JPS60149602A - Production of self-adhesive polymer - Google Patents

Abstract

PURPOSE:To obtain the titled polymer which can be easily peeled from a polymerizer and is good in a state of polymerization and a polymer conversion, by polymerizing a solution of a polymerizable monomer by using a polymerizer coated or fitted with a specified copolymer resin. CONSTITUTION:A solution of a polymerizable monomer having an unsaturated double bond [e.g., (meth)acrylamide] is placed in a cubic, cylindrical or like-form polymerization vessel whose site in contact with the monomer solution is coated or fitted with a 10-100mum-thick layer of a tetrafluoroethylene/ethylene copolymer resin or in a bag made of the resin itself, and the monomer is polymerized in the presence of a thermal initiator such as a persulfate, or alternatively, said aqueous monomer solution is continuously fed in the form of a thin layer on a movable support, such as an endless belt, coated or fitted with the above resin and polymerized. The resulting polymer is peeled from the vessel or the support to obtain a polymer having strong stickiness or adhesiveness.

Description

DETAILED DESCRIPTION OF THE INVENTION In detail, it is a method for producing a water-soluble polymer with strong adhesiveness or adhesion, which allows the obtained polymer to be easily peeled from a polymerization container, and also allows for controlling the polymerization state and polymerization. The present invention relates to a method for producing a sticky polymer that can be coated with a good polymer content.

Traditionally, for example, (meth)acrylamide; (meth)
Acrylate: NIN-dialkylaminoalkyl (
Ni-containing acrylic acid esters such as acid salts or quaternary salts of meth)acrylates, acid salts or quaternary salts of N,N-dialkylamine hydroxyalkyl (meth)acrylates; diallylamine acid salts, diallyldialkylammonium salts, etc. Diallylamine compound; sulfoalkyl acrylate ml meta] methyl acrylate, (
Meta J ethyl acrylate, butyl (meth)acrylate,
(Water-insoluble (meth)acrylic Alt! esters such as hydroxyethyl methanoacrylate and hydroxypropyl (meth)acrylate; acrylamide alkyl sulfonate, (methane acrylamide derivative of dialkyl (meth) acrylamide); acrylonitrile; vinyl sulfonic acid When producing water-soluble polymers using vinyl group-containing monomers such as vinyl group-containing monomers or their salts, polymers with a high degree of polymerization generally produce relatively hard gels, but they tend to adhere to the walls of the polymerization vessel. , the adhesion is remarkable, and it is not easy to peel the polymer from the wall of the polymerization vessel.In addition, even with a low degree of polymerization, the adhesion and adhesion to the wall are strong, and once the polymer is attached to the wall, it is difficult to peel off the polymer. As a practical matter, it cannot be peeled off.

Normally, when producing these water-soluble polymers with high adhesiveness and adhesiveness, a method of applying a mold release agent to the wall surface of the polymerization vessel to improve the releasability (for example, Japanese Patent Application Laid-open No. 53-41386) ], in order to reduce the friction resistance on the wall of the polymerization container,
For example, a method using electrolytically polished stainless steel (for example, JP-A No. 54-10387 λ) or a method of coating the polymerization vessel wall with a synthetic resin to improve releasability (for example, JP-A No. 51-73583) It is widely known that the following treatments are performed.

However, among the above methods, the method of applying a mold release agent and the method of using an electrolytically polished material improve the tackiness and adhesion of the resulting water-soluble polymer, although they improve the releasability from the polymerization container. If it is large, peeling remains difficult, and a fundamental improvement has not yet been achieved.

On the other hand, in the method of coating the wall surface of a polymerization container with a synthetic resin, it is generally recognized that the releasability between the polymer having adhesive properties and the polymerization container is significantly improved.

As such synthetic resins, polyethylene, gellipropylene, polyester, polyamide, polytetrafluoroethylene, polytrifluorochloroethylene, polyvinyl chloride, epoxy resin, etc. are widely used. Among these, it is recognized that the releasability of heptad-containing resins such as polytetrafluoroethylene and polytrifluorochloroethylene is excellent.

However, when the vinyl yarn monomer aqueous solution is polymerized using a polymerization container coated with a synthetic resin as described above, the polymerization state near the interface between the resulting water-soluble polymer gel and the synthetic resin is In extreme cases, the vinyl monomer remains in the same state as it was before the reaction started even after the reaction is completed, causing a decrease in the polymerization rate and the yield of the polymer. Furthermore, in the case of highly toxic monomers such as acrylamide and monomers with strong odors such as (meth)acrylic acid esters, if large amounts of un↑-reacted monomers remain, environmental protection This will lead to pollution problems such as operational safety.

The above-described poor alignment near the coated synthetic resin is thought to be caused by oxygen present on the film surface.

Therefore, in the method using a synthetic resin-coated polymerization container,
It is necessary to select a synthetic resin material that does not adversely affect polymerization behavior.

In view of the above-mentioned actual situation, the present inventors have eliminated the above-mentioned problems,
The result of extensive research aimed at developing a method for producing a water-soluble polymer that is inherently sticky and adhesive and that can be easily peeled off from a polymerization vessel and that has an improved polymer yield. , we have completed the present invention.

That is, the present invention is a method for producing a polymer or copolymer that essentially has adhesive or adhesive properties, in which the contact area with a solution of a polymerizable monomer having unsaturated double bonds is replaced with tetrafluoroethylene. The gist of this invention is a method for producing an adhesive polymer characterized by polymerization using a polymerization apparatus coated with or equipped with an ethylene copolymer resin.

As a result of repeated experiments on the influence of many synthetic resins on polymerization, the physical properties of the resulting polymer, and the adhesion and peelability between the synthetic resin and the resulting polymer, the present invention was developed using a tetrafluoroethylene-ethylene copolymer. It has been discovered that the resin has excellent releasability without inhibiting polymerization and eliminates the above-mentioned drawbacks.

Although the tetrafluoroethylene-ethylene copolymer resin used in the present invention-c is one of the fluorine-based synthetic resins, it has better film physical properties than so-called Teflon (polytetrafluoroethylene or polytrifluorochloride ethylene). In particular, when vinyl monomers are polymerized, the effects on polymerization are completely different, and they have usefulness that cannot be imagined when Teflon is used.

Further, there has been no specific example of the use of the tetrafluoroethylene-ethylene copolymer resin used in the present invention in a polymerization system. Furthermore, no literature has been found suggesting that it has superior polymerization properties compared to commonly used polytetrafluoroethylene. The use of tetrafluoroethylene-ethylene copolymer resin is a novel technology provided for the first time by the present invention.

For example, the advantages of tetrafluoroethylene-ethylene copolymer resin over Teflon are as follows.

(1) Excellent resin moldability. Therefore, it is easy to combine with film adhesive molding, heat sealing, rubber, and metal, and it is easier to apply to polymerization containers than Teflon.

(2) Excellent mechanical properties. In particular, it has excellent tensile strength and is suitable for use as a polymerization container.

(8) It has a much smaller gas permeability coefficient (gas permeability) than Teflon, and therefore has excellent oxygen blocking effects. In addition, since the film surface has low oxygen affinity, polymerization inhibition on the film surface, which is a serious drawback when using Teflon, can be completely eliminated. This is achieved only by the present invention, and is an important point of the present invention.

(4) Excellent weather resistance and almost no UV deterioration. In addition, it is suitable as a material for a container for ultraviolet polymerization because it has better ultraviolet transmittance than Teflon at wavelengths of 300 to 400 M, which is necessary for ultraviolet irradiation polymerization.

In the present invention, the polymerization container may be a conventional container such as a square or cylindrical container coated or fitted with a tetrafluoroethylene-ethylene copolymer resin, or a bag made of the resin itself. When coating or attaching a copolymer resin, the thickness of the film is usually 10 to 10
0 μm, preferably 25 to 75 μm.

A movable support such as an endless belt is coated with or attached to a tetrafluoroethylene-ethylene copolymer resin, and then a thin layer of an aqueous solution of a monomer having polymerizable unsaturated double bonds is continuously applied. In the method for producing an adhesive polymer, which is characterized in that the monomer is supplied to the substrate for polymerization and the obtained polymer is continuously peeled off from the support, continuous polymerization of the monomer becomes possible.

In the present invention, polymerization is carried out using commonly used thermal initiators such as persulfates, azo initiators, peroxides, redox initiators of persulfates and potassium sulfite, persulfates and amine compounds, etc. This can be carried out using a redox initiator such as Further, an ultraviolet irradiation polymerization method using benzoin, benzoin alkyl ether, benzoquinones, or a radiation polymerization method using γ rays may be employed.

Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples.

Example 1 and Comparative Example 1.2 A box-shaped stainless steel polymerization vessel (100 mm x 100 m+n
) on the inner surface of the various synthetic resin films shown in Table 1 (thickness 5
Acrylamide 100 and acrylic acid 25. and sodium hydroxide 14. Pour a monomer aqueous solution prepared by dissolving 270 m6 of distilled water, then perform nitrogen gas replacement to remove dissolved oxygen, and add 5 ml of 5% potassium persulfate solution.
and 6 ml of 5% sodium sulfite solution, and polymerized for 3 hours while passing 25 c) L3 of water into the jacket to evaluate the effect on the polymerization behavior of the synthetic resin material and the adhesion between the resulting polymer gel and the surface of the polymerization container. did. The results are shown in Table 1.

It should be noted that each evaluation method shown in Table 1 seemed to be the same.

Polymerization state: O Polymerization is uniform throughout the entire interior of the polymerization container × A large amount of unreacted liquid remains near the wall of the polymerization container Polymerization content: The center of the produced polymer is approximately 3 cm thick. After cutting it into a crosswise shape and homogenizing it with a meat grinder, KBrO
It was measured by three methods.

Peelability: Human Does it peel off naturally when the container is turned upside down?
Or one that peels off by lightly tapping the top of an inverted container B. One that peels off with some manual force, but does not peel off naturally even if the container is turned upside down. Example 2 and Comparative Example 6.4 N, N, N-1 -Trimethylaminoethyl methacrylate chloride 80% aqueous solution 500. After adjusting the pH to 4 using a 10% aqueous hydrogen chloride solution, the total amount was adjusted to 565% with distilled water. The obtained product was charged into the polymerization container used in Example 1, and polymerization, measurement, and evaluation were carried out in the same manner as in Example 1. The results are shown in Table 1.

Example 3 and Comparative Example 5.6 Acrylamide 100 acrylic acid 25 g and acrylic acid 1 thyl ester 15 were dissolved in 6009 distilled water and 40% sodium hydroxide aqueous solution 35. The aqueous monomer solution prepared by adding I) H7.5 was charged into the polymerization vessel used in Example 1, and polymerization, measurement, and evaluation were carried out in the same manner as in Example 1. The results are shown in Table 1.

Table 1 Example 4 and Comparative Example 7.8 Width 450 mm, effective length 6 with tetrafluoroethylene-ethylene copolymer film (thickness 50 μm) attached to the surface
．． A 000 mm stainless steel endless belt with a structure that allows hot to cold water to be sprayed on the back side was used as a movable support for polymerization, and was installed in a room completely filled with nitrogen gas. Move at a constant speed of minutes,
The back side of the belt was sprayed with 60% water.

Approximately 30 liters of a 75% concentration N,N,N-) dimethylami7ethyl methacrylate monomer aqueous solution adjusted to pH 4 with a 10% aqueous hydrogen chloride solution was thoroughly degassed with nitrogen gas, and 10 1/ A fixed amount was supplied from one end of the belt at a rate of 1 hour.

In addition, a temporary storage tank (51
A 5% potassium persulfate solution and a 5% potassium persulfate solution and an IJ solution were placed as polymerization initiators in the tank, and the solution was 70-70% each.
It is fed at a rate of 7 hours, added to the monomer aqueous solution while mixing, and continuously fed onto the belt while being mixed uniformly.

Under the above conditions, the time during which the monomer aqueous solution was subjected to polymerization on the belt was 100 minutes, the monomer aqueous solution layer during polymerization was about 12 mm, and the total polymerization time was 2 hours.

100 minutes after the start of supply of the monomer aqueous solution, a sorted polymer with a thickness of about 12 mm was transferred from the other end of the endless belt. The obtained polymer could be easily peeled off from the belt surface by hand, and continuous polymerization for about 6 hours was possible.

For comparison, polymerization was carried out on an endless belt in the same manner as above except that the tetrafluoroethylene-ethylene copolymer film was not attached (Comparative Example 7). was not easily peeled off. When peeling was attempted using a machine, the polymer sheet was torn, making continuous peeling impossible and making continuous polymerization impossible.

In addition, instead of the tetrafluoroethylene-ethylene J1 film, a tetrafluoroethylene polymer film (thickness 50μ
The same polymerization was carried out in accordance with Example 4 except that m) was installed (Comparative Example 8).

The resulting polymer sort could be easily peeled off manually, but a large amount of unpolymerized monomer liquid existed at the interface between the polymer sheet and the tetrafluoroethylene polymer film, making it difficult to perform continuous polymerization. No industrial value was found.

Procedural amendment (method) % formula % 1 Indication of the case Patent Application No. 5235 of 1982 2 Name of the invention 3 Process for producing adhesive polymer 3 Relationship with the case Patent applicant 5 Subject of amendment (1) Contents of amendment 6 to the application form (1) Add the indication “(Patent application pursuant to the proviso to Article 68 of the Patent Act)” to the right shoulder of the application form.

(2) After line 5 of the application, add the following statement: "Number of inventions stated in the scope of claims: 2".

that's all

Claims (1)

[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 tetrafluorinated. A method for producing an adhesive polymer, which comprises polymerizing using a polymerization device coated with or equipped with an ethylene-ethylene copolymer resin. 2. A method for producing a water-soluble polymer with strong adhesiveness by polymerizing an aqueous solution of a monomer having a polymerizable unsaturated double bond, the method comprising coating or attaching a tetrafluoroethylene-ethylene copolymer resin. adhesive, characterized in that an aqueous solution of the monomer is continuously supplied in a thin layer onto a movable support, polymerized, and the resulting polymer is continuously peeled off from the support. Polymer manufacturing method.