JPH028222A - Low-temperature plasticizer for polysulfide 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 [Field of Industrial Application] The present invention relates to a low-temperature plasticizer for polysulfide polymers, and more specifically to a polysulfide polymer that provides workability at low temperatures and low volatility at high temperatures. Low temperature plasticizer for use.

[Conventional technology and its problems]

Conventionally, plasticizers for polysulfide polymers include butylbenzyl phthalate, etc., as described in "Architectural Sealants and Their Correct Usage" edited by Japan Sealing Industry Association (Sanpo Co., Ltd.), page 135. Phthalate ester plasticizers, hydrocarbon plasticizers such as alkylene triphenyl, chlorinated paraffin, dibutyl adipate, etc. are used.

However, if a paint containing vinyl chloride resin or polyacrylic acid ester as a main component is applied on top of a polysulfide sealant containing butyl benzyl phthalate, chlorinated paraffin, dibutyl adipate, etc., the paint film will soften. This makes it easier for dirt to adhere to the surface of the paint film.

In addition, in polysulfide sealing materials that use chlorinated paraffin, alkylene triphenyl, etc. as plasticizers for polysulfide polymers, workability is extremely poor due to the high viscosity of the chlorinated paraffin, alkylene triphenyl, etc. used as plasticizers. Construction in winter was virtually impossible.

In order to improve these drawbacks, aliphatic dibasic acid glycol esters such as dibutyl diglycol adipate and dimethyltetraglycol adipate have been proposed (Japanese Patent Application Laid-Open No. 61-207451), and the cold resistance has been improved to some extent. However, because these glycol ester compounds have poor water resistance, they tend to cause thinning or cracking after application, and the sealant tends to lose a lot of heat when heated. A drug was desired.

[Means for solving problems]

In view of the above problems, the present inventors have conducted intensive studies on plasticizers that have low viscosity, are well compatible with polysulfide polymers, and have an excellent plasticizing effect on polysulfide polymers at low temperatures.As a result, the present inventors have developed the present invention. reached.

That is, the present invention relates to the following general formula (1) and/or (II
) A low-temperature plasticizer for polysulfide polymers comprising a diester compound represented by:

(In the formula, A represents an alkylene group having 2 to 4 carbon atoms,
R3 and R2 each represent an aliphatic carboxylic acid residue having 1 to 14 carbon atoms, m represents a number of 4≦m≦20, and B
represents an alkylene group having 2 to 4 carbon atoms, b and R4
each represents an alkyl group having 1 to 8 carbon atoms, p and q represent θ to 4, and 2≦p+q≦6. ) In the diester compound represented by the above general formula (1) and/or (II), A and B each have 2 to 2 carbon atoms.
4 represents an alkylene group, for example, ethylene, 1,2-
Propylene, 1,3-propylene, 1゜2-butylene,
Examples include 1.3-butylene and 1.4-butylene.

Further, R1 and R1 of the diester compound represented by the above general formula (1) each represent an aliphatic carboxylic acid residue having 1 to 14 carbon atoms, such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, Residues of saturated aliphatic carboxylic acids such as heptanoic acid, caprylic acid, octylic acid, 2-ethylhexylic acid, nonanoic acid, decylic acid, undecylic acid, lauric acid, myristic acid, acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid , unsaturated aliphatic carboxylic acid residues such as pentenoic acid, hexenoic acid, octenoic acid, decenoic acid, and dodecenoic acid.

Further, R1 and R4 of the diester compound represented by the above general formula (II) represent an alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl,
Examples include groups such as isobutyl, sec-butyl, tertiary-butyl, pentyl, heptyl, heptyl, octyl, and 2-ethylhexyl.

The diester compound represented by the above general formula (I) and/or (II) is synthesized by a conventionally known method. for example,
A dehydration condensation reaction between a hydroxy compound and an aliphatic carboxylic acid or phthalic acid, a transesterification reaction between a hydroxy compound and an aliphatic carboxylic acid ester or a phthalic acid ester, or a dehydration reaction between a hydroxy compound and an aliphatic carboxylic acid or a phthalic acid halide. It is synthesized by a reaction method using a hydrogen halide scavenger.

Synthesis Example 1 Polyethylene glycol (600) 840 g (1,
4 mol), octylic acid 524 g (3.64 mol),
6.8 g of activated carbon and 0.0 g of tetraisopropyl titanate.
68 g was stirred for 8 hours under a nitrogen stream at 220° C. while removing generated water. Add excess octylic acid to 15 o+
After removal under reduced pressure of mHg, the product was filtered through Celite to obtain 1142 g of a pale yellow transparent liquid.

Acid value 0.08, hydroxyl value 2.4, viscosity 80 cρ specific gravity 1.043 Synthesis example 2 Dibutyl glycol 878 g (7.44 mol), phthalic anhydride 459 g (3.1 mol), activated carbon 6.7g
A mixture of 0.67 g of tetraisopropyl titanate and 0.67 g of tetraisopropyl titanate was gradually heated under a nitrogen stream while removing alcohol including produced water, and the temperature reached 200° C. in 8 hours. After removing excess alcohol under reduced pressure of 15 m+sHg, the product was filtered through Celite to obtain a colorless transparent liquid 107
8 g was obtained.

Acid value 0.23, hydroxyl value 0.7, viscosity 34 cp specific gravity 1.060 Diester compound represented by general formula (1) and/or (■) used as a low temperature plasticizer for polysulfide polymer in the present invention The amount used is polysulfide polymer 10
1 to 150 parts by weight relative to 0 parts by weight, preferably 3 to 1
If the diester plasticizer exceeds 150 parts by weight, problems in construction such as slump will occur.

The polysulfide polymer blended with the low-temperature plasticizer of the present invention can be used as a one-component curing composition containing the polymer as a main ingredient and a water-activated curing agent, or both can be packaged separately. Used as a two-part curing composition. The above-mentioned water-activated hardening agents include water-activated peroxides (e.g., lead peroxide, calcium peroxide, zinc peroxide, strontium peroxide, barium peroxide, lithium peroxide, sodium peroxide, permanganese peroxide). potassium acid, sodium carbonate peroxide, and sodium pernitrate), lead dioxide, and manganese dioxide.

These are usually used in an amount of 2 to 30 parts by weight, preferably 4 to 20 parts by weight, per 100 parts by weight of the polysulfide polymer.

Regarding other compounding agents, those normally added to polysulfide polymers, such as sulfur, rubber vulcanizing agents, vulcanization accelerators, anti-aging agents, UV and ozone deterioration inhibitors, fillers, softeners, adhesives. Additives, processing aids, pigments, curing rate regulators, reinforcing agents, etc. can be added as necessary.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by the following examples.

Example 1 A polysulfide polymer composition was prepared comprising 100 parts by weight of a polysulfide polymer ("Thiokol LP-32" manufactured by Toshi Thiokol ■) and 50 parts by weight of the diester plasticizer of the present invention. After mixing, the mixture was allowed to stand at room temperature for one month, and the compatibility of the composition was observed from the state of separation and cloudiness. Also J
The viscosity at 5°C was measured according to IS K-1557r Polyether Test Method for Polyurethanes. Furthermore, the mixed composition was placed in the open at 125° C. for 70 hours, and the weight loss on heating was measured.

The results are shown in Table 1 below.

Example 2 A polysulfide polymer ("Thiokol LP-55" manufactured by Toshi Thiokol ■) and a diester plasticizer of the present invention were blended in the following composition, and the workability as a sealing material at low temperatures was measured. The workability was measured in accordance with JIS A-5758r Architectural sealing material J(5,2)r extrudability measurement method. According to this measurement method, the shorter the extrusion time, the better the workability.

JIS A-5758 requires that the extrusion time at 5° C. be 30 seconds or less.

Blended Thiokol LP-55 100 parts by weight Ester plasticizer 60 parts by weight Calcium carbonate 54 parts by weight Titanium dioxide
33 parts by weight 2-mercaptobenzothia 1 part by weight Zole sulfur 0.1 part by weight The results are shown in Table 2 below.

Table 2 Example 3 A polysulfide polymer ("Thiokol LP-56" manufactured by Toshi Thiokol ■) and the diester plasticizer of the present invention were blended in the following compositions, each of the resulting compositions was cured, and each curing The weight loss on heating was measured. Heat loss is JI
S A-57584r Architectural sealing material J (5,1
0) rHeating loss measurement method” was followed. The results are shown in Table 3 below.

Blend - 8 Main agent Thiokol LP-56 Ester plasticizer Calcium carbonate Titanium dioxide Carbon Sulfur Hardener Lead dioxide Plasticizer Stearic acid 9.8 parts by weight 3.0 parts by weight 0.2 parts by weight 100 parts by weight 60 parts by weight 54 parts by weight 33 Part by weight 0.5 part by weight 0.1 part by weight Blending-B Main ingredient Thiokol LP-56 Ester plasticizer Calcium carbonate Titanium dioxide Water-absorbing resin 2-mercaptobenzothiazole sulfur hardening agent Sodium perborate plasticizer 1 0 parts by weight 0 parts by weight 4 parts by weight 3 parts by weight 2 parts by weight 1 part by weight 0.1 parts by weight 6.1 parts by weight 0.1 parts by weight Example 4 Hydrolyzability of the diester plasticizer for polysulfide polymers of the present invention In order to see the difference between 100 parts by weight of plasticizer and 1 part by weight of distilled water, the mixture was put into a flask, sealed tightly and heated and stored in an oven at 100°C for 70 hours. The results are shown in Table 4 below.

Claims (1)

[Scope of Claims] A low-temperature plasticizer for polysulfide polymers, comprising a diester compound selected from the following general formulas (I) and/or (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, A represents an alkylene group having 2 to 4 carbon atoms,
R_1 and R_2 each represent an aliphatic carboxylic acid residue having 1 to 14 carbon atoms, m represents a number of 4≦m≦20, B represents an alkylene group having 2 to 4 carbon atoms, and R_3
and R_4 each represent an alkyl group having 1 to 8 carbon atoms, p and q represent 0 to 4, and 2≦p+q≦6. )