 6 N, N, N- adjusted to pH 4 with a 10% aqueous hydrochloric acid solution
Trimethylaminoethyl methacrylate monomer
Using 500 g of 75% aqueous solution, replace 1.5 ml of benzoin methyl ether 1% acrylic acid solution with 1.2 ml of benzoin isopropyl ether 5% methanol solution.
Polymerization was carried out and evaluated in the same manner as in Examples 1 to 3, except that ml was used. The results are shown in Table 1. For comparison, Table 1 also shows evaluations when polymerization was carried out in the same manner using a polymerization apparatus without an aluminum vapor-deposited resin film.

[Table] Examples 7 to 9 and Comparative Examples 7 to 11 Width 450 mm, effective length made of the materials shown in Table 2
A 3000 mm endless belt is equipped with a tetrafluoroethylene-ethylene copolymer film whose back side is vapor-deposited with aluminum, and the structure is such that hot to cold water can be sprayed onto the endless belt from below. The belt was placed as a support in a chamber completely filled with nitrogen gas, moved at a constant speed of 100 mm/min, and water at 20°C was sprayed from below the belt. Furthermore, a low-pressure mercury lamp was installed above the movable support as an ultraviolet irradiation source, and the intensity of ultraviolet rays was set to 50 W/m ² . A 75% aqueous N,N,N-trimethylaminoethyl methacrylate monomer aqueous solution adjusted to pH 4 with a 10% aqueous hydrochloric acid solution was sufficiently degassed with nitrogen gas, and was placed on the belt in a movable state.
The feed was metered from one end of the belt at a rate of 1/hr. In addition, 30% benzoin isopropyl ether 5% methanol solution was added as a polymerization initiator from a temporary storage tank (5 volumes) with a stirrer installed above the belt.
The monomer aqueous solution was fed into the above monomer aqueous solution at a rate of 1 ml/hour, and the monomer aqueous solution and the polymerization initiator were uniformly mixed while being fed onto the belt to carry out polymerization by ultraviolet irradiation. Under the above conditions, the time during which the aqueous monomer solution was subjected to polymerization on the belt was 30 minutes, and the layer of the aqueous monomer solution during polymerization was about 5 mm. Thirty minutes after the start of supplying the monomer aqueous solution, a sheet-like polymer having a thickness of 5 mm was obtained from the other end of the endless belt. The obtained polymer was in a state where it could be easily peeled off from the belt surface by input, and continuous polymerization for about 3 hours was possible. In addition, the polymerization rate and polymerization state were measured and evaluated. The results are shown in Table 2. For comparison, continuous polymerization was carried out in the same manner using an endless belt made of the materials shown in Table 2 without attaching an aluminum vapor-deposited resin film, and the resulting polymer could not be easily peeled off from the belt surface. When peeling was attempted using a machine, the polymer sheet was torn, making continuous peeling impossible and making continuous polymerization impossible.
Table 2 also shows the results of comparative examples.

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Claims (1)

[Scope of Claims] 1. A method for producing a polymer or copolymer that essentially has adhesive or adhesive properties, wherein the contact area with a solution of a polymerizable monomer having an unsaturated double bond is placed on the back side of the polymer or copolymer. A method for producing an adhesive polymer, which comprises polymerizing it by irradiating it with ultraviolet rays using a polymerization device covered or equipped with a fluorine-containing copolymer resin on which a metal is vapor-deposited. 2. A method for producing a water-soluble polymer with adhesive properties by polymerizing an aqueous solution of a monomer having a polymerizable unsaturated double bond, the method comprising a fluorine-containing copolymer resin with a metal vapor-deposited on the back side. An aqueous solution of the monomer containing a photopolymerization initiator is continuously supplied in a thin layer onto the coated or attached movable support, and ultraviolet rays are irradiated from above the supplied monomer. 1. A method for producing an adhesive polymer, which comprises polymerizing the adhesive and continuously peeling the obtained polymer from the support.