JPH03195750A - Curable rubber-like composition and molded and cured product thereof - Google Patents

Abstract

PURPOSE:To obtain the subject composition, composed of an organic high- molecular weight substance, composed of a high-molecular weight part of the backbone chain and specific acid anhydride groups, a polyol, sulfur, etc., rapidly curable at a rubber vulcanization temperature in spite of a sufficiently long pot life at ordinary temperature and useful as rubber tile materials. CONSTITUTION:The objective composition containing (A) 0.5-10 pts.wt. sulfur and, as necessary, (B) 100-1000 pts.wt. rubber chip material in 100 pts.wt. total amount of (C) an organic high-molecular weight substance containing (i) a high- molecular weight part (e.g. isobutylene) of the backbone chain having 300-30000 molecular weight and (ii) 0.05-0.5mol [based on 100g component (C)] acid anhydride groups, expressed by the formula (R is H, halogen or 1-3C organic group; X is H or bond), bound to the aforementioned part (i) through C-C bond or constructing part of the backbone chain and (D) a polyol (e.g. polybutadiene polyol) using a compound having C=C double bond in either of the components (C) and (D) at 0.5-1.5 equiv. ratio of hydroxyl groups in the components (C) to (D).

Description

Detailed Description of the Invention <Field of Industrial Application> The present invention relates to a curable rubber-like composition. A curable rubber-like composition that quickly hardens into a rubber-like state when heated to a sulfur temperature, and a vibration-proofing/damping material;
This invention relates to a molded and cured product of the rubber tile material, which is widely used as a rubber tile material for soundproofing materials, cushioning materials, etc.

<Conventional technology> Rubber tiles used as vibration-proofing materials, cushioning materials, etc.
Generally, they have been produced by molding and curing a molding composition obtained by mixing various compounding agents with a liquid binder that can be hardened into an elastic body. Various types of liquid binders that can be cured into an elastic body are known, but the ones that have been widely used are (1) a system consisting of a polyol and an organic polyisocyanate, and (2) a system consisting of a liquid diene rubber and sulfur. Broadly divided into systems. Products with good performance can be obtained by both of these systems (1) and (2), however, system (1) requires the reaction of a compound having active hydrogen with a polyisocyanate compound. Therefore, the reaction proceeds quickly and it is difficult to control the pot life.There is a risk of reaction with moisture in the air and foaming occurs easily when heated.Polyisocyanate compounds are highly toxic and difficult to handle. There are drawbacks such as the need for caution.

On the other hand, system (2) does not have such drawbacks, but it takes a long time to heat and harden, and for example, in the case of thick-walled products of 10 mm or more, the molding cycle is extremely long and productivity is low. .

<Problems to be Solved by the Invention> The present invention does not have the drawbacks of the systems (1) and (2) described above, that is, it has a sufficiently long pot life and is easy to control, and moreover, it can be heated quickly. The object of the present invention is to provide a curable rubber-like composition that can be cured into a molded cured product exhibiting excellent properties.

Means for Solving the Problems> Therefore, the present invention provides (A) (a) a main chain high molecular weight portion having a molecular weight of 300 to 30,000, and (b) a carbon-carbon in the main chain high molecular weight portion. A general formula that is bonded by a bond or forms part of the main chain: In the formula, R represents hydrogen, halogen, or a C8~ organic group, and X represents hydrogen or a bond. (A) an organic high molecular weight substance consisting of acid anhydride groups contained in a proportion of 0.05 to 0.5 mol per 100 g, (B) a polyol, (C) sulfur, and (D) optionally a rubber chip material. and at least one of both components (A) and (B) is a compound having a carbon-carbon double bond that can form a crosslinking bond by reaction with sulfur. In the present invention, as will be explained in detail later, two completely different crosslinking means are used, namely, a crosslinking method between the acid anhydride group of the component (A) and the hydroxyl group of the component (B). By introducing the ester crosslinking and the crosslinking between the carbon-carbon double bonds of the component (A) and/or the component CB) using sulfur in the above-described manner, the above-mentioned problems could be solved.

The present invention will be explained in more detail below.

The main chain high molecular weight portion (a) of component (A) used in the present invention preferably has an iodine value of 50 to 500, more preferably 100 to 470 and has a number average molecular weight (hereinafter simply (referred to as molecular weight) 300 to 30
．． 000 high molecular weight compounds are used. When a polyol having a carbon-carbon double bond is used as the component (B), the component (A) may not have a carbon-carbon double bond.

Examples of such high molecular weight compounds include natural oils and fats such as linseed oil, tung oil, soybean oil, and dehydrated castor oil, so-called stand oils whose molecular weights are increased by heat-treating these natural oils, butadiene, isoprene, and Low polymers of conjugated diolefins such as piperylene, low polymerization degree copolymers of two or more of these conjugated diolefins, vinyl having one or more of these conjugated diolefins and ethylenically unsaturated groups Nanatsumer-1, especially inbutylene, diisobutylene,
Aliphatic or aromatic vinyl monomers such as styrene, alpha-methylstyrene, vinyltoluene, and divinylbenzene.
Examples include low polymerization degree copolymers with A mixture of two or more of these can also be used. These low polymers are produced by conventionally known methods (U.S. Pat.
No. 2-7446, No. 34-10188, No. 45-50
(See No. 7, etc.)

The low polymerization degree polymer or copolymer of the natural oil or fat or conjugated diolefin used has a molecular weight in the range of 300 to 30.000, preferably 500 to 5,000. If the molecular weight is greater than 30,000, the viscosity will be high and the fluidity will be poor, making mixing difficult. If the molecular weight is less than 300, the strength of the cured product is too low to be used practically. The above natural oils and fats or low polymerization degree conjugated diolefin polymers or copolymers preferably have an iodine value of 5.
0 to 500, more preferably 100 to 470. If the iodine value is less than 50, it is difficult to introduce the group (b) when acid anhydride (b) is introduced into these by maleation reaction, and if it is greater than 500, the storage stability is poor and it is not practical. It cannot be offered to

The iodine value used in the present invention is determined by taking 0.1 g of a sample into a 500 mQ iodine value measurement flask, adding chloroform 100a+ff and p-dichlorobenzene looog, and dissolving the iodine value at 0.1N. After adding 60 m<1 of a carbon tetrachloride solution of iodine chloride and reacting on a shaker for 1 hour at room temperature, 10 mQ of θ% potassium iodide aqueous solution was added and shaken for 5 minutes.Next, using starch as an indicator, 0. Titration method with 1N sodium thiosulfate aqueous solution (A, Kemp and H, Peters,
Ind, Eng, Chem, Anal, E
d, 15.453 (1943)).

As a method for introducing an acid anhydride group (b) represented by -irradiation (where R and X are the same as above) into the above natural oils and fats or conjugated diolefin low polymer or copolymer. A conventionally known method can be used (Japanese Patent Publication No. 46-11195,
West German Publication No. 2362534, etc.).

The amount of acid anhydride group (b) shown in the above - cutting is 100% of component (A)
ranging from 0.05 to 0.5 mol per g, preferably 0.1
~0.3 mol. The amount of group (b) is component (A) 100
If it is less than 0.05 mole per g, the strength of the composition will be low, and if it is more than 0.5 mole, the viscosity will be high.
It cannot be used practically.

As the polyol which is component (B) of the composition of the present invention, an organic compound having usually 2 to 500 carbon atoms, preferably 2 to 200 carbon atoms is used. For example, polybutadiene polyol (trade name: Poly-bdR-45HT manufactured by Idemitsu Petrochemical Co., Ltd., trade name: N15s).

Pb G-2000 manufactured by Nippon Soda Co., Ltd., product name: B
utarez HT L Polymers
Phillips 66Co), polyolefin polyol (product name: Polytail HA%H Mitsubishi Kasei (product name: Polytail HA%H)
Co., Ltd.), polyisobutylene diol (product name: PIB
Diol, Akron Cationic P
olymer D ev.

Co, ), modified liquid polyisoprene rubber (product name: Kuraprene LIR-503,506, manufactured by Kuraray Co., Ltd.),
Castor oil, polyethylene glycol, polypropylene glycol, polyester polyol, acrylic polyol, trimethylolpropane, glycerin, ethylene glycol, 1.4-butanediol, ■, 4-cyclohexanediol, 1.6-hexanediol, bis(hydroxymethyl) Tricyclo[5,2,1,0”・61
Decane and the like are used, and a mixture of these may be used.

There is no particular restriction on the amount of polyol used, but the equivalent ratio of the acid anhydride (b) of component (A) to the hydroxyl group of component (B) is 0.
5 to 1.5, more preferably 0°8 to 1.2.

Although the combination of components (A) and (B) is arbitrary, at least one of them should be a compound having a carbon-carbon double bond. Preferably, both component (A) and component (B) are compounds having a carbon-carbon double bond.

The sulfur component (C) may be in any form, but from the viewpoint of mixing and dispersibility, it is preferably in the form of a fine powder to a colloid. There is no particular restriction on the amount used, but component (A) and C
The amount is preferably 0.5 to 10 parts by weight based on a total of 100 parts by weight of component B).

In order to promote heat assimilation, vulcanization accelerators which are usually used in combination with sulfur in the rubber industry, such as dialkyldithiocarbamates, thiuram accelerators, thiazole accelerators, etc., may be added.

As the rubber chip material, which is component (D), used as necessary in the present invention, examples include granular materials obtained by crushing vulcanized rubber and materials obtained by cutting by-product rubber fibers (rubber fibers) during tire retreading. . The blending ratio of the rubber chip material varies depending on the properties of the target rubber composition, but it is preferably 100 to 1000 parts by weight of the rubber chip material based on a total of 100 parts by weight of components (A) and (B).

Furthermore, in the present invention, in order to control the pot life of the mixture and solidify it in a short period of time, compounds commonly used as esterification catalysts, such as triethylamine, tributylamine, dimethylbenzylamine, 2,4,6-tris( amines such as dimethylaminomethyl)phenol,
Imidazoles such as 2-ethyl-4-methylimidazole, 2-methylimidazole and 2-phenylimidazole, phosphines such as triphenylphosphine, etc. may be added.

Although the composition of the present invention has sufficient performance after solidification, it may be necessary to add a compound having a high boiling point plasticizing action, such as Hysol 5AS-296, condenser oil S (both of which are chemically Co., Ltd. product name), NeoSK
-OIL l 400 (product name of Dengoku Kagaku Co., Ltd.),
Dioctyl phthalate, tricresyl phosphate,
Dioctyl sebacate, process oil, etc. may be added. Furthermore, flame retardants, antioxidants, ultraviolet absorbers, metal deactivators, inorganic fillers, dyes, pigments, etc. may be added.

The mixture obtained as described above is cured by heating, and the vulcanization conditions normally used in rubber factories are sufficient, for example, 120 to 200 °C for 5
All you have to do is heat it for about 30 minutes.

The rubber composition of the present invention generates bonds with sulfur in addition to bonds due to the reaction between the acidic group (b) in component (A) and the hydroxyl group in component (B), and has increased strength and rubber chips. When a rubber chip material is added, sulfur vulcanization causes rubber chip material and (
Adhesion with components A) and (B) is also improved.

<Example> Next, the present invention will be explained in more detail with reference to Examples.

Synthesis Example 1 1000 g of polybutadiene B-1000 (manufactured by IE1 Petrochemical Co., Ltd.) having 58% of 1.2 bonds and a number average molecular weight of 1000, 163 g of maleic anhydride, and Antigen 6C (Sumiman Chemical Co., Ltd.) as a gelling inhibitor. Manufactured by Kogyo Co., Ltd.) 2
Antigen 6C pre-dissolved in 10g of xylene
The solution was charged into a separable 7 rusk equipped with a 2a reflux condenser, and a maleation reaction was carried out at 195° C. for 5 hours under a nitrogen stream. After the reaction, nitrogen bubbling was performed to drive out xylene to obtain maleated polybutadiene (referred to as [F, component (A-1)). The acid value of component (A-1) produced above was 80 mg KOH/g.

Synthesis Example 2 Polybutadiene B-2000 (manufactured by Nippon Petrochemical Co., Ltd.) having 65% of 1.2 bonds and a number average molecular weight of 2000
1000 g, 163 g of maleic anhydride8 and 2 g of Antigen 6C (manufactured by Sumitomo Kagaku Kogyo Co., Ltd.) as an anti-gelling agent.
A solution of antigen 6C preliminarily dissolved in log xylene was charged into a 2a separable flask equipped with a reflux condenser, and a maleation reaction was carried out at 195° C. for 15 hours under a nitrogen stream. After the reaction, nitrogen bubbling was performed to drive out xylene to obtain maleated polybutadiene (hereinafter referred to as component (A-2)). The acid value of component (A-2) produced above was 80 mg KOH/g.

Example 1 100 g of component (A-1) obtained in Synthesis Example 1 and polybutadiene polyol (Poly-bd
177 g of R-45HT (manufactured by Idemitsu Petrochemical Co., Ltd.) was thoroughly mixed, and then 8.3 g of sublimated sulfur was added and thoroughly mixed again. The resulting mixture was placed in a mold preheated to 150°C and heated at the same temperature for 5 minutes at 50 kgf/cm.
A rubber composition was obtained by pressure molding. The results are shown in Table 1.

The obtained mixture and rubber composition were evaluated as follows.

(1) Pot life The mixture was left at room temperature, and the time required for the viscosity to double was measured.

(2) Tensile strength, elongation Measured in accordance with JIS K6301.

(3) Hardness Measured according to JIS K7215 durometer A hardness.

Examples 2 to 3 The same procedure as in Example 1 was carried out except that 2-ethyl-4-methylimidazole was further added to the mixture obtained in Example 1 in the amount shown in Table 1, and a rubber-like composition and its molding and curing were prepared. I got something. The results are shown in Table 1.

Comparative Example 1 Table 1 shows the results of the same procedure as in Example 1 except that sulfur was not added.

Example 4 Same mixture as Example 2 with screen grade 2-3m
Add 300g of recycled rubber chip material and stir well using a mixer.
Pressure molding was performed at 150° C. for 5 minutes to obtain a molded cured product. The results are shown in Table 1.

Example 5 Example 4 except that component (A-2) obtained in Synthesis Example 2 was used.
I did the same thing. The results are shown in Table 1.

<Curing of the invention> As is clear from the results summarized in Table 1, in the present invention, the pot life can be controlled over a wide range, and by adding component (C) sulfur, curing It can significantly improve the mechanical properties of objects. Furthermore, by adding recycled rubber chip material as component (D), it was possible to further improve the mechanical properties, which was unexpected from conventional knowledge, and also from an economic point of view. This is extremely advantageous.

1 other person

Claims (1)

[Scope of Claims] 1. (A) (a) a main chain high molecular weight portion having a molecular weight of 300 to 30,000, and (b) bonded to the main chain high molecular weight portion via a carbon-carbon bond, or General formulas that form part of the main chain: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R represents hydrogen, halogen, or an organic group of C_1_ to_3, and X represents hydrogen or a bond. As shown, (A) 10
An organic high molecular weight substance consisting of an acid anhydride group contained in a proportion of 0.05 to 0.5 mol per 0 g, (B) a polyol and (C) sulfur, and (D) optionally containing a rubber chip material, and (A), (
B) A curable rubber-like composition characterized in that at least one of the two components is a compound having a carbon-carbon double bond that can form a crosslinking bond by reaction with sulfur. 2. The composition according to claim 1, which is molded and cured.