JPS5984911A - Manufacture of chloroprene polymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

The present invention relates to a method for producing υchloroprene polymers by polymerizing dienes and alpha-olefins in the presence of functionalized xanthocarbon disulfides. The xanthone sosulfide of the present invention has the general formula [wherein,
Two R's are the same or different and represent the following group: Here, X is alkyl having 1 to 6 carbon atoms (methyl, ethyl, isopropyl, hexyl),
Phenyl, naphthyl, benzyl, chlorine, odorant and iodine are preferred. The invention particularly relates to the general group 1-gen disulfide in which the two radicals R are identical and the radical X represents hydrogen or alkino (preferably 'i'-Ct~c6). Another object of the invention is to react the alcohol of ROIi, where R has the same meaning as above, with carbon disulfide to form an alkali metal kibuntate, and then to oxidize it. The purpose of the present invention is to present a process for the preparation of kipuntogen disulfide according to I, which is characterized in that it gives xa71-gen disulfide.For this purpose, alcohols having the following radicals R are particularly suitable: This method generally works as follows:
Start with an alkaline aqueous solution, for example, a 20-50% potassium or sodium hydroxide aqueous solution. Approximately equimolar amounts of alcohol RQ Ii (where Ru has the same meaning as above) are added. Carbon disulfide is gradually added to this mixture. This carbon disulfide can be added in equimolar amounts or in excess. An exothermic reaction immediately occurs and gyzantate is formed. During this reaction, the reaction temperature was 50'C.
Cool the mixture so that it does not overcoat. This reaction can be expressed as: R011+A
iυIi+C8, →R-0-C-S-Afl-1420
1 In the formula, 14=alkali metal 1. and R has the same meaning as above]. The resulting aqueous xanthate solution is then oxidized to xanthate disulfide by adding (as an aqueous solution) a suitable oxidizing agent such as hydrogen peroxide or potassium peroxydityl phate. At this time, water-insoluble xanthogen disulfide precipitates. This is then separated from the aqueous phase, e.g. by filtration or decantation.
1. L and dry. This reaction can be expressed as follows: S s S where R is as defined above. This reaction is carried out by one example, Kirk-Othmer (Kirk-Oth).
mer), [Encyclopedia of Chemical Technology, ia ofC
Chemical Technology) J, 2nd edition +
Volume 22. pp. 419-429 (1970), and Ullmann (Ul.
1mann), “Encycloperlie”
Der Tech. Chimi e”, Volume 18, pp. 718-728 (
The process is analogous to the method for preparing dialkylxanthogen disulfides as described in (1967). Another object of the present invention is to polymerize one or more conjugated diolefins in the presence of a radical-forming initiator in the presence of a general xanthogen disulfide as a molecular weight modifier, or one or more An object of the present invention is to provide a method for copolymerizing a conjugated diolefin with an α-olefin. Particularly suitable 1. The c-conjugated Geo1/fin is butadiene. Imprene, hyperylene, chlorofucin and D2r
It has 4 to 8 carbon atoms, such as 3-dichlorobutadiene. More specifically, 1) CL) 60 to 100 parts by weight of chloroprene and raw hydrogen are mixed in an aqueous dispersion with 0.05 to 30 parts by weight, preferably 0.15 to 5 parts by weight, of &I xanthogen disulfide. The present invention relates to a simple process for the preparation of chloroprene polymers, characterized in that they are polymerized under a spinal pressure of 0.815 to 1 part by weight. The α-olefins used are preferably acrylonitrile, styrene and ethyl acrylate. These comonomers are usually present in amounts up to 40 parts by weight based on the diolefin. Suitable radicals forming polymerization catalysts are, for example, peroxides and azo compounds or so-called redox systems. The following are examples: cumene hydroperleoxide. Pinene hydroperoxide, potassium peroxydisulfate, tert-butyl peroxide. Azobisisobutyronitrile. The redox system. peroxide 1 e.g. cumene hydroperoxide and reduction a
A combination of compounds such as formaldehyde sulfoxylate), iron salts or formamidine sulfinate. The polymerization reaction is preferably carried out in an aqueous emulsion. an "aqueous phase" containing at least 0.1 to 5 parts by weight of emulsifier;
Starting from , give an aqueous emulsifier solution. Suitable emulsifiers are, for example, alkali metal salts of alkylsulfonic acids, alkali metal salts of sulfonic acids, long-chain carboxylic acids, resin acids and polyether alcohols. Monomer is then added to this aqueous phase at a concentration of 0, fl 5 to 30 weight M, based on the monomer.
, 15 to 1 xanthogen disulfide tow, ltI [emulsify and add radical generation initiator. Polymerization reaction at -50 to 100°C, preferably 5 to 50°C
It is carried out at a temperature of This process is described in US Pat.
, No. 042,652, No. 3,147,317 and No. 3
．． No. 147,318 is essentially known regarding the polymerization of chloroprene. When 50 to 100% of monomer is polymerized, preferably 50 to 70%, unreacted monomers are removed and polymerized by precipitation with an electrolyte or freezing and drying of the aggregate. The polymer is recovered from the aqueous emulsion. In this polymerization, the xanthogen disulfides of &I act as molecular weight modifiers, i.e. they reduce the molecular weight of the polymer obtained in the absence of xanthogen disulfide. The xanthogen disulphides of Formula I are particularly suitable for modifying the molecular weight of chloroprene polymers. The chloroprene polymer produced gives a vulcanizate with improved mechanical properties, which is a mixture of non-crosslinked benzene-soluble polychloroprene and slightly cross-linked benzene-insoluble polychloroprene prepared according to the invention. These mixtures are easy to process and their vulcanizates have particularly high tensile strength. The tensile strength of the vulcanized polymers is due to the reaction with the terminal groups of the The reagent 1 is further improved by vulcanization, for example in the presence of a masked diincyanate.It is therefore another object of the invention to
A non-crosslinked benzene-soluble compound prepared from chloroprene and optionally up to 40% by weight (based on the monomer mixture) of an alpha-olefin in the presence of 0.05 to 30% by weight of xanthogen disulfide. The purpose of the present invention is to provide a mixture of chloroprene polymer+Gl and cross-linked benzene-insoluble chloroprene polymer. The benzene-soluble chloroprene polymer (a
) is the above product. More specifically, 1 the present invention provides (a) a diene and/or an α-olefin in which the chloroblef 60 and 100 overlapped parts and the water atoms are partially or completely substituted with rogen atoms; xanthogen disulfide (&I) in an aqueous dispersion.
1,05 to 30 parts by weight, preferably 0.15 to 5 parts by weight and especially 0.15 to 1 part by weight, crosslinked to give a weak penzene-soluble polymer, and then (b) Chloroprene 80-1 (,1(1
Part by weight and novinyl compound and/or α-olefin 2
0 to 0 parts by weight of a cross-linked benzene-non-G chloroprene homopolymer or copolymer, with components I and B being mixed in a ratio of 20=1 to 1:20;
Preferably, they are mixed in a weight ratio of 1:1 to 7:1. It is characterized by The present invention relates to a simple method for producing Rolobrene polymer mixtures that are easy to process. Furthermore, the present invention provides a xanthogen disulfide of formula I (1,
05 to 30 parts by weight, 60 to 10 parts by weight of chloroprene prepared under pressure (<0.115 to 5 parts by weight and especially 0.15 to 1 part by weight) and hydrogen atoms partially or completely... 5 to 95 parts by weight of a non-crosslinked benzene-soluble chloroprene homopolymer or copolymer consisting of 40 to 0 parts by weight of a diene and/or α-olefin which may be substituted with a chlorogen atom; 55 to 90 parts by weight,
and 95 to 5 parts by weight of a cross-linked benzene-insoluble chloroprene homopolymer or copolymer consisting of 780 to 100 parts by weight of chlorapre and 20 to 0 parts by weight of a novinyl compound and/or an α-olefin. It also relates to mixtures with Suitable benzene-insoluble crosslinked chloroprene polymers can be prepared by various methods that provide the crosslinked polymer in latex form. Chloroprene can be converted to high conversions in the absence of chain transfer agents, such as alkyl mercaptans or dialkyl xanthogen disulfides, or in the presence of only small amounts of such agents.
Suitable methods for carrying out such processes to high degrees of polymerization are described, for example, in U.S. Pat. No. 3,147;
It is described in No. 317. In another method for producing cross-linked chloroprene, a comonomer that is copolymerizable with chloroprene and that contains two or more polymerizable double bonds is added to the polymerization reaction. Added. Suitable comonomers for this purpose are, for example, divinylbenzene, and methacrylic acid and polyhydroxy compounds such as esters of alkylene glycols, dihydroxybenzene or trimethylolpropane. The cross-linked chloroprene polymer can be prepared in the same manner as is known for preparing benzene-soluble chloroprene polymers, but in this case the monomer conversion is increased to, for example, 90 to 100 parts. . Another method of preparing suitable crosslinked chloroprene polymers involves subjecting the non-crosslinked chloroprene polymer latex to post-treatment to effect the crosslinking. Such post-treatments are described, for example, in U.S. Pat. No. 3,042,65.
2 and treatment with peroxy compounds according to US Pat. No. 3,147,318. In cross-linked polymers, a portion of chloroprene,
That is, up to about 20% can be replaced with other monomers. Suitable comonomers are the same as those described above for the benzene soluble polymers. The benzene-insoluble chloroprene polymer is preferably a copolymer of chloroprene and a diester of dihydric aliphatic alcohol and acrylic acid from 2 to 20 parts by weight (chloroprene base). These diesters have the general formula: R, Q Q R2 [wherein R1 and R1 represent hydrogen, alkyl having 1 to 4 carbon atoms, or chlorine, and X represents 2 to 20 carbon atoms]
represents an alkylene group]. The following are examples of such compounds: ethylene dimethacrylate, propylene dimethacrylate, ethylene diacrylate, propylene diacrylate, phethylene diacrylate, and isobutylene diacrylate. These products are prepared by polymerization of chloroprene and copolymerization of butadiene and acryloni-1-lyl in conventional aqueous emulsions. This process and the products obtained thereby are disclosed in British Patent No. 1,158,970. The components of the elastomer mixture are preferably brought together by vigorously stirring the latex. Then conventional methods 1 such as freeze aggregation (U.S. Pat. No. 2.1
87,146) or dried on rollers (U.S. Pat. No. 2,914,497). Precipitation with electrolytes is also possible. Alternatively, the components may be kneaded and recovered individually in a conventional manner and then mechanically mixed, for example on mixing rollers or by Banbury mixing (sometimes a Werner-Pféiderer). Internal mixing like a machine (kneading in the table)
g). In the case of polychloroprene, the benzene soluble component (CL)
The weight ratio of burning to the cross-linked component (b) is 20:1.
~1:20. Preferably, the ratio may be 1:1 to 7:1. This mixture should contain at least 50% by weight of the benzene soluble component (α). The polychloroprene mixture according to the invention forms a vulcanizable rubber mixture when kneaded and can be vulcanized in the same way as conventional polychloroprene. They can be used as vcB for all purposes for which chloroprene polymers are suitable. Their primary advantage is improved processability when compared to benzene-poured polychloroprene and hbenzene-insoluble polychloroprene, each alone. Soi
The thermal stability of T et al. is substantially improved compared to known mixtures of benzene soluble and benzene insoluble polychloroprenes. When comparing the benzene-soluble polychloroprene prepared in the presence of xylene disulfide of &I with that prepared in the presence of mercaptan as a molecular modifier,
It has been found that they are very good in terms of the tensile strength of the vulcanizate. This tensile strength can be further improved when vulcanized with masked diisocyanates. -That’s it! What does it mean? -Production example of disulfide To produce xanthogen disulfide of hexanetriol monoacetal, 88 g of sodium hydroxide and 9]j of distilled water were placed in a 3e flask, and while stirring the sodium hydroxide ( Hydroxy-hexibun-1,2-diol acetal 2921 of formula a below was then added and the reaction mixture was stirred for 2 hours. It was then cooled to 10°C and carbon disulfide 184z was stirred. The xanthate was then added dropwise.During this reaction, the temperature should not be allowed to rise above 20°C, when all the carbon disulfide had been added.The whole mixture was stirred for a further 2 hours.The xanthate was then formed. A solution consisting of ammonium persulfate 3 (10!?) and distilled water was added dropwise to the reaction mixture. The xanthogen disulfide formed by the oxidation was then removed from the aqueous phase, washed with distilled water and taken up in ether. The ether phase was dried over anhydrous sodium sulfate. The solvent was removed on a rotary evaporator. The yield of xanthogen disulfide was 36 og. To prepare, put 881 g of sodium hydroxide and 90 g of distilled water into a 3e flask,
The IJum was dissolved while stirring. Next, 348 g of the formula 6-hydroxy-hexane-1,2-diol-monocool (hexanetriol monoatar)
- was added and the mixture was stirred for an additional 2 hours if1. The reaction mixture was cooled to 10°C and carbon disulfide 184
1 was added dropwise without stirring. During this period, the temperature
Do not allow the temperature to rise above 0℃/ζ. Stirring was continued for an additional 2 hours after all the carbon disulfide had been added. Next, 300 g of ammonium persulfate and 2 ml of distilled water were added to the reaction mixture containing the xanthate produced in this reaction.
A δ solution consisting of e was added one after another. Subsequently, the xanthogen disulf.f obtained by oxidation
7. Separate the liquid from the aqueous phase, wash with distilled water, and collect in a refrigerator. This ether phase was dried over anhydrous sodium sulfate. The solvent was then evaporated on a rotary evaporator. The yield of xanthogen disulfide was 358 g. In order to produce xanthogen disulfide of -di, - and 1-10glycero-nobimonoacetal, 88g of sodium hydroxide and 90p of distilled water were placed in a flask No. 31, and 1-lium hydroxide was dissolved with stirring. did. A mixture of clycerol monoacetals of formulas CI and G2 obtained by reacting chrycerol with formaldehyde was then added completely and stirring was continued for 2 hours. C.I.G.
2 The reaction mixture was cooled to 10°C. Next, 184f of carbon disulfide was added dropwise while stirring. The temperature was not allowed to rise above 20°C during this operation. Stirring was continued for 2 hours after all the carbon disulfide was added. A solution consisting of 30 oz of ammonium persulfate and 2 parts of distilled water was then added dropwise to the resulting xanthate reaction mixture. The xanthogen disulfide produced by oxidation is separated from the aqueous phase. It was washed with distilled water, taken up in ether, and the ether phase was dried over anhydrous sulfuric acid. The solvent was evaporated on a rotary evaporator. The yield of xanthogen disulfide was 250P. To prepare the xanthogen disulfide of chrycerol monoketal, 887 g of sodium hydroxide and 90 g of distilled water were placed in a 32 flask, and the sodium hydroxide was dissolved with stirring. Then 266 g of nocrycerol monoketal of formula d was added. Stirring was continued for 2 hours. The reaction mixture was then cooled to 10°C. Carbon dimonide was then added with stirring. The temperature was not allowed to rise above 20'C during this operation. After adding all the carbon disulfide, add 1 additional 2 ml of the reaction mixture.
Stir for hours. A solution consisting of 300 g of ammonium persulfate and 2 g of distilled water was then added dropwise to the reaction mixture containing the xanthate. The xanthogen disulfide obtained by this oxidation was separated from the aqueous phase, washed with distilled water, taken up in ether, and the ether phase was dried over anhydrous sodium sulfate. The solvent was evaporated on a rotary evaporator. The yield of xanthogen disulfide was 2,701. 1.1.To produce xanthogen disulfide of 1-tris-hydroxymethyl-propane monoacetal, 88 g of IJum and 90 P of distilled water were mixed with 3
1, and 1-lium hydroxide was dissolved therein while stirring. 292 g of monoacetal of formula e were then added and stirring continued for 2 hours. This reaction mixture was heated to 10°C.
Cool until cool. 176 g of carbon disulfide was added with stirring. During the addition of carbon disulfide, the temperature was not allowed to rise above 20'C. V after adding all the binary f-carbons? - Stir the reaction mixture for 2 hours. A solution consisting of ammonium persulfate 3 (107) and distilled water 2e was then added dropwise to the resulting reaction mixture containing the xanthate. The xanthogen disulfide obtained by oxidation was then separated from the aqueous phase and washed with distilled water. The ether phase was taken up in ether and dried over anhydrous sodium sulfate. The solvent was removed on a rotary evaporator. The yield of xanthogen disulfide was about 3,507. Prepared and introduced into the palm reactor: Monomer phase chloroprene ioo parts by weight hexanetriol monoacetal (7)
v II xanthogen disulfide aqueous phase distilled water 120 parts by weight Sodium salt of disproportionated abietic acid 5
〃Naphthalenesulfonic acid and formalte o, 5〃Sodium salt of human condensation product Sothorium hydroxide (1,
5〃H: Tetrasodium phosphate 0
- 5 parts by weight of the modifier was changed as follows: 1/, = 0.5 parts by weight p, = 0.7511? / a= 0.8 Q u? /co=1.00 Il After mixing the two phases, the temperature was raised to 43° C. and the polymerization was initiated with an activation side solution consisting of 2.5 parts by weight of formamidine sulfinic acid and 97.5 parts by weight of distilled water. . This activator was added dropwise as needed. When the monomers 65-7() were converted to polymer, the remaining monomer was removed by steam distillation and the polymer was separated from the latex by electrolyte precipitation and dried. The Mooney viscosity 1 degree changed as follows with the amount of the modifier. o,,o℃yI 0.5 13
0uz O,7557 1J8 0.80 50Y4
1. flo 32■0 Polymerization Example The following phases were prepared separately and introduced into the polymerization reactor: monomer phase chlorogrene], O0 parts by weight disulfide aqueous phase distillation water 120 parts by weight disproportionated abietic acid Sodium salt of 5 parts by weight Sodium salt of condensation product of naphthalene sulfonic acid and formaldehyde 0.5 Sodium hydroxide (+,5
〃Tetrasodium pyrophosphate 0.5
Modifier @2 was changed as follows: z, = Q, 1 part by weight Z, = O15 Za = 1. When the two Q n phases were mixed, the temperature was raised to 43° C. and the polymerization was initiated with an activator solution consisting of 2.5 parts by weight of formamidine sulfinic acid and 97.5 parts by weight of distilled water. This activating agent solution was added dropwise as needed. When 65-70% of the monomer was converted to polymer, the remaining monomer was removed by steam distillation and the polymer was separated from the latex by electrolyte precipitation and dried. Mooney viscosity was then measured. The force depended on the amount of modifier 2 as follows: z, (1,1140 2110,592 zB' 1.0 23■1 Polymerization Example (Comparative Example) The following phases were prepared separately and the polymerization reaction Introduced into the vessel: 100 parts by weight of monomer-phase chloroprene 0.45 parts by weight of diimbrobyl xanthogen disulfide
〃Aqueous phase distilled water 120 parts by weight Sodium salt of disproportionated abietic acid 5 ”
Sodium salt of condensation product of naphthalene sulfonic acid and formaldehyde 0.5 "Sodium hydroxide 0.5" Tetrasodium pyrophosphate oj tt2
When the phases were mixed, the temperature was raised to 43° C. and polymerization was initiated by an activated opening consisting of 2.5 parts by weight of formamidine sulfinic acid and 97.5 parts by weight of distilled water. The activator solution was added dropwise as needed. When 65-70% of the monomer was converted to polymer, the remaining monomer was removed by steam distillation and the polymer was separated from the latex by precipitation with electrolyte and dried. This polymer had a Mooney viscosity of approximately 44 (A. n -DDAI (?t-dodecy/l/mercaptan) 0.28 tr Aqueous phase distilled water 120 parts by weight Heterogeneous sodium salt of abietic acid 5 Condensation product of naphthalenesulfonic acid and formaldehyde 1- Lium salt o, 5 Sodium hydroxide
(1,5tr tetrasodium pyrophosphate 0.5〃 Mix the two phases and raise the temperature to 43℃, formamidine sulfinic acid 2
．． Polymerization was initiated with an activator solution consisting of 5 parts by weight and 97.5 parts by weight of distilled water. This activator solution was added dropwise as needed. When 65-70% of the monomer was converted to polymer, the remaining monomer was removed by steam distillation, and the polymer was separated from the latex by precipitation with an electrolyte and dried. This polymer had a Mooney viscosity of about 43. ■1 Polymerization Example (Comparative Example) The following phases were prepared separately and introduced into the polymerization reactor: Monomer phase Chloroprene 100i Diethene disulfite (1,4) Aqueous phase Distilled water 120 Parts by weight Sodium salt of disproportionated abietic acid 5
Sodium salt of condensation product of naphthalene sulfonic acid and formaldehyde 0.5 Sodium hydroxide 0.5 Quaternary sodium pyrophosphate Polymerization was initiated with an activator solution consisting of 2.5 parts by weight of sulfinic acid and 97.5 parts of distilled water. This activator solution was added dropwise as needed. Monomer 65-7
When Part 0 was added to the polymer, the remaining monomer was removed by steam distillation, and the polymer was separated from the latex by precipitation with an electrolyte and dried. This polymer is approximately 43
It had a Mooney viscosity of ■2 Polymerization Example (Comparative Example) The following phases were prepared separately and introduced into the polymerization reaction vessel: Monomer phase Chloroprene 100 parts by weight Ethylene glycol monomethyl ether (kidantogen disulfide)' 0.5
5 Aqueous phase distilled water 120 parts by weight Sodium salt of disproportionated abietic acid 5 Solu-IJium salt of the condensation product of naphthalene sulfonic acid and formaldehyde 0.
5 Sodium hydroxide 0.
5〃Tetrasodium pyrophosphate 0,
5. When the two phases were mixed, the temperature was raised to 43°C, and 2.5 parts by weight of formamidine sulfinic acid and 97% of distilled water were added.
The polymerization reaction was initiated with an activator solution consisting of 5 parts by weight. This activator solution was added dropwise as needed. When 65-70% of the monomer was converted to polymer, the remaining monomer was removed by steam distillation, and the polymer was separated from the latex by precipitation with an electrolyte and dried. This polymer had a Mooney viscosity of about 43. The following phases were prepared separately and introduced into the polymerization reactor: mono[soup phase] 100 parts by weight of chloroprene, xanthogen disulfide of glycol monol, ether, 0.55% of sulfur.
. , 3.9 Aqueous phase distilled water 120 parts by weight Disproportionated abietic acid) sodium salt +t57
″Sodium salt of condensation product of naphthalenesulfonic acid and formaldehyde 0.9〃
Sodium hydroxide o, 8
Tetrasodium pyrophosphate O5"When the two phases were mixed, the temperature was raised to 43°C and the following composition, P["1.3 parts of distilled water, 0.0 potassium persulfate
4 parts and 0.0 parts of sodium anthraquinone sulfonate
Polymerization was initiated with an activated polymer containing 4 parts. This deactivator solution was added as needed. Monomer 65~
When 95% (relative to the expected viscosity) was added to the polymer, the remaining monomer was removed by steam distillation, the polymer was separated by electrolyte precipitation, and dried. ■0 Polymerization Example (Comparative Example) The following phases were prepared separately and introduced into the polymerization reactor: Monomer phase Chloroprene 100 parts by weight of ethanol xanthogen disulfide
(+, 4 〃Sulfur (1,35' aqueous phase distilled water 120 parts by weight disproportionated abietin m sodium salt 5 〃condensation product of naphthalene sulfonic acid and formaldehyde) IJium salt o,
7 Sodium hydroxide. ,
8. Tetrasodium pyrophosphate 0.5
When the two phases were mixed, the temperature was raised to 43°C and the following composition: 1.3 parts of ground distilled water, 0.04 parts of potassium peroxide and 0.04 parts of sodium anthraquinone sulfonate. Polymerization was initiated with an activation solution of This activating agent solution was added as needed. When 65 to 95 of the monomer (1 relationship with the expected viscosity) has been added to the polymer, the remaining monomer is removed by steam distillation,
The polymer was separated by precipitation with electrolyte and dried. IX, Polymerization Example The following phases were prepared separately and introduced into the polymerization reactor: Monomer phase of chitin triol monoacetal to 100 parts by weight of chloroprene.
0.85 xanthogen disulfide sulfur 0.35 parts by weight - aqueous one-phase distilled water 120 parts by weight Sodium salt of disproportionated abietic acid 5 Sodium salt of the condensation product of naphthalene sulfone e and formaldehyde U 0 .7
To sodium hydroxide. ,
8 □Tetrasodium pyrophosphate 0
．． 5. When these two phases were mixed, the temperature was raised to 43°C and the following composition was added: 1.3 parts of distilled water, potassium persulfate o
, o 4 , B and sodium hyanthraquinone sulfonate 0. (Polymerization was initiated with 14 parts of activator solution M. This activator solution was added as needed. 65 to 95 parts of the monomer (relative to the expected viscosity) were converted to the polymer. When the remaining monomers were steam distilled, the polymers were separated by electrolyte precipitation and dried. The polymers prepared in I to IX were then mixed on a roller according to the usual method with the following components: Mixed with: Composition (a) Polychloroprene 100 parts by weight Inert carbon blank 2911 stearic acid 0.5''
Phenyl-β-naphthyl 7mi7 2.0
“Magnesium oxide 4, O〃
Lead oxide 5.0″ Ethylene thiourine 1), 511 Composition (β) Polychloroprene 100 Weight e Inert carbon blank 2911
Stearic acid 0.5”
Phenyl-β-naphthylamine 2,0 Magnesium oxide 1.0
1F lead oxide 5.0 TA-1
1(,7n) 3jl
II [Note] (R) = Vulcanization Accelerator 1 from DuPont. Vulcanization 1 was carried out at 151° C. for 30 minutes. The obtained vulcanizate had the properties shown in Table 1.
d, it can be seen that the highest intensity values are obtained (composition α) when using the specific xanthoge/disulfide form of the modifier of formula 1 (Example I). The difference is particularly significant when a vulcanization accelerator corresponding to the modified xanthogen disulfide of Mr. 1 (Example I) is used (composition β). 1X1 Polymerization Example A) Preparation of benzene-insoluble polychloroprene as one of the components of the mixture with good properties for processing 1 cup of unsalted water in the autoclave
4.4β, 815 S' of the sodium salt of the disproportionated abietic acid mixture, 72 g of the condensation product of alkylnaphthalene sulfonic acid and formaldehyde, and 60 g of tetrasodium pyrophosphate were introduced. Then chloroprene 10
．． 6207, ethylene glycol dimethacrylate) 1
．． 380! ? , a solution containing n-dodenlumerbutan 341 was added. The reaction mixture was then heated to 43 DEG C. and the polymerization was initiated by dropwise addition of a catalyst solution consisting of 2.5 g of formamidine sulfinic acid and 97.59 g of distilled water. When about 80% of the monomers are polymerized, 5g of phenothiazine and 500P of toluene
Medium P -tert -b'f-/l/-bir:y h
Polymerization was stopped by adding 5 g of Teco/Lz stabilizer solution. Unreacted monomers were then removed from the latex. B) Preparation of benzene-soluble polychloroprene as one of the components of a mixture with good processing properties The preparation of benzene-soluble polychloroprene is described in Polymerization Example 1.
Performed according to IV, ■ and ■. 85 parts by weight of the benzene-soluble polymer component was added to the benzene-insoluble i
It was mixed in latex form with 15 parts by weight of raw polymer component (X) and the polymer was then separated from the latex (Table 11). Table ■ Benzene Soluble Benzene Insoluble Polychloroprene Polychloroprene XI 85 parts by weight 15 parts by weight Polymer Example I
Polymer example Xi3 u ■I
I XC〃 V 〃 X D 〃 ■ 〃
n aqueous phase salt-free water 12 t), 0 parts by weight disproportionated sulfur lithium salt of abietic acid 5.0
"Sodium salt of condensation product of naphthalene sulfonic acid and hypoformaldehyde" 0.5
Sodium hydroxide 0.5〃
Tetrasodium pyrophosphate 0.5
When the two phases were mixed, the temperature was raised to 43° C. and polymerization was initiated with an activation side solution consisting of 2-5 parts by weight of formamidine sulfinic acid and 97.5 parts by weight of salt-free water. . This activation side solution was added dropwise as needed. When 65 to 70 units of monomer were polymerized, the polymerization was stopped by adding a radical scavenger, such as tert-butylpyrocatechol, and the remaining monomer was removed by steam distillation. Mooney viscosity M'L-4'/100'C of sample obtained by separation by precipitation with electrolyte and drying
was 45.洟-1'-pJ 7゜monomer phase-chloroprene 100. (10
Part by weight of xanthogen disulfide)” 0.8
4 〃Aqueous phase salt-free water 120.0 parts by weight Sodium salt of disproportionated abietic acid,
5.0 Sodium li of the condensation product of naphthalene sulfonic acid and hypoformaldehyde 0.5
``Sodium hydroxide Q,
5H Tetrasodium pyrophosphate
0.5 When the two phases were mixed, the temperature was increased to 43°C, and the activation side consisted of 2,5 g of formamidine sulfinic acid and 97.5 parts by weight of 7' water containing the salt. Polymerization was initiated in solution. This activated chloride was added dropwise as needed. When 65 to 70 units of monomer were converted to polymer, the polymerization was stopped by adding radical scavenger B, tert-butylpyrocatechol, and the remaining monomer was removed by steam distillation. . Mooney viscosity ML-4'/10oC of the sample then separated by electrolytic precipitation and dried
was 45. Implementation example 8. (Comparative example) Drug phase chloroprene 1 (10,00
Part by weight n-dodecyl mercaptan 0.
28 #Aqueous phase salt-free water 12 (,1
0ri # part disproportionated abietic acid sodium salt
5. o Sodium salt of condensation product of naphthalenesulfonic acid and bormalthehyde 0.5
Sodium hydroxide 0.5
〃Tetrasodium pyrophosphate 0,
5 Polymerization was carried out as in Examples 1 and 2. The obtained polymer had a Mooney viscosity ML-4'/100°C of 45. Implementation example 9. Comparative Example Example 9 was the same as Example 8 except that 0.4 part of diethylxanthogen disulfide was used instead of 28 parts by weight of n-dodecylmercaptan. Mooney viscosity of stagnant polymer ML -4'/100
The temperature was 45°C. ■、 Original ≦−zuku】Question Gousunza □2ζ−Nimi≧ri−(
Manufacturing Example 1 of Dotomi (Part 4 Doshi-Re2-W-Rewet-0 Blend) The following ingredients were introduced into a 40e autoclave equipped with a 40° stirrer, a thermometer, a supply pipe, and a cooling system. :Water without salt
14.4 to 9-disproportionated sodium abieterate D (1,81
5tt alkylnaphthalene sulfone 2 and tric” salt 0.0
72Kg sodium hydroxide
○, (J 36 L'tetrasodium pyrophosphate
0.06 (1. When these ingredients were thoroughly mixed, the following was added: Chloroprene 10.62
0 Rg ethylene glycol dimethacrylate
1.380 n-dotesyl mercaptan
The autoclave was then heated to 43° C. and the polymerization was initiated by dropwise addition of a catalyst solution of 2.57 g of porumamidine sulfinic acid dissolved in 97.5 g of salt-free water. Approximately 80
When % of monomer is converted to polymer, phenothiazine 5
ψ'fl ” tert-butyl birOyte:7-)b
57-Toluene
50 (10) was added to stop the polymerization. The uncured G (D) monomer was then removed from the latex by steam distillation. The Mooney viscosity of this polymer was 70. Example 6 In each of Examples 1c to 9, 55 parts by weight of the polymer latex from Examples 1c to 4 (solids content base) was substituted with 45 parts by weight of the polymer latex from Example 5 (solids content base).
and precipitated by freeze condensation and dried. In each of Examples 10 to 13, Examples 1 to 4
85 parts by weight (based on solids content) of the polymer latex from Example 5 were mixed with 15 parts by weight (solids content basis) of the polymer latex from Example 5, precipitated by freeze condensation and dried. The polymer mixtures of Examples 6 to 13 were then mixed on a roller with the following components according to Nishinomiya's method to form a double polymer mixture:
10 (1.0 parts by weight inert carbon blank 29.0 stearic acid 0.5 phenyl-
β-Naphthyl 7 Mi7 2.0 Magnesium oxide 4.0 Zinc oxide 5.0 Ethylenethiourea 0.5 Add this mixture to 1
Vulcanization was performed at 50°C for 30 minutes. This vulcanizate is
It had the properties shown in the table. This result shows that the mixture is a specific is a group of the formula;

[and n2 are the same or different and represent an integer of 1 to 2°]. 2) A disulfide of the above 1 in which two R's are the same. 3) A disulfide of the above, wherein the group X is hydrogen or alkyl. 1; 4) Civil RυH [In the formula, R is a family group, X is the same or different, hydrogen,
represents an alkyl, aryl, aralkyl or...rogen atom, and n and n are the same or different,
represents an integer from 1 to 2o] is reacted with KC8 in the presence of an alkali to produce a kidantate salt, which is then oxidized to form a compound of the formula IS [wherein the two R's are the same or mutually exclusive. 9, which is the same as the above] xanthogen disulfide,
A method for producing a xanthogen disulfide of the superior arch formula I. 5) Method 4 above, substantially as described with respect to the Examples. 6) Xanthogen disulfide produced by the method 4 or 5 above. 7) 60 to 100 parts by weight of chloroblef and 0.05 parts of the xanthogen disulfide of Group I of 1 to 3 and 6 above in an aqueous dispersion in which the hydrogen atoms are partially or completely substituted with rogen atoms. A method for producing a chloroprene polymer, which comprises polymerizing in the presence of ~30 parts by weight. 8) The method of 7 above, using xanthogen disulfide in an amount of 0.05 to 1 weight. 9) Methods 7 and 8 above, wherein the polymerization is carried out in the presence of sulfur. 10) Method 5 of above 8 or 9, in which sulfur is used in an amount of 0.1 to 0.6% by weight based on the monomer. 11) Method 7 of above, substantially as described in connection with the Examples. 12) Benzene-capable fg PI polychloroprene produced by any of the methods 7 to 11 above. 13) (, J Chlorobutene 60-1 (Diene having 10 superpositions and 4 to 8 carbon atoms, and in which some or all hydrogen atoms may be substituted with... rogene atoms) and/or 40 to 0 parts by weight of α-olefin is added to xanthogen disulfide (1, (15 to 30 The resulting polymer was polymerized in the presence of (l?l chloroplast 8
0 to 100 diphthong IX and a diviny polymer or copolymer, wherein components A and B are mixed at a ratio of Δ:B, -20:1
A method for preparing a roloprene polymer mixture, which is easy to process, by mixing at a ratio of ~1:20.

Claims (1)

[Scope of Claims] 60 to 100 parts by weight of chloroprene and 40 to 0 parts by weight of a diene and/or an α-olefin in which hydrogen atoms may be partially or completely substituted with halogen atoms are prepared in an aqueous dispersion according to the formula ■ S [In the formula, the two R's are the same or different groups of the formula, the group X is the same or different, and each represents hydrogen, alkyl, aryl, aralkyl, or halogen atom, and n , and tL2 are the same or different and represent an integer of 1 to 20.] A method for producing a chloroprene polymer, characterized in that it is polymerized in the presence of xanthogunso sulfide 0.05 to 30 times JHB.