JPS6031854B2 - Emulsification method - Google Patents

Description

[Detailed Description of the Invention] Sulfohalogenated polyolefin is an elastomer with excellent weather resistance, ozone resistance, etc., and its latex is also widely used, taking advantage of these characteristics.

In particular, terpolymer rubber (hereinafter referred to as EPDM) is composed of a Q-olefin higher than ethylene and a non-conjugated diolefin.
(hereinafter abbreviated as 11R) or an adhesive between rubbers such as isobutylene-isoprene copolymer rubber (hereinafter abbreviated as 11R) and fibers such as polyamide, aromatic polyamide, polyester, pinylon, rayon, etc., or other adhesives as adhesive raw materials. It is useful because it exhibits characteristics that cannot be simulated. In this case, a sulfohalogenated polyolefin is generally used, and a solcine-formalin-latex adhesive (hereinafter abbreviated as RFL) is used.
used as a latex component. As a method for latexizing sulfohalogenated polyolefins, US Pat. -Methyl-7-ethyl unde force noru 4
-Examples include the use of emulsifiers such as sulfuric acid ester 1'2 soda salts, high molecular weight carboxyl esters, alkylaryl polyether alcohols, long chain sulfonated alcohols, and high molecular weight carboxylic acids and their metal salts. However, the sulfohalogenated polyolefin latex obtained using these emulsifiers has poor mechanical stability and causes disadvantageous phenomena such as agglomeration during pumping.

Further, especially when the latex is concentrated to a solid content of 30% or more, the storage stability is poor, and problems such as latex particles settling over time tend to occur. On the other hand, Sulhoha.

As mentioned above, the polyolefin latex has the following properties:
In the form of RFL, it is used as a bonding agent between rubber such as EPDM or 11R and fibers (Hakamabuta 1986-12).
7425) Its usage is usually pre-prepared RF
Fibers are continuously immersed in a tank of L liquid, dried and aged (generally called baking), and then vulcanized and bonded to rubber. In this case, the RFL liquid is often prepared in batches. , it often takes a very long time to use it. Therefore, it is desired that the expedient time of the RFL liquid (referring to the period until it solidifies into agar-like form; if such solidification occurs, it will not be able to smoothly soak into fibers) is as long as possible.
Although there may be slight changes depending on the temperature at which the RFL liquid is prepared or other preparation conditions, if a conventional emulsifier is used to emulsify and a sulfohalogenated polyolefin latex is obtained, the release time of the RFL liquid will be approximately the same. , 2~
It is not possible to apply the above conditions of use within about 3 days.

The present inventors conducted intensive studies on a method for obtaining a sulfohalogenated polyolefin latex with excellent mechanical stability, storage stability, and RFL liquid stability, and surprisingly found that polyoxyethylene alkyl phenyl ether sulfate The present invention was based on the finding that a utex satisfying all of these conditions can be produced when emulsified using an ester salt.

That is, the gist of the present invention is to disperse a solution of a sulfohalogenated polyolefin in an organic solvent in water in the presence of an emulsifier, and then to distill off the organic solvent to produce a sulfohalogenated polyolefin latex. This is an emulsification method characterized by using at least one kind of tyrene alkyl phenyl ether sulfate ester salt.

The emulsifier used in the present invention has the general formula [wherein R: a hydrocarbon group having 2 to 20 carbon atoms, n=
1 to 99 (representing the average number of moles of EO added to 1 mole of phenol group), ×=sodium, potassium or ammonium], which can be used alone or Two or more types can be used.

The number of added moles of EO constituting polyethylene oxide can usually be 1 to 99, but preferably 3 to 50.
Good results are often obtained using molar additions.

The amount of emulsifier used is 1 sulfohalogenated polyolefin
The amount is 0.1 to 2 parts by weight per 00 parts by weight.

If the amount used is less than that, sufficient emulsification will not be possible, and if more than that is used, it will not only be economically disadvantageous but also have negative effects such as a decrease in the adhesive strength between the target rubber and fibers. It cannot be said that it is advantageous in that there are cases where it has no effect. It is also possible and often advantageous to use a combination of the emulsifier of the present invention and conventional emulsifiers such as polyoxyethylene sorbitan monolaurate and organic carboxylic acid salts.

The sulfohalogenated polyolefins used in the present invention include homopolymers of ethylene, propylene, n-butylene, isobutylene, ptagene, isoprene, mutual copolymers of any two or more of these, and ethylidenenorbornene, 5-methyl-2-norbornene, 1,4
- Non-conjugated dienes such as hexadiene, dicyclobentadiene, 1,5-cyclooctadiene, divinylbenzene, styrene, vinyl chloride, vinyl acetate, acrylic acid,
Copolymers of methacrylic acid, various acrylic acid esters, and various methacrylic acid esters are combined with halogen and sulfur dioxide or C.

It is a polymer with a structure thought to have been produced by treatment with sulfuryl genide, and is usually produced by sulfohalogenation of an appropriate polymer, either alone or as a mixture. The organic solvent for dissolving the sulfohalogenated polyolefin is not particularly limited, and may be selected from aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated hydrocarbons such as trichlorethylene and carbon tetrachloride. You may select and use the appropriate one.

After preparing the emulsion, the organic solvent is distilled off by heating under reduced pressure, and water is removed as necessary by heating, far-D separation, furnace filtration, etc. until the latex reaches the desired concentration. good.

The method for preparing the RFL liquid is as shown in the preparation of the RFL liquid in Examples below.

The emulsification method is generally carried out by mixing an organic solvent solution of a sulfohalogenated polyolefin with an aqueous solution containing at least one emulsifier used in the present invention. The sulfohalogenated polyolefin latex obtained by the method of the present invention shows no precipitate even after being stored for several months, and when it is mixed with RFL liquid, no solidification phenomenon is observed even when it is left at room temperature for more than 10 days. Ta.

Furthermore, no coagulum was observed in tests using a stability tester. Examples will be described below, but it goes without saying that the present invention is not limited thereto.

Example 1 Sulfochlorinated polyethylene (chlorine content 35%, sulfur content 1
%) 12k9 was dissolved in toluene 68k9.

On the other hand, polyoxyethylene (addition of 0.4 mol of E) octylphenyl ether sulfate ester sodium salt [manufactured by Nippon Oil & Fats ■, trade name: Trax H-45] 1.2 to 40 kg of water
k9 (purity 30%) and polyoxyethylene (E.0.
30 mol addition) nonyl phenyl ether sulfate ester soda salt (manufactured by NOF ■, trade name Trax N-300)
] 690 (purity 35%) and caustic potash 84 were prepared, and the two solutions were thoroughly emulsified using a milk-equipment machine (T.K. homo mixer manufactured by Tokushu Kika Kogyo Co., Ltd.). The emulsion thus obtained was transferred to a stainless steel container of 200 mm and heated by circulating 70 mm of hot water through the jacket under reduced pressure of 150 to 100 Hg to distill off toluene and the like.

After cooling, product 30k9 was obtained.

The solids content of the product was 40%. (Storage Stability) A product similar to LOO was placed in a graduated test tube with an inner diameter of 200 mm and observed after being left for several months, but almost no sediment was observed.

(RFL liquid stability) Preparation of ORF liquid 11 parts of resorcinol and 162 parts of a 37% formalin aqueous solution were mixed with a solution prepared by dissolving 0.4 parts of caustic soda in 24 parts of water, and the mixture was left to age at room temperature for 5 hours.

Adjustment of ORFL liquid Mix 27.5 minutes of the above product latex and 20 minutes of RF liquid.
The mixture was left to ripen at room temperature for 2 hours.

Even when the RFL liquid was left at room temperature for 10 days, no phenomenon of solidification into an agar-like state was observed.

An adhesion test between an EPDM compound and a nylon cord was measured by the method described in (Samurai Iso-sho 56-127425), but 5.
The adhesive strength was on the 9k9/9 side.

(Mechanical stability) The product was tested at 1400p using a Klaxon type stability tester.
A test was conducted for 1500 seconds at m, but no coagulum was observed.

Comparative Example 1 Latex 3 was prepared in the same manner as in Example 1 except that polyoxyethylene (E, 0.5 mol added) sorbitan monooleate 2k9 (purity 30%) was used as the hair thinning agent.
Got 0k9.

(Storage Stability) When 100 skins of the product were placed in a graduated test tube with an inner diameter of 200 and allowed to settle for one week, there was a precipitate of approximately 5'.

(RFL liquid stability) An RFL liquid was prepared in the same manner as in Example 1, but after 3 days of preparation, it solidified into an agar-like state, and after that, it was difficult to soak the fibers.

Examples 2 to 4 Latex was obtained by using a sulfochloride made from the polyolefin shown in the table below instead of the polyethylene of Example 1,
The four items shown in Example 1 were tested, and the results were almost the same in all cases.

Example 5 A latex 30 was prepared in the same manner as in Example 1, except that polyoxyethylene (E.0.20 mole addition) nonylphenyl ether sulfate potassium salt was used as the emulsifier.
I got k9.

Tests on storage stability, RFL liquid stability, adhesive strength, and mechanical stability were conducted using this product, and almost the same results were obtained.

Example 6 The polyoxyethylene used in Example 1 (E.0.30
All procedures were carried out except that polyoxyethylene (E.0.20 molar addition) sorbitan monolaurate (manufactured by Atlas, trade name Tween 20) 240 molar addition was used instead of nyl phenyl ether sulfate ester sodium salt. Latex was obtained in the same manner as in Example 1, and four tests were conducted, with almost the same results in all cases.

Example 7 EPDM [manufactured by Sumitomo Chemical ■, trade name Esplen 501A]
Sulfochlorinated EPDM (chlorine content 25%
, sulfur content 1%) 6k9 was dissolved in kg of toluene.

On the other hand, 1.2 kg of polyoxyethylene (addition of 0.4 mol of E) octyl phenyl ether sulfate ester sodium salt and 120 kg of sorbitan monolaurate (addition of 0.2 mol of E) were added to 60 k9 of water. A dissolved solution was prepared, and this solution was thoroughly emulsified using a milk emulsion machine. Thereafter, the same treatment as in Example 1 was carried out to obtain product 15k9.

Four items were tested, and good results were shown in all cases.

Claims (1)

[Claims] 1. A method for producing a sulfohalogenated polyolefin latex by dispersing an organic solvent solution of a sulfohalogenated polyolefin in water in the presence of an emulsifier, and then distilling off the organic solvent, in which polyoxyethylene is used as an emulsifier. At least one alkyl phenyl ether sulfate salt
An emulsification method characterized by using seeds. 2. The method according to claim 1, wherein 0.1 to 20 parts by weight of the polyoxyethylene alkyl phenyl ether sulfate salt is used per 100 parts by weight of the sulfohalogenated polyolefin. 3. The method according to claim 1, wherein the sulfohalogenated polyolefin is sulfochlorinated polyethylene. 4. The method according to claim 1, wherein the sulfohalogenated polyolefin is sulfochlorinated EPDM.