JPS5850614B2 - Inorganic-containing unsaturated polyester resin composition for plastic concrete - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stable inorganic-containing unsaturated polyester resin composition for plastic concrete that has low shrinkage and excellent workability.

More specifically, it consists of an unsaturated polyester resin containing an amount of styrene monomer in a specific range, polystyrene, an inorganic mineral material such as sand or gravel, and a specific comb copolymer as a dispersion stabilizer at room temperature or at a heated temperature. The present invention relates to a composition for plastic concrete that can be hardened by a method, has low shrinkage, and has excellent workability.

Generally, structures called polyester-mortar and polyester-concrete are made by using unsaturated polyester resin as a binding material instead of cement, and mixing this with aggregate such as sand and gravel and, if necessary, inorganic powder such as calcium carbonate. Although the material is more expensive than conventional cement-mortar and cement-concrete, it is used in civil engineering, electrical, and chemical industries due to its excellent acid resistance, electrical insulation, light weight, and fast curing properties. It is used for.

However, due to the large curing shrinkage of unsaturated polyester resins, polyester-mortar and polyester-concrete generally have the essential drawback of exhibiting large shrinkage upon curing.

For this reason, various improvements have been made to reduce shrinkage during curing.

For example, a method in which a large amount of styrene monomer, which is a component of general unsaturated polyester resin, is mixed to lower the viscosity, and a large amount of aggregate is added to this, and a known method in the heat-pressing molding method. Accordingly, methods have been proposed in which various polymers are mixed with commercially available unsaturated polyester resins.

Although it is possible to slightly reduce curing shrinkage using these known methods, it is impossible to obtain a shrinkage rate of 0 with any of these methods, and they also have drawbacks such as reduced workability and reduced mechanical strength of the cured product. be.

In addition, as a method for producing a polyester mixture that can be made to expand if necessary, the shrinkage rate O1 includes linear glycols such as ethylene glycol, diethylene glycol, and butanediol, aliphatic dibasic acids such as succinic acid, adipic acid, and cepatic acid, and maleic acid. , an amount of styrene monomer that is soluble in styrene monomer in an amount exceeding the compatibility limit with an unsaturated polyester of a special composition that has fumaric acid as the main raw material for polycondensation and has a certain compatibility limit with styrene monomer. A method of blending polymers and inorganic mineral powders and granules was proposed.

(% Publication No. 47-33075) In this method, it is possible to reduce the curing shrinkage to O or conversely to expand it under limited conditions, but the temperature during storage of the unsaturated polyester resin before use If the conditions are not strictly controlled, phase separation will occur and the composition will become unusable for the intended purpose, and if the composition is not thoroughly stirred and mixed and immediately put into use, it has the disadvantage that separation of components will occur.

In addition, in order to limit compatibility with styrene monomers, it is essential to use unsaturated polyesters containing a large amount of aliphatic raw materials such as diethylene glycol, adipic acid, and sepatic acid. Compared to compositions using polyester made from raw materials, it has lower mechanical strength, inferior heat resistance, and has the disadvantage that only cured products can be obtained with inferior water resistance and chemical resistance. .

Furthermore, instead of using special polyesters that have the disadvantages of the above-mentioned conventional techniques, a general-purpose unsaturated polyester with suitable properties of the cured product can be used, and it can be manufactured by an extremely easy method and has excellent workability. As a low shrinkage unsaturated polyester resin composition (N unsaturated polyester, (B) styrene monomer in a specific range of amount, (C
) A composition comprising specific amounts of polystyrene, (D) inorganic minerals was proposed.

(Japanese Patent Publication No. 51-7095). The composition can use any general-purpose unsaturated polyester with well-balanced properties, has low viscosity, excellent workability, and has the excellent characteristics of zero curing shrinkage or, conversely, the ability to expand during curing. However, if the composition is not used for a short period of time with stirring and mixing waves, the polystyrene in the composition will separate, resulting in roughening of the surface of the molded product.
The occurrence of defects such as distortion of molded products due to uneven shrinkage was unavoidable.

As a result of intensive studies aimed at improving the dispersion stability of polystyrene in the composition according to the prior art, the present inventor discovered a specific dispersion stabilizer that has a remarkable effect on stabilizing the dispersion of polystyrene and unsaturated polyester resin. A composition for plastic concrete having the excellent characteristics of the invention has now been discovered.

That is, the characteristics of the composition for plastic concrete of the present invention are (A) unsaturated polyester, (B) styrene monomer in an amount 1.35 times or more in weight relative to the unsaturated polyester in (A), and (C) polyethylene 0. Inorganic minerals and 4)
The main feature is that the dispersion stabilizer is composed of a comb-shaped copolymer having a styrene polymer chain as a trunk and polyester segments as branches.

(A) As the unsaturated polyester, any known unsaturated polyester selected in consideration of various properties such as mechanical properties, water resistance, chemical resistance, heat resistance, and electrical properties depending on the final use of the composition. It can be used as a component of the composition for plastic concrete of the present invention.

That is, as raw materials for unsaturated dibasic acids, for example, maleic anhydride,
Fumaric acid, itaconic acid, polyhydric alcohol raw materials such as propylene glycol, ethylene glycol, diethylene glycol, cyfropylene glycol, butanediol, glycerin, pentaerythritol, triethylene glycol, bentanediol, hexanediol,
Neopentyl glycol, hydrogenated bisphenol A1 bisphenol A, alkylene oxide adducts, propylene oxide, ethylene oxide, etc., polybasic acid raw materials such as phthalic acid, inphthalic acid, terephthalic acid, endomethylenetetrahydrophthalic acid, tetrahydrophthalic acid, tetrachloro Unsaturated polyester soluble in styrene monomers produced by known methods using phthalic acid, tetrabromophthalic acid, hetonic acid, hexahydrophthalic acid, succinic acid, adipic acid, trimellitic acid, and their acid anhydrides. If so, both can be used.

It is particularly important to use the styrene monomer as a component of the composition for plastic concrete of the present invention in an amount of 1.35 times or more, preferably 1.5 times or more, relative to the unsaturated polyester component.

In other words, commercially available unsaturated polyester resins usually have an equivalent weight of 1 or less based on the unsaturated polyester (alkyd solid content).
Although the composition for plastic concrete of the present invention contains more than the weight of styrene monomer, the amount within this range is too small for the composition for plastic concrete of the present invention to achieve the desired curing shrinkage O or conversely, curing expansion. When using (mixture of unsaturated polyester and styrene monomer) as a raw material for the composition for plastic concrete of the present invention, the total amount of styrene monomer is 135 times or more, preferably 1.5 times or more, relative to the unsaturated polyester. You need to add it accordingly.

The polystyrene as a component of the composition for plastic concrete of the present invention is a polymer whose main raw material is styrene monomer. Also included are styrene copolymers containing butadiene, acrylonitrile, and other monomers as comonomers.

Although there is no particular restriction on the molecular weight of polystyrene, polystyrene having a relatively low molecular weight is preferred from the viewpoint of workability in producing and curing the composition.

The content of polystyrene in the composition should be at least 100 times the total weight of the unsaturated polyester and styrene monomer, preferably ≦H100, and at least 100 times the weight of the total amount of the unsaturated polyester and styrene monomer in order to obtain a sufficient low shrinkage (expansion) effect. In order to obtain good handling properties and good mechanical properties in manufacturing and curing operations, it is desirable to use up to 3 L times the weight of the total amount of unsaturated polyester and styrene monomer.

The inorganic mineral substances used in the composition for plastic concrete of the present invention include at least one kind of sand, gravel, crushed stone, silica sand, lightweight aggregate, clay, hydrated alumina, calcium carbonate, etc. in the form of granules or powders. used in

Furthermore, the comb-shaped copolymer having a styrene polymer chain as a trunk and polyester segments as branches, which is used as a dispersion stabilizer in the composition for plastic concrete of the present invention, prevents separation of polystyrene during storage of the composition of the present invention. In addition to suppressing the styrene solution of polystyrene from floating on the surface of the composition when the composition is cured, it also suppresses the embossment of the styrene solution of polystyrene onto the surface of the composition. It has the function of suppressing stickiness and increase in resin liquid viscosity, and is important in imparting excellent workability to the composition of the present invention.

The above-mentioned comb-shaped copolymer can be produced by, for example, synthesizing a saturated polyester having an unsaturated double bond at one end, and radically copolymerizing this with styrene alone or a monomer mixture containing styrene as the main component, or using maleic anhydride. A method of reacting a copolymer of a vinyl monomer with an aromatic vinyl monomer with a saturated or unsaturated polyester having a hydroxyl group at one end, or a method of reacting a copolymer of a vinyl monomer with an epoxy group and an aromatic vinyl monomer with a carboxyl group at one end. It can be produced by a method of reacting with a saturated or unsaturated polyester having the following.

The amount of the thus obtained comb copolymer used as a dispersion stabilizer is 0.00% based on the polystyrene in the composition.
It is effective at 5 times (weight) or more, preferably 0.01 times or more.

The composition for plastic concrete of the present invention contains each component as detailed above, namely, unsaturated polyester,
It is produced by mixing a styrene monomer, a polystyrene inorganic mineral, and a dispersion stabilizer, and there is no particular restriction on the order in which they are added and mixed. A method in which a mixture of a solution of polystyrene dissolved in the remaining styrene monomer and a dispersion stabilizer is stirred and mixed with inorganic mineral particles or powder is easy to work with.

The composition for plastic concrete of the present invention is a known curing catalyst used when curing unsaturated polyester resin and, if necessary, a curing accelerator is added and mixed, and the composition is cured at room temperature or by heating, and shrinks during curing. The ratio is close to O or shows slight expansion, and a cured product with no cracks and excellent mechanical properties is obtained.

Furthermore, by adding a dispersion stabilizer made of a specific comb-shaped copolymer, the separation of the polystyrene component in the composition is almost prevented even under harsh conditions such as when standing before curing, during curing, and during rotational molding. Another major advantage of the plastic concrete composition of the present invention is that it has excellent workability, such as no stickiness or increase in resin liquid viscosity caused by embossment on the surface of the composition. It is.

The inorganic-containing unsaturated polyester resin composition for plastic concrete of the present invention is widely used in fields other than filling, such as waste liquid ditches, U-shaped grooves, block manholes, electrolytic cells, machine mountings, foundations, etc.

The present invention will be further explained below with reference to Examples and Comparative Examples.

Example (a) Preparation of unsaturated polyester resin (UP) and styrene monomer solution (TP) of polystyrene 2 moles of maleic anhydride, 3 moles of phthalic anhydride, and 5.3 moles of propylene glycol were mixed in a reaction vessel by a conventional method. The mixture was heated at 200° C. while passing through a nitrogen gas stream to carry out an esterification reaction to obtain an unsaturated polyester (AL) having an acid value of 45.

43 parts of the AL was dissolved in 57 parts of styrene monomer, and 0.011 part of hydroquinone was mixed therein to obtain an unsaturated polyester resin (UP).

Separately, 30 parts of polystyrene (Styron 666 manufactured by Asahi Dow Industries, Ltd.) was dissolved in 70 parts of styrene monomer to obtain a polystyrene solution (TP).

(b) Production of dispersion stabilizer (STA') Phthalic anhydride 1 mol, succinic anhydride 1 mol, ethylene glycol 2,
One mole of the mixture was heated to 150° C. in a reaction vessel in a conventional manner while passing a nitrogen gas stream therethrough, and reacted for 2 hours to obtain a halfester compound.

Thereafter, the mixture was heated to 200° C. to advance the esterification reaction, resulting in a saturated polyester having an acid value of 17.

This saturated polyester was cooled to 150°C, 7.11 parts of maleic anhydride was added, and the reaction was allowed to proceed for 2 hours to add maleic anhydride to the hydroxyl group terminals of the saturated polyester.

Then dibutyl phthalate was added to saturated polyester 100
After cooling to 80° C., 50 parts of styrene monomer were added to form a uniform solution.

Further, 1 part of benzoyl peroxide was added, a radical copolymerization reaction was carried out at 80°C, and after 4 hours, 0.2 parts of hydroquinone was added.
The polymerization was completed and a comb-shaped copolymer was obtained.

This was further diluted with 50 parts of cellosolve acetate to prepare a dispersion stabilizer solution (STA).

(Preparation of resin composition and study of molding workability and curing shrinkage rate) 80 parts of UP was added to 20 parts of the above-mentioned TP with STA added so that the weight of STA was 0.16 times the weight of polystyrene. A resin liquid was obtained.

To this resin solution, 0.4 PHR of a cobalt octylate solution containing 8% cobalt (Nitsuka Octics Co 8% manufactured by Nihon Kagaku Sangyo Co., Ltd.) and a 55% solution of methyl ethyl ketone peroxide (Permec N manufactured by Nippon Oil & Fats Co., Ltd.) were added. 1.0 PHR was added, stirred and mixed thoroughly, and then poured into 170 parts of calcium carbonate (Nitto Konka NZ) and 330 parts of river sand, stirred and mixed well to form a resin mortar (holyester mortar).

This resin mortar had very good fluidity and good workability.

This resin mortar was cured for one week at room temperature of 18-25° C. to prepare a 40×40×160% test block.

The dimensional change before and after curing was 0.01% shrinkage, which was almost no shrinkage.

Further, there was no protrusion of polystyrene on the surface and no stickiness was observed at all.

Comparative Example A cobalt octylate solution and a 55% methyl ethyl ketone peroxide solution were added to 20 parts of TP and 80 parts of UP in the same manner as in Example 1, and mixed with 170 parts of calcium carbonate and 330 parts of river sand to obtain a resin mortar.

The fluidity of this mortar was also considerably poorer than that of the resin mortar of the example.

This resin mortar was cured for one week at room temperature of 18-25° C. to prepare a 40×40×160% test block.

The dimensional change before and after curing was 0.02% expansion.

However, during curing, the styrene solution of polystyrene floated onto the surface of the resin mortar, making the surface sticky, and a thin film of polystyrene was formed on the surface of the cured product.

Claims (1)

[Scope of Claims] 1 (A) unsaturated polyester, (BXA) styrene monomer in an amount of 1.35 times or more by weight relative to unsaturated polyester, (C) polystyrene, 0 inorganic mineral material, and (D styrene-based An inorganic-containing unsaturated polyester resin composition for plastic concrete with low shrinkage and excellent workability, which comprises a dispersion stabilizer made of a comb-shaped polymer having a polymer chain as a trunk and polyester segments as branches. (However, excluding for filling)