JPH0314016B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel sulfur-containing oligomers. The present invention has thermal stability, lubricity, transparency, weather resistance,
As a result of intensive research into a sulfur-containing oligomer that has excellent yoking resistance, does not easily cause blooming, and has excellent foam cell control ability,
This led to the present invention. That is, the present invention is based on the general formula However, l: an integer of 1 to 2 m: an integer of 1 to 50 n: an integer of 1 to 3 R ₁ , R ₂ : H, or CH ₃ R ₃ : COOR ₄ ,

[Formula] Alkyl group, allyl group R ₄ , R ₅ : Alkyl group M: H, NH ₄ , Li, Na, K, Mg, Ca, Sr,
Ba, Zn, Al, Sn, Sb, R ₆ Sn, (R ₆ ) ₂ Sn R ₆ : Provides a novel sulfur-containing oligomer represented by an alkyl group or alkoxycarbonylalkyl. The compound of the present invention is, for example, a sulfur-containing oligomer having a number average degree of polymerization of 50 or less and having a terminal carboxyl group obtained by polymerizing a polymerizable unsaturated monomer in the presence of a mercaptocarboxylic acid, or a metal salt thereof.
Examples of such mercaptocarboxylic acids include mercaptoacetic acid and β-mercaptopropionic acid. In addition, the polymerizable unsaturated monomer has the general formula

[Formula] (where R ₁ , R ₂ , and R ₃ are as shown above), such as styrene, methylstyrene, ethylene, propylene, vinyl acetate, methyl acrylate, ethyl acrylate, acrylic acid Butyl, 2-ethylhexyl acrylate,
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, ethyl crotonate, etc., and these monomers may be used alone or in combination of two or more. good. As the metal in the oligomer of the present invention,
Li, Na, K, Mg, Ca, Sr, Ba, Zn, Al, Sn,
Examples include metal atoms of Sb. In addition to the tin atom, organic tin compounds such as R ₆ Sn or (R ₆ ) ₂ Sn (R ₆ is an alkyl group or alkoxycarbonylalkyl) may also be used, such as monoalkyltin, dialkyltin, monoestertin, etc. Examples of the alkyl groups include methyl, butyl, octyl, etc., and examples of the ester residue include alkoxycarbonyl alkyl such as β-(butoxycarbonyl)ethyl. Further, when M in the above general formula is H, the oligomer having a terminal carboxyl group has a number average degree of polymerization of 50 or less, preferably 2 to 40. For example, when the compound is used as a stabilizer for a halogen-containing resin, one having a number average degree of polymerization of 50 or more is not preferred because the metal content decreases and the effect in terms of heat resistance is significantly inferior. The oligomer of the present invention can be easily synthesized, for example, as follows. (1) Using di-tertiary butyl peroxide as an initiator in a toluene solvent, heating at 108 to 112°C with the required molar ratio of mercaptocarboxylic acid and polymerizable unsaturated monomer under reflux for 8 hours. After the reaction is completed, toluene is removed under reduced pressure to obtain a compound having a carboxy group at the terminal. In addition, for the metal salt, the terminal carboxy compound synthesized above is reacted with a metal hydroxide or metal oxide in a toluene solvent, and dehydration is performed by toluene azeotropy at around 110°C. After the reaction is completed, toluene is removed. It can be obtained by Incidentally, m in the oligomer represented by the general formula of the present invention is usually greatly influenced by the molar ratio of the mercaptocarboxylic acid and the polymerizable unsaturated monomer, and n is determined by the valence of the metal of M. Therefore, the compound of the present invention is generally formed by reacting a polymerizable unsaturated monomer in a ratio of 2 to 51 moles, preferably 2 to 40 moles, per mole of mercaptocarboxylic acid. It is what it is. Therefore, the oligomer of the present invention has a general formula in which m is 1.
Although it is an integer of ~50, it is actually an average value of several kinds. The compound of the present invention can be used for various purposes, but
It is particularly useful as a stabilizer for halogen-containing resins, an anti-shrinkage agent for unsaturated polyesters, and a raw material for solid paints. The oligomer of the present invention can exhibit particularly excellent effects when used as a stabilizer for halogen-containing resins. In general, halogen-containing resins such as polyvinyl chloride tend to undergo thermal decomposition mainly due to dehydrohalogenation during hot molding, and furthermore, the resin sticks to the metal surface of the processing machine, making it difficult to flow. Stabilizers and lubricants have traditionally been added to avoid such disadvantages. Many metal soaps have been used as these stabilizers, but among them, cadmium soap and lead soap, which are particularly effective in terms of heat resistance, have been considered useful, but their toxicity has been pointed out. For this reason, research has been carried out on combinations of calcium soap, barium soap, zinc soap, etc., but it has not yet been possible to achieve effects comparable to those of cadmium soap and lead soap. On the other hand, examples of lubricants include fatty acids such as stearic acid and their esters, amides such as methylene bisamide, paraffin, and low molecular weight polyethylene wax. However, these lubricants, such as stearic acid, methylene bisamide, paraffin, and polyethylene wax, have the drawback of impairing transparency and causing a bloom phenomenon, and are therefore not sufficient. Furthermore, esters such as butyl stearate do not have sufficient lubricity, and when used alone, they impair moldability. In order to solve these problems, metal salts of acrylic acid ester oligomers have been studied, as seen in JP-A-51-28848, but when synthesized by normal methods, intramolecular cross-linking occurs due to the presence of carboxyl groups in the molecule. It tends to form and cannot exhibit sufficient lubricity. However, the oligomer of the present invention surprisingly has these drawbacks improved. When the compound of the present invention is used as a stabilizer for halogen-containing resins, the amount used is usually 0.1 to 20 parts by weight per 100 parts by weight of the resin. If the amount is less than 0.1 part by weight, almost no effect will be observed, and if it is added in excess of 20 parts by weight, no significant improvement in effect will be observed. In order to improve the thermal stability of the halogen-containing resin containing the oligomer of the present invention, fatty acid salts such as barium, calcium, zinc, magnesium, and aluminum, organic tin fatty acid salts, organic tin mercapto compounds, organic tin maleates, Stabilizers such as organotin maleate salts, triphenyl phosphite, tricresyl phosphite, diphenyl phosphite, diphenyl isodecyl phosphite,
Diphenylnonylphosphite, phenylisodecylphosphite, phenyldinonylphosphite, trisnonylphenylphosphite, 4,
Stabilizing aids such as organic phosphorous esters represented by 4'-isopropylidene diphenol dodecyl phosphite, epoxidized soybean oil, epoxidized linseed oil, and epoxy compounds represented by epoxy resins are used alone or in combination. Can be used. Furthermore, phthalate ester plasticizers, other acid ester plasticizers, polycondensation polyester plasticizers, phosphate ester plasticizers, epoxy plasticizers,
Chlorine plasticizers and other plasticizers can be used as appropriate depending on the application. Others as necessary, such as antioxidants, ultraviolet absorbers, organic chelators, pigments, fillers, foaming agents, antistatic agents, antifogging agents, plate-out inhibitors, surface treatment agents, lubricants, flame retardants, photostabilizers, etc. Agents, fluorescent agents, microbicides, bactericides, metal deactivators, nonmetal stabilizers, processing aids, mold release agents, impact modifiers, and the like may be used in combination. Examples of halogen-containing resins in which the oligomer of the present invention can be blended include the following. For example, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, Vinyl chloride-styrene copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic These include acid ester copolymers, vinyl chloride-acrylonitrile copolymers, and internally plasticized polyvinyl chloride. Examples are given to further illustrate the invention. However, the present invention is not limited to these examples. Examples 1 to 3 show the synthesis of the oligomer of the present invention, and Examples 4 to 6 show compositions of halogen-containing resins to which the oligomer of the invention was added and their stabilizing effects. Example 1 (Synthesis of β-mercaptopropionic acid/isobutyl acrylate oligomer) 214 g (1.67 mol) of isobutyl acrylate and 607 g of toluene were placed in two four-neck ground round bottom flasks.
g, β-mercaptopropionic acid 58 g (0.63 mol), ditertiary butyl peroxide 13.29 g
(0.091 mol) was charged, and N ₂ gas was blown under the liquid surface. After 15 minutes, the temperature was raised to 105-110°C and maintained at 110°C under reflux for 1 hour. After that, while maintaining the temperature at 110℃, 490g (3.83mol) of isobutyl acrylate
and β-mercaptopropionic acid 135g (1.47mol)
were added dropwise from separate dropping funnels over a period of 3 hours, and after the completion of the addition, the reaction was continued for 4 hours while maintaining the temperature at around 110°C to obtain a toluene solution () of β-mercaptopropionic acid/isobutyl acrylate oligomer. Non-volatile content of () 59.3%, viscosity (25℃)
60cp, hue (Gardner method) 1>, acid value 67.8. Furthermore, toluene was removed from ( ) to obtain β-mercaptopropionic acid/isobutyl acrylate oligomer (No. 1). Such oligomer No. 1 has a number average molecular weight of 530, a non-volatile content of 99.4%, and a viscosity (at 25°C).
5800cp, hue (Gardner method) 1>, acid value 112.2
It was hot. The structure of the obtained oligomer was identified from the characteristic values shown in Table 1. Example 2 (Synthesis of β-mercaptopropionic acid/isobutyl acrylate oligomer Ba salt) 500 g of the oligomer toluene solution of Example 1 (acid value 67.8) and hydroxyl value barium (Ba(OH) ₂ .
A round bottom flask was charged with 95.5 g (0.3 mol) of 8H ₂ O) and reacted at around 110° C. under toluene reflux for 4 hours, and 53 g of the produced water was distilled off. After the reaction is complete,
After filtration, toluene was further distilled off under reduced pressure to obtain β-mercaptopropionic acid/isobutyl acrylate oligomer Ba salt (No. 2). This product has a nonvolatile content of 99.0%, a viscosity (25℃) of 148P<, and a Ba content.
It was 12.0% (atomic absorption spectrophotometry). The structure of the obtained oligomer was identified from the characteristic values shown in Table 1. Example 3 Oligomer Nos. 3 to 20 were obtained in the same manner as in Examples 1 and 2 using the raw materials shown in Table 1. The structure of each oligomer obtained was identified from the characteristic values shown in Table 1.

【table】

[Table] Example 4 Compounds shown in Table 2 were blended with 100 parts by weight of polyvinyl chloride resin (=800), and the surface temperature was 165°C.
Knead for 5 minutes with two 8-inch rolls to form a 0.6mm
A thick test piece was made and a thermal stability test was conducted with the gear open at 170℃, and a 2mm thick test piece was made with a press at 170℃
A thick plate was prepared and a transparency test was conducted. Furthermore, a test using a Brabender plastograph and a weather resistance test using an outdoor Bacro were conducted. The results are shown in Table 2. Example 5 A test piece was prepared using the same procedure as in Example 4 using the formulation shown in Table 3, and a thermal stability test and a transparency test were conducted. An adhesion test was also conducted on two 8-inch rolls at a surface temperature of 170°C. The results are shown in Table 3. Example 6 A test bead was made using the same procedure as in Example 4 with the following composition, and a thermal stability test at 180°C, a transparency test of a 2 mm thick plate by press molding at 160°C, and a test bead with 170° C.
Adhesion tests and bloom tests were conducted on two 8-inch rolls at .degree. The results are shown in Table 4. (Composition) PVC (=1050) 100 parts by weight DOP 48 Epoxidized soybean oil (Eposizer W-100EL) 2 Diphenylnonyl phosphorite 0.8 Stabilizer (as shown in Table 4) Amount shown in Table 4 Example 7 The following formulation A test piece with a thickness of 0.6 mm was prepared by kneading the compound based on the following for 5 minutes using two 8-inch rolls with a surface temperature of 150°C, and foaming it at regular intervals in a gear oven at 200°C. The expansion ratio and the cell state were observed. The results are shown in Table 5. (Composition) PVC (=1050) 100 parts by weight DOP 60 Azodicarbonamide 3 Stabilizer (shown in Table 5) Amount shown in Table 5

【table】

[Table] Transparency: ◎Very good ○Good △Slightly cloudy ×Opaque metal molar ratio (Ca/Zn or Ba/Zn)

[Table] Stabilizer No. is the oligomer shown in Table 1.

[Table] Stabilizer No. is the oligomer shown in Table 1.

【table】

【table】

Claims (1)

[Claims] 1. General formula However, l: an integer of 1 to 2 m: an integer of 1 to 50 n: an integer of 1 to 3 R ₁ , R ₂ : H, CH ₃ R ₃ : COOR ₄ , [Formula] alkyl group, allyl group R ₄ , R ₅ : Alkyl group M: H, NH ₄ , Li, Na, K, Mg, Ca, Sr,
Ba, Zn, Al, Sn, Sb, R ₆ Sn, (R ₆ ) ₂ Sn R ₆ : Sulfur-containing oligomer represented by an alkyl group or alkoxycarbonyl alkyl. 2. The sulfur-containing oligomer according to claim 1, wherein M is a metal. 3. The sulfur-containing oligomer according to claim 1, which is used as a stabilizer for halogen-containing resins.