JPS61120810A - Production of chlorosulfonated polyolefin - Google Patents

Abstract

PURPOSE:To improve the dynamic properties, low-temperature properties and adhesiveness without detriment to the features of a conventional chlorosulfonated polyolefin, by chlorinating and chlorosulfonating a specified polyolefin polymer. CONSTITUTION:A polyolefin polymer having a density <0.90 is used. As said polymer which can meet this property, a copolymer of ethylene with an alpha-olefin is desirable. Examples of other alpha-olefins include butene-1, hexene-1 and octene-1. Said polyolefin polymer is dissolved in an organic solvent (e.g., carbon tetrachloride or chloroform) in a concentration of, usually, about 2-40wt% and reacted at about 60-120 deg.C in the presence of a radical generator as a catalyst by adding both of chlorine gas and sulfur dioxide gas and/or sulfonyl chloride to the reaction system to obtain a chlorosulfonated polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing a chlorosulfonated polyolefin with excellent dynamic properties.

(Prior Art) Conventionally, as chlorosulfonated polyolefins, those made from low-pressure processed high-density polyethylene and those made from high-pressure processed low-density polyethylene are known. Recently, low-pressure linear low-density polyethylene (so-called L-L
It is known that chlorosulfonated polyolefins made from DPE) have excellent mechanical strength and low-temperature properties (for example, Japanese Patent Application Laid-Open No. 1983-1999).
201805). Taking advantage of its performance, these C chlorosulfonated polyolefin vulcanizates are also used as industrial materials such as electric wires, belts, bosses, gaskets, and canvases, as well as paints and adhesives.

(Problems to be solved by the present invention) Conventionally known chlorosulfonated polyolefin polymers are used for various purposes as rubber materials, but because of the structure derived from the raw material polyolefin, they have poor mechanical strength and dynamic properties. They did not necessarily have satisfactory properties for the required uses.

(Means for Solving the Problem) As a result of studies aimed at obtaining a chlorosulfonated polyolefin with excellent dynamic properties, the inventors of the present invention found that a polyolefin having a density of less than 0.90 was used as the raw material polyolefin. Through chlorination and chlorosulfonation, we have achieved a technology that allows a chlorosulfonated polyolefin with excellent dynamic properties to be obtained while retaining the properties of rice chlorosulfonated polyolefin.

According to the present invention, a rubber material can be obtained which has excellent dynamic properties, which could not be achieved with conventional chlorosulfonated polyethylene, as well as excellent low temperature properties and adhesive properties. Furthermore, when compared with other types of rubber, it can be said to be a chlorosulfonated polyolefin that has properties as a durable rubber material, with improved heat resistance of chloroprene rubber, and improved oil resistance and adhesive properties of ethylene propylene rubber.

The polyolefin polymer used in the present invention has a density of less than 0.90 f//Cr.

Although this polymer originally has some rubber-like properties, it does not have a normal vulcanization reaction point, so it is not used as a rubber material for industrial materials. A typical polyolefin polymer that satisfies this property is a copolymer of ethylene and α-olefin.

Other α-olefins include butene-1, hexene-1, octene-1,4-methylpentene-1,
etc. Commercially available polyolefins in this range include Tafmer manufactured by Mitsui Petrochemicals and Mitsui EPT.

The polyolefin polymer used in the present invention has a density of less than 0.90 r. 1,000
Each piece requires 55 or more pieces. In addition, main chain carbon atoms 1,0
The number of methyl branches per 00 is measured by 13C-NMR spectrum or infrared absorption spectrum.

Further, the melt index of the raw material polyolefin is not particularly limited, but it is preferably 05 to 50 f/10 min.

Note that the measurement method is based on JIS K-7210.

In the present invention, the reaction for chlorinating and chlorosulfonating a polyolefin polymer can be carried out by dissolving the polyolefin polymer in an organic solvent, suspending it in a solvent, or carrying out the reaction in a gas phase without using a solvent. However, since a uniform reaction is desired in order to exhibit the performance as a rubber material, it is preferable to carry out the method by dissolving it in a solvent. These polyolefin polymers are usually dissolved in an organic solvent at a concentration of 2 to 40 percent by weight, and then reacted with a radical generator as a catalyst at a temperature of 60 to 120°C by adding chlorine and sulfur dioxide gas and/or sulfuryl chloride. , resulting in a chlorosulfonated polyolefin polymer.

The organic solvent used in the reaction includes a solvent inert to the chlorosulfonation reaction, such as carbon tetrachloride, chloroform, tetrachloroethane, trim-ethane, ethylene tetrachloride, chlorobenzene, fluorobenzene, trichlorofluoromethane. etc., etc., are used. A good example is carbon tetrachloride.

As the radical generator, an azo catalyst such as α,α-azobisisobutyronitrile or azobiscyclohexanecarbonitrile or an organic peroxide catalyst such as benzoyl peroxide is used. Preferred is α,α'-azobisisobutyronitrile. Light, especially ultraviolet light, can also be used instead of radical generators. In addition, in this reaction, a small amount of an amine compound such as pyridine, quinoline, or tri-n-butylamine may be added as a cocatalyst, if necessary.

In particular, when using sulfuryl chloride, amine compounds are often used.

After the reaction is completed, the acidic dissolved gas remaining in the solution is removed by lowering the pressure. Add an epoxy compound as a stabilizer if necessary.

Methods for separating and drying the chlorosulfonated polyolefin from this reaction solution include (1) a steam distillation method in which the polymer liquid is fed into hot water, and (2) a dry film is formed by feeding the polymer liquid into a heated rotating drum. (3) an extrusion drying method in which the polymer liquid is concentrated if necessary and then separated using a vented extruder; any of these methods can be used.

The amount of chlorine and sulfur in the produced chlorosulfonated polyolefin are usually 5 to 50% by weight, respectively) and 0.1
~4. oz-1%, and is not particularly limited. However, when the raw material is a polyolefin polymer with low density as in the present invention, the amount of chlorine is 15 to 3.
At 0% by weight, crystallinity disappears and it becomes rubbery, which is preferable. However, when oil resistance is required, 30 to 45 weight percent is preferred. Further, the sulfur content is preferably 0.5 to 1.5 weight percent from the viewpoint of the balance of vulcanized physical properties.

The obtained chlorosulfonated polyolefin is suitably blended and vulcanized to form a vulcanizate. The vulcanizing agent is an essential component of the compounding agents added to chlorosulfonated polyolefin, and in addition, vulcanization accelerators, reinforcing agents, fillers, plasticizers, softeners, anti-aging agents, processing aids, and colorants are also included. There are other rubber chemicals.

Vulcanizing agents include metal oxides such as magnesia, litharge, tribasic lead maleate, dibasic lead phosphite, bisphenol epoxy resins, polyhydric alcohols such as pentaerythritol, and vulcanization accelerators such as: Thiuram series such as TRA (dipentamethylenethiuram, tetrasulfide), TET (tetraethylthiuram, disulfide), TT (tetramethylthiuram disulfide), DM (dibenzothiazyl disulfide), M (2-mercaptobenzothiazole), etc. Those used in ordinary chlorosulfonated polyethylene, such as thiazole type, sulfur, and ethylene thiourea, can be used. In addition, the total amount used is 1~
The amount may be 30 parts by weight; if it is too small, vulcanization will not occur, and if it is too large, it is not preferable.

As reinforcing agents and fillers, carbon black, silica,
Clay, calcium carbonate, acid, titanium oxide, organic reinforcing agents such as high styrene resin, talc, molten algae, mica powder, asbestos, aluminum sulfate, barium sulfate, calcium sulfate, glass fiber, wood powder, etc., as well as plasticizers, Softeners include phthalic acid derivatives, adipic acid derivatives, sebacic acid derivatives, petroleum-based softeners, vegetable oil-based softeners, etc. Anti-aging agents include naphthylamine-based, P-phenylenediamine-based, hindered phenol group, NBC (dibutyl-dithiocarbaminated nickel), etc., processing aids such as stearic acid, waxes, low molecular weight polyethylene, etc., and colorants such as inorganic organic pigments, which are used for ordinary chlorosulfonated polyethylene. Optionally, they can be added and used, but these are not limited to the above.

The rubber compound thus obtained usually has a 120 to 20
Although vulcanization is carried out at 0°C, the obtained rubber vulcanizate not only has excellent dynamic properties without impairing the mechanical properties of conventional chlorosulfonated polyethylene rubber vulcanizates, but also has low-temperature properties and It also has excellent adhesion.

(Example) In order to explain the present invention in more detail, examples are shown below. Departments and sections are based on weight.

Example 1 25 carbon tetrachloride odor was added to a reaction vessel made of 301 glass lining.
Density 0.88 f/IL, melt index (MI)
4.5.Propylene content by C-NMR 12
Mo1% ethylene and propylene copolymer (manufactured by Mitsui Petrochemicals Co., Ltd.; product name: Tafmer P-0180) 3K
After charging q and pressurizing to 2.0 gauge (gauge) with nitrogen,
The internal temperature was set to 100°C to dissolve the copolymer. After adding pyridine 0151 to this solution, α,α'-azobisinbutyronitrile 7? 30 kg of sulfuryl chloride was added while introducing a solution of 1.8 odor of sulfuryl chloride in carbon tetrachloride.

The addition time was approximately 4 hours. During this reaction, the temperature was 1-00'C and the pressure was 2.0 M (gauge). After the completion of the reaction, the internal pressure was reduced to 2.0 V in 2 hours.
(gauge) to 300 yrrn Hgabs to remove dissolved acidic gases. At this time, the temperature of the jacket Ittli of the reaction vessel was controlled so as not to differ from the temperature of the polymer solution.

After adding 50 r of bisphenol-based epoxy resin (manufactured by Yuka Shell Epoxy ■, trade name: Epicoat 828) as a stabilizer, the product was separated using a drum dryer in a conventional manner. The content of chlorine and sulfur in the product is 205 cm each,
It was 1.03%. Thermal analysis of the polymer was performed using a digital scanning calorimeter (DSC), but no melting behavior based on crystallinity was observed.

This chlorosulfonated polyethylene was compounded according to the following formulation, and then press vulcanized at 160° C. for 30 minutes, and the physical properties of the vulcanized product were measured. The results are shown in Table-1.

Compounding recipe Parts by weight Chlorosulfonated polyolefin 100 Stearic acid Magnesium monoxide
20FEF carbon
40 naphthenic oil
10 dipentamethylenethiuram tetrasulfide 2 Example 2 A chlorosulfonated polyolefin was obtained in the same manner as in Example 1 except that the sulfuryl chloride added was changed to 4.25 KF. As a result of analysis, this polymer contained 26.5% chlorine.
, and 1.1 h of sulfur. The blending and vulcanization were carried out in the same manner as in Example 1. These results are also shown in Table 1.

Comparative Example 1 Density 0.965 as raw material polyolefin, MI 7
．． 6. Using sulfuryl chloride using bird density polyethylene of 5.
Chlorosulfonated polyethylene was obtained in the same manner as in Example 1 except that 4 Kf was used. Analysis of this polymer revealed that it contained 35.2% chlorine and 1.05% sulfur.

The blending and vulcanization were carried out in the same manner as in Example 1.

The results are shown in Table 1.

Comparative Example 2 The raw material polyolefin has a density of 0.922 f/ω, Ml
is high-pressure low-density polyethylene of 7.2 and sulfuryl chloride of 5. A product was obtained in the same manner as in Example 1 except for 9 except for OKp. This polymer has an analysis result of 29.5
% chlorine and 1.41% sulfur. The blending and vulcanization were carried out in the same manner as in Example 1. These results are shown in Table 1. - Comparative Example 3 The raw material polyolefin has a density of 0.922 and an MI of 8.0.
It is a linear low-density polyethylene of
．． Chlorosulfonated polyethylene was obtained in the same manner as in Example 1 except that 6 was changed to 9. Chlorine and sulfur in the product were 321% and 1.03%, respectively. The blending and vulcanization were carried out in the same manner as in Example 1.

The results are shown in Table 1.

Comparative Example 4 Commercially available chloroprenecomb (CR) as an existing rubber material
Denka Chlorobrene M-40 and EPT (manufactured by Mitsui Petrochemicals, trade name: Mitsui EPT3045) were blended and vulcanized according to the formulation shown below, and their physical properties were measured. The results are summarized in Table 1.

Formula CR system (parts by weight) EPT system (parts by weight) M-40100Ep'r 100 magnesium oxide 4 Stearic acid Zinc monoxide 5 W zinc oxide 5
FEF carbon 40 FEF carbon
40 Naphthenic oil 1O Naphthenic oil 1゜2-Mercaptoimidacillin 0.35
Tetramethylthiuram 1 Monosulfide sulfur 1 Vulcanization conditions: 160°C x 30.160°C x 307 Among the physical properties, the measurement of heat generation increase temperature using a Gutdrich flexometer conforms to ASTM D62378 Meth
Measured based on odA. Other physical properties are JIS K
Measured according to 6301.

(Effects of the invention) As shown in Table 1, the chlorosulfonated polyolefin obtained by the production method of the present invention has a low exothermic upflow rate measured by a Gutdrich 7 rexometer, and has excellent dynamic properties comparable to chloroprene rubber and ethylene propylene rubber. I understand that.

According to the method for producing a chlorosulfonated polyolefin of the present invention, a chlorosulfonated polyolefin having excellent dynamic properties that could not be achieved with conventional chlorosulfonated polyolefins can be produced.

Procedural amendment January 17, 1985 Manabu Shiga, Commissioner of the Patent Office 1 Display of the case 1988 Patent Application No. 240540 2 Name of the invention Process for producing chlorosulfonated polyolefin 3 Person making the amendment Relationship with the case Patent Applicant address: 1-4-4, Yurakucho, Chiyoda-ku, Tokyo Name (329) Denki Kagaku Kogyo Co., Ltd. Contents of amendments to Column 5 of the detailed description of the invention in the specification (1) Meijyo Jwa page 9 Correct lines 12-13 to read "chlorosulfonated polyethylene."

Claims (1)

[Claims] A method for producing a chlorosulfonated polyolefin, which comprises chlorinating and chlorosulfonating a polyolefin polymer having a density of less than 0.90.