JPS59102926A - Production of sulfur-containing polymer - Google Patents

Abstract

PURPOSE:To produce easily a novel sulfur-containing polymer useful as a flame- retardance imparter, weather resistance improver, etc., by reacting a dimercaptocarboxylic acid ester with sulfur in the presence of a nitrogen-containing compound catalyst. CONSTITUTION:At least one dimethylmercaptocarboxylic acid ester shown by the formula I (R is 1-6C alkylene; R' is 1-3C alkylene) is reacted with sulfur (e.g., sublimed sulfur, liquid sulfur, etc.) in the presence of at least one nitrogen- containing compound catalyst(e.g., N,N'-diethylthiourea, hexamethylenetetramine, etc.) selected from compounds having (substituted)amino group or nitrogen- containing hetero ring, to give a novel sulfur-containing polymer[compound shown by the formula II(p is 1-10; k is 1-40)]. One or more of the compounds shown by the formula I and one or more polymercaptocarboxylic acid esters shown by the formula III(R'' is H, CH3, or C2H5; R'') is as shown for R'; m is 3 or 4) are reacted with sulfur in the presence of a catalyst, to give a compound wherein the compound shown by the formula III is crosslinked with S of the compound shown by the formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a sulfur-containing polymer, and more specifically, the present invention relates to a method for producing a sulfur-containing polymer, and more specifically, a method for producing a sulfur-containing polymer, in which a dimercaptocarboxylic acid ester, or a dimercaptocarboxylic acid ester and a polymercaptocarboxylic acid ester are mixed in the presence of a nitrogen-containing compound catalyst. This invention relates to a method for producing a sulfur-containing polymer that is reacted with sulfur.

Conventionally, sulfur-containing polymers include thiocol as a liquid rubber and PM polymer as a liquid polymer for elastic sealants. The former is a type of polysulfide polymer obtained by combining an organic compound with chlorine atoms at both ends with an alkali polysulfide, and has mercapto groups at the ends, and the mercapto groups at both ends are oxidized with various oxidizing agents to form S-8. The combination results in a high molecular weight polymer. It is used as a sealant for buildings such as high-rise buildings.

The latter is a polyester obtained by reacting a polyol with a mixture of a mercaptoalkanonic acid and a thiodiallic acid starting from the reaction of acrylonitrile with sulfur, as described in Japanese Patent Publication No. 52-34677, and has a mercapto group at the end. With a vulcanizing agent, it becomes an elastic solid product and is used as a construction sealant.

The present inventors have worked hard to develop a new method for producing sulfur-containing polymers (σ). It has been discovered that novel sulfur-containing polymers can be produced very easily by reacting them with sulfur in the presence of sulfur.

That is, according to the present invention, the general formula % formula % (1) (wherein R represents a straight chain or branched alkylene group having 1 to 6 carbon atoms, and R' represents a straight chain or branched alkylene group having 1 to 3 carbon atoms) The presence of at least one nitrogen-containing compound catalyst selected from compounds having an amino group, a substituted amino group, and a nitrogen-containing heterocycle Below, a method for producing a sulfur-containing copolymer is provided, which comprises reacting with sulfur.

According to the present invention, the dimercaptocarboxylic acid ester of the general formula (1) and the general formula (wherein Rn represents a hydrogen atom, a methyl group, or an ethyl group, and R″′ has a carbon number of 1 to 3
represents a straight or branched alkylene group, and 1 is 3 or 4
is an integer of ), in the presence of at least one nitrogen-containing compound catalyst selected from compounds having an amine group, a substituted amino group, and a nitrogen-containing heterocycle. Provided is a method for producing a sulfur-containing polymer, which comprises reacting with a sulfur-containing polymer.

The method of the present invention will be further explained below.

The dimercaptocarboxylic acid ester of formula (1) used in the method of the present invention can be easily synthesized by an esterification reaction between the corresponding mercaptocarboxylic acid and a diol. For example, mercaptocarboxylic acids such as thioglycolic acid, α-mercaptopropionic acid, β-mercap1-propionic acid, α-mercapto-α-methylpropionic acid, ethylene glycol, propylene glycol, 1. 3-butylene glycol, 2.3-
Butylene glycol, l, 4-butylene glycol, 1
．． Dimercaptocaln J mate ester of the general formula (1) is produced by reacting with a diol such as 6-hexanediol according to a conventional method, for example, by heating and stirring in the presence of a trace amount of p-toluenesulfonic acid. You can force it.

The polymercap 1 to carboxylic acid ester of formula (11) used in the method of the present invention is synthesized by esterifying the mercaptocarboxylic acid and an aliphatic polyol such as trimethylolpropane or pentaerythritol in the same manner as described above. can do.

In the method of the present invention, the compound of formula (1) or the formula (
As the sulfur to be reacted with the compounds of 1) and (II), any type of sulfur can be suitably used, such as solid sulfur such as sublimated sulfur, precipitated sulfur, ellipsoidal sulfur, colloidal sulfur, or liquid sulfur. However, it is particularly preferable to use freshly prepared ones. There is no particular limit to the amount of sulfur used, but if the amount of sulfur used is too small, the physical properties of the resulting polymer will deteriorate, while if the amount of sulfur used is too large, sulfur will precipitate and the reactants will be non-uniform. This makes handling difficult. Therefore, ζ is generally at least 0.1 gram atom, preferably at least 0.5 gram atom, more preferably at least 0.5 gram atom per mole of mercapto group contained in the ester monomer of formula (1) or formulas (1) and (II). Amounts of 0.5 to 15 gram atoms are used.

When the compound of formula (1) and the compound of formula (II) are used together, the amount is generally 0 per mol of the compound of formula (1).
．． of the formula (I) in an amount of up to 10 mol, preferably 0.03 mol
The compound of I) is used. Formula (If the amount of the old compound used is too large, the viscosity of the resulting polymer becomes too crystalline, which is undesirable because it causes problems in operation.

Examples of the nitrogen-containing compound catalyst that can be used in the method of the present invention include compounds having an amine group, a substituted amino group, or a nitrogen-containing heterocycle, and specifically, N
, N'-diphenylthiourea, N,N'-diethylthiourea, N,N'-dilaurylthiourea, Ukawa-ramethylthiuram disulfide, tetrabutylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide, urea , 1,3-Diphenyl-2-thiourea, and other ureas or thioureas; hexamethylenetetramine, 2-mercapi-2-imidapurine, 2-mercapi-hendithiazole, dihenzothiazyldisulphy F, 2- Mercaptohendithiazole cyclohexylamine salt, 2-(4'-morpholinodithio)-hendithiazole, N-cyclohexyl-2-benzothiazolylsulfenamide, N-oxydiethylene-2-benzothiazolylsulfenamide, N -t-
Butyl-2-benzothiazolylsulfenamide, poly-(2,2,4)-1-dimethyl-1゜2-dihydroxyquinoline, 2-mercaptohenzimidazole, quinoline, 2-aminohenzodiazole, amino Nitrogen-containing heterocyclic compounds such as triazole, pyridine, morboline; guanidine, dicyandiamide, aminoguanidine, ■.

3-diphenylguanidine, 1,2.3-1 rifhenylguanidine, di-o-1-lylguanidine, dicatecholbore-1. - Guanidine salts such as tolylguanidine salt; pentamethylene dithiocarbamic acid piperidine salt, pipecolyldithiocarhamic acid pipecoline salt, zinc dimethyldithiocarbamate, diethyldithiocarbamate, dibutyldithiocarbamate, N-ethyl-N-phenyldithiocarbamate Thiocarbamates such as salts; diphenylamine, dimethylaminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, 1-(N-phenylamino)-naphthalene , diphenylamine-acetone reactants, diarylamines such as p-aminodiphenylamine; aniline;
Monoalkylaniline, dialkylaniline, toluidine, monoalkyltoluidine, dialkyltoluidine,
Aniline compounds such as n-butyraldehyde-aniline III compounds; aliphatic primary amines such as ethylamine, propylamine, butylamine; aliphatic secondary amines such as diethylamine, dibutylamine; aliphatic tertiary amines such as triethylamine, dibutylamine, etc. Amines; alicyclic amines such as cyclobutylamine and cyclohexylamine; diamines such as ethylenediamine; substituted alkyldiamines with N,N-diethylethylenecyamine; diethylene 1
~triamines such as liamine, or substituted alkyltriamines; polyamines such as triethylenetetramine;
Alternatively, substituted alkyl polyamines; oxyalkylene amines such as echnolamine; or compounds having aziridinyl groups in which some of the above amino groups are substituted with ethyleneimine; and other nitrogen-containing compounds such as dimethylpolamide. . By using such a catalyst, the reaction proceeds even at a relatively low temperature, and the desired sulfur-containing polymer can be obtained. There is no particular limit to the amount of these catalysts used, but if the amount used is small, there will be no effect of promoting the reaction,
On the other hand, if the amount is too high, the reaction will become violent and the physical properties of the resulting polymer will deteriorate, so it cannot be lit. Therefore, it is generally used in an amount of 0.01 to 30% by weight, preferably 0.1 to 5% by weight, based on the weight of the raw ester, although it depends on the type of catalyst used.

The reaction of the compound of formula (1) or the compounds of formulas (1) and (b) with sulfur can be carried out, for example, as follows.

The dimercaptocarboxylic acid ester monomer prepared by the method described above, or this and the polymercaptocarboxylic acid ester monomer (crosslinking agent) are dissolved in an appropriate solvent if necessary, the above catalyst is added thereto, and the mixture is heated at room temperature. Mix thoroughly. The solvent can be used, for example, to adjust the viscosity of the produced polymer liquid, and specifically includes toluene, 0-xylene, m-xylene, mixed xylene, ethylhenzene,
Aromatic hydrocarbons such as cumene can be suitably used. Next, sulfur is gradually added to the catalyst-containing monomer liquid while stirring to cause a reaction. The reaction temperature is not particularly limited, but since foaming occurs due to the hydrogen sulfide gas generated by the reaction, it is generally preferable to carry out the reaction at a temperature of about 20 to 80°C. The reaction can be suitably carried out even at room temperature. After the addition of sulfur is completed, the final step is to heat the reaction solution to a temperature of 120'C or higher, depending on the type of catalyst, to drive out the hydrogen sulfide residue dissolved in the reaction solution and remove the odor of the produced polymer. preferable.

Completion of the reaction can be confirmed by no generation of hydrogen sulfide gas.Instead of the above method, sulfur is suspended in a solvent in advance, and while stirring, the formula ( 1
) or compounds of formula (1) and formula (II) can also be added to produce the desired polymer by TM. In this case, the temperature and the formula (1) or the formula (I
) and (11) are preferably carried out while controlling the rate of addition.

When the compound of formula (1) is used alone, the polymer synthesized according to the method of the present invention has the following structure, as determined by infrared absorption spectroscopy and G
I) Confirmed by C analysis.

0 0 (In the formula, p is an integer of 1 to IO, and k is an integer of 1 to 40.) In addition, when the compound of formula (II) is used in combination, the repeating unit of the above (III) The sulfur atom has the formula (I
It is thought that compounds having various crosslinked structures of I) are produced.

Such polymers are new and can be used, for example, as flame retardant agents that impart flame retardancy to thermosetting resins, thermoplastic resins, rubber, etc.; curing agents such as epoxy resins; and/or Alternatively, it can be suitably used as a plasticizer; a surface weathering improver that improves the weather resistance of urethane resins, etc.

Hereinafter, the present invention will be explained in more detail in accordance with Examples. However, it goes without saying that the scope of the present invention is not limited to these Examples. In addition, in the following examples, "1 part" and "%" are based on Shigesato standards unless otherwise specified.

Example I A thermometer, gas outlet, stirring device and sulfur inlet (j!
192 parts of ethylene glycol dithioglycolate (hereinafter referred to as IEG
1'), 835 parts of 1,4-butanediol dithioglycolate (hereinafter referred to as BDT G),
26.4 parts of pentaerythritol tetrakis-β-mercaptopropione-1- (hereinafter referred to as PTMP), 1
36 parts of mixed xylene and 4.4 parts of n-butylamine were charged, and 283 parts of
'5) Unsulfur was slowly added over 90 minutes. Vigorous foaming was observed due to hydrogen sulfide gas foaming, and the temperature reached 2.
Since the temperature had dropped to 1℃, the temperature was stirred for another 30 minutes, and then the temperature was gradually increased to 130℃ over 120 minutes while continuing to stir.
The mixture was heated to °C and stirring continued at the same temperature for 3 hours. Generation of hydrogen sulfide gas stopped, foaming almost disappeared, and 1221 parts of a viscous yellow polymer was obtained. The average molecular weight of the obtained polymer (measured by GPC Chroma 1 to Craffy) was 180
0, and the sulfur content was 33.6%.

Example 2 48 parts of EGTG, 0209 parts of BDT and P T MP
1/8 was dissolved in 33 parts of mixed xylene and reacted by gradually adding 70.8 parts of powdered sulfur over 80 minutes in the same manner as in Example 1 in the presence of 1.1 parts of n-butylamine. Sa-
U, yellow rubbery η-composition 3 in the same manner as in Example 1
Got 19 copies. The average molecular weight of the f4 polymer is 150
0, the sulfur content was 35.6%.

Example 3 B I) 1177 parts of TG was added to n without using a solvent.
-U was reacted with sulfur in the same manner as in Example 1 in the presence of 74.7 parts of butylamide. 1'5) The amount of unsulfur added is 15
2 parts, addition time was 60 minutes. In this way, 1194 parts of a polymer in the form of yellow viscous 11 was obtained.

The average molecular weight of the obtained polymer was 2900, and the sulfur content was 2.
It was 0.1 part.

1124.6 parts of 1''G was reacted with sulfur in the same manner as in Example 1 in the presence of 4.3 parts of n-butylamine without using a solvent.4 '5) The amount of unsulfur added was 2 U 9.7 fil!, and the addition time was 90 minutes.

In this way, 1273.5 parts of the dry f+I former II polymer was added to j! It's I. The average molecular weight of OI Radar polymer is 2000
, the sulfur content was 28.6%.

1,194 parts of 4-butanediol di-β-mercaptopropione-1-(BDMP) were prepared in the same manner as in Example 1 in the presence of 4.8 parts of n-butylamine without using a solvent. Reacted with powdered sulfur.

The amount of sulfur added was 289.7 parts, and the addition time was 90 minutes.

In this way, 1337.3 parts of a viscous liquid polymer was obtained. The average molecular m of the obtained polymer was 2300, and the sulfur content was 24.8%.

Example 6 28 parts of EGT01 were reacted with powdered sulfur as in Example I in the presence of 4.1 parts of n-butylamine without using a solvent. The amount of sulfur added was 289.7 parts, and the addition time was 90 minutes.

In this way, 1175 parts of a viscous liquid polymer was obtained. The average molecular weight of the obtained polymer was 1800, and the sulfur content was 31.
It was 2%.

Example 7 i G-hex9-dioldithioglycolate (I
1 part of F was reacted with powdered sulfur in the presence of 4.8 parts of rl-butylamine using a solvent. The amount of sulfur added was 289.7 parts.
Addition time was 90 minutes.

1334 parts of a yellow-orange viscous liquid polymer is called fjF. The average molecular weight of the obtained polymer was 2300,
The sulfur content was 27.4%.

In the same manner as in Example 1, 150 parts of Kasei ■cho T31) 0.1" was reacted with powdered sulfur in the presence of 70.6 parts of n-butyl amine without using a solvent. The amount of sulfur added was 174 parts,
Addition time was 120 minutes.

In this way, 304.2 parts of a viscous liquid polymer was obtained. The average molecular weight of the obtained polymer was 750, and the sulfur content was 5.
It was 6.7%.

4.5 parts of r)-butylamine in 136 parts of xylene solvent mixed with 13 D'VG l 043 fill and 1-18.4 parts of trimethylolecne I lithioglycole
was reacted with powdered sulfur in the presence of The amount of sulfur added is 2
83° 2 parts, addition time was 90 minutes.

In this way, 1235 parts of a viscous liquid polymer was obtained. The average molecular weight of the obtained polymer was 1900, and the sulfur content was 30.
．． It was 8%.

Examples 10-21 13 was carried out in the same manner as in Example 1, except that the type and amount of catalyst used, the final reaction temperature and reaction time were changed as shown in Table 1.
A sulfur-containing polymer was obtained by reacting 112.5 parts of DTG with 29 parts of powdered sulfur.

(The yield of the polymer produced is shown in Table 1.

Below is the margin for the first table. Type Amount used Temperature Time Yield (parts) (
'c) (hours) (parts) 10n-butyl 1 130 1.5 128.
2 amine 11 0.1 130 8 127.0
12 Urea 5 140 20 132.113
Hexamethylene 2 140 6 129.0 Tetramine 14 Diphenyl 0.4 130 5 12
7.4 Guanidine 15 1 + 2 + 3 l・li 1 13
0 5 12B, 0 phenylguanidine 16 dimethylborum 2 140 6 129
．． 2 Zinc Carbamate Table 1 (continued) Type Amount used Temperature Time Yield (parts) (
'C) (time) (parts) 17 p-amino 4 140 16
131.4 Diphenylamine 18 Aniline 4 140 20 13
1.219 Dibutylamine 1 130 3
128.420 Ethylene 0.4 130
5 127.5 Diamine 21 Dimethylborum l 140 20
12B, 2Ami1 Application Example The sulfur-containing polymer produced in Example 1 was blended into a commercially available unsaturated polyester (Rigorasoku 158 B QT manufactured by Showa Kobunshi (11)) in the following formulation.

Below is the margin composition: Partially unsaturated polyester Contains 100'f! rL yellow polymer 5 hardening agent *12 aluminum hydroxide 20 calcium carbonate 40 glass fiber
50 hexabromobenzene 20*1
The mixture thus obtained was cured at a temperature of 140°C for 80 minutes according to its density, and the resulting cured resin molded product was tested for combustion (fire extinguished within 1 and 20 seconds of ignition). !lJ, find the elementary concentration)
The result was 28%, which was 17% compared to the test result of 24% for the formulation containing no sulfur-containing polymer. Q showed a remarkable flammability imparting effect.

Claims (1)

[Claims] 1. General formula % Formula % (1) (wherein R represents a straight chain or branched alkylene group having 1 to 6 carbon atoms, and R' represents a straight chain having 1 to 3 carbon atoms. or a branched chain alkylene group) is combined with at least one nitrogen-containing compound M selected from compounds having an amino group, a substituted amino group, and a nitrogen-containing heterocycle. 1. A method for producing a sulfur-containing polymer, comprising reacting it with sulfur in the presence of. 2. General formula % Formula % (1) (In the formula, 1z represents a straight or branched alkylene group having 1 to 6 carbon atoms, and ■?' represents a straight or branched alkylene group having 1 to 3 carbon atoms. At least one type of dimercaptocarboxylic acid ester represented by the general formula At least one polymercaptocarboxylic acid ester represented by (representing a straight or branched alkylene group, where m is an integer of 3 or 4) is prepared from a compound having an amino group, a substituted amino group, and a nitrogen-containing heterocycle. A method for producing a sulfur-containing polymer, comprising reacting it with sulfur in the presence of at least one selected nitrogen-containing compound catalyst.