JPS59155445A - Composite material - Google Patents

Abstract

PURPOSE:To provide a composite material useful as flame-retardant wall, flame- retardant floor, vibration insulator, soundproofing material, electromagnetic wave shielding material, radiation shielding material, heat insulating material, etc., by uniformly dispersing a hydrated particulate inorg. material in a specified modified low-molecular diene polymer. CONSTITUTION:A peracid or hydrogen peroxide and a carboxylic acid are reacted with a low-molecular diene polymer having an MW of 4,000-100,000, such as polybutadiene or a modified diene polymer obtd. by adding 0.1-30mol (for 100 monomer units of said polymer) of maleic anhydride or its derivative to said low-molecular diene polymer to convert double bonds in the polymer into 0.1- 30mol (for 100 double bonds) of epoxy groups, thus obtaining a modified low- molecular diene polymer. The desired composite material can be obtd. from the resulting modified polymer and a hydrated particulate inorg. material having a water content of 5wt% or above, such as calcium hydroxide.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composite comprising a water-containing particulate inorganic material and a modified low molecular weight diene polymer.

In general, the inorganic photonic agent in the composite is usually used in a dried form with a low water content; however, depending on the field in which the composite is applied, it may be in a water-containing state before drying. But sometimes it's enough. If hydrated granular inorganic materials can be used, it will be possible to rationalize the manufacturing process of the filler, and it will also be good for dust prevention and environmental hygiene. It is expected that it will work advantageously in terms of performance such as heat retention. Furthermore, if water-containing particulate inorganic substances produced as by-products or waste in various industrial fields can be effectively utilized, it will be of great significance in terms of resource and energy conservation.

However, when creating a composite of water-containing particulate inorganic material (referred to as water-containing particulate inorganic material) and organic polymer, a technique is first required to uniformly mix the water-containing particulate inorganic material and the polymer. . Generally thermoplastic resin, thermosetting resin,
When rubber is used, it is difficult to obtain a homogeneous mixture because the mixing operation does not proceed normally due to the presence of water.

The present inventors have conducted extensive studies with the aim of creating an organic polymer that is effective for producing composites using particulate inorganic materials with a high water content, and have found that the molecular weight (viscosity average molecular weight) is 4.00
A modified low molecular weight diene polymer having a molecular weight of 4,000 or 0.1 to 30 mol of maleic anhydride or its derivative added per 100 monomers of the polymer to a low molecular weight diene polymer having a molecular weight of 0 to 100.0[10] ~i
A low molecular weight diene polymer, o o, o o o, is reacted with peracid or hydrogen peroxide and a carboxylic acid to remove 100 of the double bonds. The present inventors have discovered that water-containing particulate inorganic substances can be uniformly mixed and dispersed by using a modified low molecular weight diene polymer converted into 1 to 50 mo/I/mold epoxy groups, and have completed the present invention.

That is, in the present invention, maleic anhydride or a derivative thereof is added to a water-containing particulate inorganic material containing 5 weight percent or more of water, a low molecular weight diene polymer having a molecular weight of 4,000 to 100,000, and 100% of the monomer of the polymer. Atta. ! 1l
A modified low-molecular-weight diene-based polymer with 11 to 30 10 mol added thereto, or a low-molecular-weight diene-based polymer with a molecular weight of 4.00-0 to 100.000, is reacted with peracid or hydrogen peroxide and a carboxylic acid to form a diacetate of the polymer. It is a composite that does not seep out water and exhibits rubber elasticity, consisting of a modified low molecular weight diene polymer in which 100 to 60 moles of heavy bonds are converted to epoxy groups.

The hydrated granular inorganic material used in the present invention is composed of water existing as free water in the granular inorganic material and the granular inorganic material.
Water content is 5-300% by weight, particularly preferably 15-100%
It is outside the weight range. Note that water that is fixed in inorganic substances as crystal water is excluded from the calculation of water content.

Here, examples of particulate inorganic substances include calcium hydroxide,
Polyvalent metal hydroxides such as magnesium hydroxide, barium hydroxide or aluminum hydroxide, calcium carbonate,
Carbonates of polyvalent metals such as magnesium carbonate or zinc carbonate, oxides of polyvalent metals such as zinc oxide, magnesium oxide, lead oxide, titanium oxide, aluminum oxide or iron oxide (ferrite), aluminum sulfate, calcium sulfate ( gypsum) or barium sulfate, polyvalent metal sulfates, zinc powder, aluminum powder, brass powder 1. - Metal powders such as iron powder, magnesium powder, or copper powder, and other metal powders such as V-, silica, curcum, mica, silica, and litho can be used alone or in combination of two or more. These granular inorganic substances may be in a water-containing state at the time of production, or they may be by-products as waste from various industries. When the water content is relatively low, the water-containing particulate inorganic material is in the form of a powder or small lumps, but when the water content is high, it becomes a paste or slurry.

Next, the modified low molecular weight diene polymer, which is an important component in the present invention, will be explained. Here, the modified low molecular weight diene polymer is a modified low molecular weight polymer obtained by adding maleic anhydride or its derivative to a low molecular weight diene polymer. This is a modified low molecular weight diene polymer (■) in which the double bonds of the above polymer were converted into epoxy groups.

Examples of diene-based polymers include polybutadiene, polyisoprene, polypentadiene, butadiene-isoprene copolymer, butadiene-styrene copolymer, isoprene-styrene copolymer, and acrylonitrile-butadiene copolymer. , acrylonitrile-isoprene copolymer, or ethylene-propylene-diene copolymer - in addition to these, partially hydrogenated products of these can also be used. These polymers may be used alone or in combination of two or more.

If the molecular weight of the diene polymer is too high or too low, it will become unsuitable for mixing with water-containing granular inorganic materials, and the water will separate, making mixing impossible.
,000-100,000, especially 10,000-,
-'75,000 is preferred.

Although the microstructure of the low molecular weight diene polymer is not particularly limited, 1. When flexibility, especially flexibility at low temperatures, is required for the finally obtained composite, it is preferable that the diene polymer has a small amount of vinyl bonds. Furthermore, since the viscosity of the polymer tends to be lower when there are fewer vinyl bonds, it is preferable to have a smaller amount of vinyl bonds from the viewpoint of mixing workability.

From this point of view, the vinyl bond amount is 60% or less, especially 60% or less.
% or less.

The above-mentioned modified low molecular weight diene polymer (1) is a modified polymer obtained by adding maleic anhydride or a maleic anhydride derivative such as maleic acid, maleic acid ester, maleic acid amide or maleic acid imide to a low molecular weight diene polymer; Furthermore, the above-mentioned modified polymer, particularly a maleic anhydride-modified polymer to which maleic anhydride has been added, is reacted with alcohol to convert one or both of the carboxyl groups of maleic anhydride into an ester, ammonia,
n-butylamine, diethylamine, aminoalco-p
etc., by reacting with amines such as maleic anhydride to amidate one or both of the carboxyl groups, further modifying the amidated product to imidize it, and reacting with an epoxy compound to amidate one or both of the carboxyl groups based on maleic anhydride. Examples include those with a modified carboxyl group, and those with an alkali metal hydroxide reacted to form an alkali metal carboxylate partially or entirely based on maleic anhydride.

The above-mentioned modified low molecular weight diene thread polymer (II) is a low molecular weight diene polymer whose double bonds are converted into epoxy groups by a known method using peracid or hydrogen peroxide and a carboxylic acid.

Note that these modified low molecular weight diene polymers may be partially or completely hydrogenated after modification.

In a modified low molecular weight diene polymer, what is important in addition to the molecular weight is the amount of functional groups introduced (added amount), whether it is a functional group based on added maleic anhydride or a derivative thereof, or a functional group exclusively based on an epoxy group. If the amount of functional groups introduced (added amount) is too small or too large, water dispersion will be poor when the water-containing particulate inorganic material is mixed, making the mixing process itself difficult, and the resulting composite becomes extremely non-uniform, resulting in poor mechanical properties of the composite, making it impractical. Therefore, the amount of functional groups introduced (added amount) is in the range of 0.1 to 60 moles, or 1 to 10 moles, per 100 monomers or 100 double bonds of the low molecular weight diene polymer. It is preferable to have one.

In the composite of the present invention, it is effective to use a relatively large amount of the water-containing particulate inorganic material. For example, the water-containing particulate inorganic material is 6 parts per 100 parts by weight of a modified low molecular weight diene polymer.
It is used in a range of 0 to 2.000 parts by weight. When it is necessary to process a large amount of water-containing particulate inorganic material and when the mechanical performance of the final molded composite is required, the amount of water-containing particulate inorganic material to be used is equal to 100 parts by weight of the modified diene polymer. A suitable amount is 80 to 1,000 parts by weight. .

In producing the composite, a crosslinking agent may be used as necessary. Examples of crosslinking agents include sulfur, peroxides, metal compounds such as zinc, calcium or titanium, polyamino compounds, epoxy resins or phenolic resins.

When a modified low molecular weight diene polymer containing a carboxyl group is combined with a metal compound as a water-containing particulate inorganic substance, the metal compound itself may function as a crosslinking agent, so there is no need to add a crosslinking agent. . Of course, when crosslinking is carried out using radiation or radiation, it is not necessary to add a crosslinking agent.

In addition, the composite of the present invention may optionally contain oil, a plasticizer such as lanolin, dioctyl phthalate, a liquid polydiene having no liquid polybutene functional group, a thermoplastic resin, a wax, a tackifying resin, a surfactant, water-soluble polymer,
It may contain a super absorbent resin, a filler with a low water content, carbon black, glass fiber, polyester fiber, metal fiber, carbon fiber, or metal flake. In addition, solid rubber may be used in part as long as it does not reduce mixing workability.

The water-containing particulate inorganic material and the modified low molecular weight diene polymer are mixed using a general tank mixer, Nigoo, Brabender Plasty Coder, Pan Bali mixer, or the like. The mixing may be carried out at room temperature or may be carried out under heating.

The mixture of the water-containing particulate inorganic material and the modified low molecular weight diene polymer thus obtained is made into a composite by press molding or extrusion molding. It is common to heat the molding process, but it is also possible to mold it at room temperature.

Furthermore, when the viscosity of the mixture is relatively low, it is advantageous because it can be poured or embedded into a required location and then cured.

The composite of the present invention can be used for flame-retardant walls, flame-retardant floors, vibration-proofing materials, sound-proofing materials,
It is used in a wide range of applications such as electromagnetic shielding materials, radiation layer shielding materials, cold insulation materials, and heat insulation materials.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 A modified low molecular weight polyisophone having a viscosity average molecular i of 42,000 and a vinyl bond content of 8% was reacted with maleic anhydride to add 5 mol of maleic anhydride per 100 isoprene monomers. Isoprene was prepared.

After 100 parts by weight of the modified low molecular weight polyisoprene was placed in a double-arm kneader, 150 parts by weight of granular zinc carbonate containing 50% water was added and mixed with stirring. The mixing operation was carried out without any problems, and the resulting mixture was homogeneous. After adding and mixing zinc carbonate, rubber chemicals, 47
94M parts, sodium dibutyldithiocarbamate (vulcanization accelerator) 6 type manufacturing part, dibenzothiazi) V 7.
2 parts by weight of l-phyto (vulcanization accelerator), 6 parts by weight of zinc white, and 1 part by weight of stearic acid were added and mixed.

The mixture thus obtained was press vulcanized at 95'C for 20 minutes to obtain a composite.

On the other hand, for comparison, a mixture was prepared in the same manner as above except that unmodified low molecular weight polyisoprene was used instead of modified low molecular weight polyisoprene, and then press molded to obtain a composite. In this case, the above mixing was extremely difficult and a homogeneous mixture could not be easily obtained.

When we looked at the resulting composite, we found that when unmodified low molecular weight polyisoprene was used, water partially oozed out and it was extremely brittle, but when modified low molecular weight polyisoprene was used, it was found to be extremely brittle. No oozing of moisture was observed, and the material had excellent physical properties.

Example 2 A low molecular weight polybutadiene with a viscosity average molecular weight of 18,000 and a vinyl bond amount of 21 was reacted with maleic anhydride, and then ethyl alcohol was added to cause an etherification reaction, and ethyl maleate was converted into a butadiene monobutylene 100%. Ata 9
A modified low molecular weight polybutadiene with 2 moles added was prepared.

After adding 100 parts by weight of the modified low-molecular-weight polyguac diene described above to a double-arm Nigu, 200 parts by weight of granular aluminum hydroxide with a water content of 65% and the rubber chemicals used in Example 1 (
Sulfur, vulcanization accelerator, zinc white, stearic acid) were added in the same proportions as in Example 1, and mixed with stirring. The mixing operation proceeded very smoothly and a homogeneous mixture was obtained. on the other hand,
For comparison, the same mixing operation as above was carried out using the unmodified low molecular weight 7J selibucdiene as a substitute for the modified low molecular weight polybutadiene, but water separation was severe and a homogeneous mixture could not be obtained.

When the above mixture was press-molded in a hot press at 80°C, a uniform and rubber-elastic sheet-like composite was obtained when modified low molecular weight polybutadiene was used;
When unmodified low molecular weight polybutadiene was used, sheet molding was impossible due to a large amount of water separation.

Example 3 Low molecular weight polyisoprene/polybutadiene/polyisoprene polymer lock copolymer with a viscosity average molecular weight of 25,000 and a vinyl bond content of 15% (weight ratio of polyisoprene/polybutadiene/polyisoprene -3s/6o/3s) Then, formic acid and hydrogen peroxide were reacted to obtain a modified low molecular weight block copolymer in which 920 moles per 100 double grafting of the block copolymer were converted to epoxy.

After adding 100 parts by weight of this modified low molecular weight block copolymer to a tank type mixer with a propeller-type stirrer, and then adding 20 parts of bisphenol-type epoxy resin, mixing work of Portland cement outside of the water-containing light 25 was not possible. The process proceeded smoothly and no separation of water was observed. During molding, add trisdimethylamine methylphenol/I15, a curing agent for epoxy resin, to the mixture.
77II parts by weight were mixed. Next, the obtained mixture was sandwiched between (V-) plates and cured at room temperature to produce a composite. The adhesion between the slate board and the composite was examined after two weeks, and it was found to be good, almost unchanged from immediately after preparation.

On the other hand, the unmodified low-molecular strength Lovelock copolymer was used as a substitute for its modified product, and the same mixing operation as above was carried out, but water separation was severe and mixing was difficult, resulting in a uniform mixture. I couldn't get it.

Claims (1)

[Claims] Maleic anhydride or a derivative thereof is added to a water-containing particulate inorganic material containing 1.5 weight or more of water and a low molecular weight diene polymer having a molecular weight of 4,000 to 100,000 per 100 monomer units of the polymer. The modified diene yarn polymer or the low molecular weight diene polymer added with 1 to 60 moles is reacted with peracid or hydrogen peroxide and a carboxylic acid to reduce the number of double bonds per 100 of the polymer to 0.
A composite consisting of a modified low molecular weight diene yarn polymer in which 1 to 60 moles are converted into epoxy groups.