JPH05320231A - Mercaptide polymer and its production - Google Patents

Abstract

PURPOSE:To provide a new mercaptide polymer not described in literature and being useful as a rubber sealant, a coating material, ultraviolet-curing coating material or the like and to provide its production process. CONSTITUTION:The mercaptide polymer is represented by the general formula: HS-R<1>-COO(CH2)m[OCOR<2>-kCOO(CH2)m]lOCOR<1>-SH (wherein R<1> is a 1-6C bivalent hydrocarbon group; X<2> is a 1-12C bivalent hydrocarbon group or a 4C or lower bivalent organic group containing a thioether bond; m is 50-400; l is 1-20; and k is 0 or 1). The production process comprises reacting a polyolefin polyol of the general formula: HO(CH2)mOH (wherein m is 50-400) with a mercaptoalkanoic acid of the general formula: HS-R<1>-COOH (wherein R<1> is a 1-6C bivalent hydrocarbon group) and a dicarboxylic acid of the general formula: HOCOR<2>COOH (wherein R<2> is a 1-12C bivalent hydrocarbon group or a 4C or lower bivalent organic group containing a thioether bond) through the elimination of water.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel mercapto group-containing polymer which has not been published in the literature, particularly a rubber-like sealant, a coating material, a mercapto group-containing polymer which is useful as an ultraviolet curable coating material and a method for producing the same. It is a thing.

[0002]

The present invention comprises a sealant, a coating material,
The present invention relates to a novel mercapto group-containing polymer that has not been published in the literature and is useful for UV-curable coatings and the like, which has the general formula HS-R ¹ -COO (CH ₂ ) _m [OCOR ² _k COO (CH ₂ ) _m ] _l OCOR ¹ -SH (1) (wherein R ¹ contains a divalent hydrocarbon group having 1 to 6 carbon atoms, and R ² contains a divalent hydrocarbon group having 1 to 12 carbon atoms or a thioether bond. Divalent organic group having 4 or less carbon atoms, m is 50 to 40
0 and 1 are 1 to 20, and k is a positive number of 0 or 1).

[0003] The divalent hydrocarbon group of 1 to 6 carbon atoms represented by the _{^{R 1, -CH 2 -, -}} C 2 H 4 -, - CH
_{(CH 3) -, - C} 6 H 4 - Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms represented such that, or R ² -CH _{2
-, - C 2 H 4 -} , C 4 H 8 -, - C 6 H 12 -, - C 6
_{H 4 -, - C 8 H} 16 -, - C 10 H 20 -, - C 12 H 24 - , etc. are exemplified, and as the number 4 below the organic group having a carbon containing this thioether group -CH ₂ -S-CH ₂ −, −C ₂ H _{4
-S-C 2 H 4 -,} - CH (CH 3) -S-CH (CH
₃ )-, etc.

The SH group-containing polymer represented by the general formula (1) has the following formula: HSC ₂ H ₄ COO (CH ₂ ) ₁₆₀ OCOC ₂ H ₄ SC ₂ H ₄ COO (CH ₂ ) ₁₆₀ OCOC ₂ H ₄ SH _, HSC ₂ H ₄ COO (CH ₂ ) ₁₆₀ OCOC ₂ H ₄ SC ₂ H ₄ COO (CH ₂ ) ₁₆₀ OCOC ₂ H ₄ SC ₂ H ₄ COO (CH ₂ ) ₁₆₀ -OCOC ₂ H ₄ SH, HSCH ₂ COO ( CH ₂ ) ₁₆₀ OCOC ₄ H ₈ SC ₄ H ₈ COO (CH ₂ ) ₁₆₀ -COOC ₄ H ₈ SC ₄ H ₈ COO (CH ₂ ) ₁₆₀ OCOCH ₂ SH, HSCH ₂ COO (CH ₂ ) ₁₆₀ OCOC ₂ H ₄ SC _A typical example is ₂ H ₄ COO (CH ₂ ) ₁₆₀ OCOCH ₂ SH.

The SH group-containing polymer represented by the above general formula (1) is obtained by using, for example, a polyolefin polyol represented by the general formula HO (CH ₂ ) _m OH (2) (where m is the same as above) as a raw material. As hydroxyl groups at both ends of this compound, mercaptoalkanoic acid represented by the general formula HS-R ¹ COOH (3) (where R ¹ is the same as above) and general formula HOCOR ² COOH (4) (R ² Can be obtained by reacting a dicarboxylic acid represented by the above). Particularly, the chain length is extended by reacting the above-mentioned polyolefin polyol with the dicarboxylic acid represented by the general formula (4) in advance. Then, by reacting with the above-mentioned mercaptoalkanoic acid represented by the general formula (3), a target product having a large molecular weight can be obtained.

The polyolefin polyol represented by the general formula (2) is a polymer having a saturated hydrocarbon skeleton and blocked at both ends with hydroxyl groups and having a molecular weight of 1,000 to 5,000, which is liquid at room temperature. Examples include those from wax to solids having a melting point of 75 ° C. or higher, which are generally commercially available Polytail H, Polytail HA, and Polytail HE (all are trade names manufactured by Mitsubishi Kasei Kogyo Co., Ltd.). Often, these physical properties are shown in Table 1.

[Table 1]

The mercaptoalkanoic acid represented by the above general formula (3) includes mercaptoacetic acid, 2-mercaptopropionic acid, α-mercaptopropionic acid,
Thiosalicylic acid and the like are exemplified, and the above general formula (4) is used.
As the dicarboxylic acid represented by, oxalic acid, malonic acid,
Succinic acid, glutaric acid, adipic acid, vimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid,
Aliphatic dicarboxylic acids such as dodecadioic acid, brassylic acid, and tetradecanedioic acid, aromatic dicarboxylic acids such as orthophthalic acid, isophthalic acid, and terephthalic acid, β,
Examples include β'-thiodipropionic acid, thiodiacetic acid, α, α'-thiodipropionic acid and the like.

The reaction of the above-mentioned polyolefin polyol represented by the general formula (2) with the mercaptoalkanoic acid represented by the general formula (3) is carried out at a stoichiometric molar ratio of -OH / -COOH of 0.8-1. It suffices to mix them at a compounding ratio in the range of 0.2 and react in the temperature range of 50 to 250 ° C.
This reaction is preferably carried out in the coexistence of an acidic esterification catalyst such as paratoluenesulfonic acid, benzenesulfonic acid, sulfuric acid and trifluoroacetic acid, but it is also formed in order to carry out the reaction easily and uniformly. In order to remove water out of the system, it is advisable to carry out this in a solvent such as toluene, benzene, xylene, or cyclohexane. Although this reaction can be carried out at normal pressure,
Well-known techniques relating to esterification techniques such as water traps may be used to remove the water produced.

The SH group-containing polymer of the present invention is used in various applications, to which metal oxides, metal peroxides, organic peroxides and the like as plasticizers, fillers and curing agents have been added. The composition is useful as a sealing material for construction, a coating material for waterproofing and antifouling, and when this compound is used in combination with a vinyl group-containing compound and a sensitizer, it is easily cured by UV irradiation, so it is an ultraviolet curing coating material. , Can be used as a vehicle for paints.

[0010]

EXAMPLES Next, examples of the present invention will be given. Example 1 To a 1-liter reaction flask equipped with a condenser, an ester adapter, and a thermometer, 227 g of polyolefin polyol / polytail HA (described above), 9 g of thiodipropionic acid, 250 g of toluene, and 1 g of paratoluenesulfonic acid were added and stirred. While the temperature was raised, the reaction was carried out at the reflux temperature of toluene, and the produced water was removed from the system with an ester adapter and allowed to react for 3 hours.
The reaction was terminated when the amount reached 8 g.

Next, the temperature was lowered to 50 to 60 ° C., 5 g of sodium carbonate was added to neutralize the paratoluenesulfonic acid and then filtered, and toluene was distilled off at 120 ° C./20 mmHg. As a result, 238 g of a viscous liquid was obtained. Was obtained, an infrared spectrophotometer chart (see FIG. 1) was taken for this, and its physical properties were measured. As a result, this product had a viscosity of 1,350 poises (25 ° C.) and a refractive index of 1. 47
97 (25 ° C.), specific gravity 0.889 (25 ° C.), SH group contained therein is 0.040 mol / 100 g,
Since the elemental analysis value is C H OS theoretical value (%) 81.89 13.51 2.63 1.97 Analytical value (%) 81.90 13.47 2.65 1.98, the following formula HSC ₂ It was confirmed that this is represented by H ₄ COO (CH ₂ ) ₁₆₀ OCOC ₂ H ₄ SC ₂ H ₄ COO (CH ₂ ) ₁₆₀ OCOC ₂ H ₄ SH.

Example 2 In the same reaction flask used in Example 1, 340 g of polyolefin polyol Polytail HA (supra),
Thiodipropionic acid 18 g, toluene 350 g and paratoluene sulfonic acid 2 g were added, the temperature was raised with stirring to cause a reaction at the toluene reflux temperature, and the reaction was continued for 3 hours while removing the water produced with an ester adapter, and the amount of water produced. When the amount became 1.8 g, 11 g of β-mercaptopropion was added to this system and the reaction was further continued for 3 hours. When the amount of water produced became 3.6 g, the reaction was terminated.

Next, the temperature was lowered to 50 to 60 ° C., 10 g of sodium carbonate was added to neutralize paratoluenesulfonic acid, and the mixture was filtered, and toluene was distilled off at 120 ° C./20 mmHg. As a result, 355 g of a viscous liquid was obtained. Was obtained,
An infrared spectrophotometer chart for this (see FIG. 2) was taken and the physical properties were examined. As a result, the viscosity was 6,300 poises (25 ° C.) and the refractive index was 1.48.
00 (25 ° C), specific gravity is 0.890 (25 ° C),
SH group contained here is 0.027 mol / 100 g
And the elemental analysis values are C H OS theoretical value (%) 82.11 13.50 2.63 1.76 analytical value (%) 82.10 13.45 2.55 1.80, The following formula HSC ₂ H ₄ COO (CH ₂ ) ₁₆₀ OCOC ₂ H ₄ SC ₂ H ₄ COO (CH ₂ ) ₁₆₀ -COOC ₂ H ₄ SC ₂ H ₄ COO (CH ₂ ) ₁₆₀ OCOC ₂ H ₄ SH Was confirmed.

[0014]

INDUSTRIAL APPLICABILITY The present invention relates to a mercapto group-containing polymer and a method for producing the same, which relates to a novel mercapto group-containing polymer of the above-mentioned general formula (1) which has not been described in any literature. The production method is characterized by dehydrating a polyolefin polyol with a mercaptoalkanoic acid and a dicarboxylic acid, which is useful as a rubber sealant, a coating material, and an ultraviolet curable coating material.

[Brief description of drawings]

FIG. 1 shows a chart of an SH group-containing polymer obtained in Example 1 of the present invention by an infrared spectrophotometer.

FIG. 2 shows a chart of an SH group-containing polymer obtained in Example 2 of the present invention by an infrared spectrophotometer.

Claims (2)

[Claims] 1. A general formula HS-R ¹ -COO (CH ₂ ) _m [OCOR ² _k COO (CH ₂ ) _m ] _l OCOR ¹ -SH (wherein R ¹ is a divalent hydrocarbon having 1 to 6 carbon atoms). Group, R ² is a divalent hydrocarbon group having 1 to 12 carbon atoms or a divalent organic group having 4 or less carbon atoms and containing a thioether bond, and m is 50 to 40
A mercapto group-containing polymer represented by 0, 1 is 1 to 20, and k is a number of 0 or 1. 2. The general formula HO (CH ₂ ) _m OH (m is 50 to ₄ ).
00)), a mercaptoalkanoic acid represented by the general formula HS-R ¹ -COOH (R ¹ is a divalent hydrocarbon group having 1 to 6 carbon atoms) and a general formula HOCOR ² COOH (R ² Is a dicarboxylic acid represented by a divalent hydrocarbon group having 1 to 12 carbon atoms or a divalent organic group having 4 or less carbon atoms containing a thioether bond), and the dehydration reaction is carried out with the general formula HS-R ¹ -COO. (CH ₂ ) _m [OCOR ² _k COO (CH ₂ ) _m ] _l OCOR ¹ -SH (R ¹ , R ² and m are the same as above, l is 1 to 20 and k is 0.
Alternatively, the method for producing a mercapto group-containing polymer represented by 1).