JPH0242092B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a hydrous polyester resin. More specifically, an unsaturated polyester oil phase,
A method for producing a hydrous polyester resin by crosslinking and curing an oil/water/oil or water/oil/water double emulsion obtained from a cement hydration supernatant or a cement dispersion, wherein a cement swelling agent is present in the double emulsion. The present invention relates to a method characterized in that: BACKGROUND ART Conventionally, cured hydrous resins are known, which are obtained by forming an inverse emulsion (ie, water-in-oil type) in which water is dispersed as minute droplets in an unsaturated polyester oil phase containing a vinyl monomer, and then curing this. The manufacturing method involves adding a surfactant with high lipophilicity of HLB 3 to 8 to an unsaturated polyester oil phase containing a vinyl monomer, specifically sorbitan monostearate, sorbitan isostearate, sorbitan monooleate, sorbitan. A method of forming a water-in-oil emulsion by adding a sorbitan derivative such as monopalmitate, a nonionic surfactant such as glycerin monostearate (Japanese Patent Application Laid-open No. 17895-1983), vinyl monomers such as styrene, vinyl acetate, and polyethylene. A method of forming a water-in-oil emulsion using a kraft polymer with a hydrophilic polymer compound such as glycol, polyethylene oxide, polypropylene oxide, etc. as an emulsifier [Bartl, H. und W.
von Bonin, Makromol.Chem., 57 , 74
(1962)]; alternatively, basic substances that can form salts with the terminal carboxyl groups of unsaturated polyester resins to form polyester salts, specifically symmetrical or asymmetrical alkylamines such as triethanolamine, diethanolamine, and triethylamine; Diamines such as methylenediamine and ethylenediamine, organic amines such as triaminotriethylamine, nitrogen-containing basic substances such as ammonia and hydrazine, sodium hydroxide, potassium hydroxide,
There is a method of forming a water-in-oil emulsion using an alkali metal hydroxide such as lithium hydroxide, an alkaline earth metal hydroxide such as calcium hydroxide, magnesium hydroxide, etc. (Belgian Patent No. 622034). Among these emulsifiers, triethanolamine is said to be particularly preferred since it has the potential to form a structural film at the interface between the unsaturated polyester and water. The cured resin product obtained by the above method contains a large amount of water in the form of a dispersed liquid in the resin, so in addition to the heat resistance of the resin itself, water has a high specific heat, a large latent heat of vaporization, and the water itself is nonflammable. In addition to significantly increasing the heat resistance of the polymer due to properties such as heat resistance, numerous advantages have been reported. The above-mentioned cured resin contains a large amount of water as a component, so its production cost is low, and its mechanical strength is quite high, so it can be used as a structural material, a floor coating material, and a secondary product.
However, when the cured product obtained by the above method is left in the air, moisture gradually escapes and shrinks, and sometimes the difference in the amount of moisture escaping from the surface of the cured product causes twisting, warping, and cracking. Because it can be caused by
It has the disadvantage that it cannot be used in items that require dimensional stability. In addition, the amount of water escaping depends on the external atmosphere, and in order to improve this drawback, for example, the surface of the cured product may be coated with an integral skin layer of a suitable resin such as unsaturated polyester resin, or When forming a water-type emulsion, methods have been used such as adding a water-soluble resin such as polyacrylamide, polyvinyl alcohol, carboxymethyl cellulose, etc. to the water phase to increase water retention. However, sufficient effects have not been obtained. Furthermore, when water is dispersed in the form of minute droplets using the above-mentioned basic substance capable of forming a polyester salt as an emulsifier, the viscosity of the inverse emulsion increases rapidly above the critical base concentration (stable water-in-oil region).
It is also known that the higher the water content, the higher the viscosity. Furthermore, when forming the emulsion, as an aqueous phase,
Stable, relatively low viscosity oil/water/oil or water/oil/water double emulsions are obtained by using a cement hydration supernatant or by using a cement dispersion; curing the emulsions; The cured resin material contains water in the form of minute droplets and at the same time contains soluble and eluted components associated with the cement hydration reaction. It is known that there is no shrinkage, cracking, etc. even when it is used, and it also has excellent dimensional stability and water retention (Japanese Patent Application Laid-Open No. 55-29552). As a result of further research on the above method, it was found that by further adding a cement expansion agent to the above emulsion, it had the same advantages as above, and improved mechanical properties such as mechanical strength and abrasion resistance. It has been found that a hydrous polyester resin can be obtained. Next, the present invention will be explained in more detail. The unsaturated polyester that can be used in the present invention includes any unsaturated polyester that can form an oil/water/oil or water/oil/water double emulsion with a cement hydration supernatant or a cement dispersion. Polyester can also be used. Suitable unsaturated polyesters include unsaturated polyesters containing vinyl monomers. Although commercially available unsaturated polyesters containing vinyl monomers can be used, α- and β-unsaturated dibasic acids and saturated dibasic acids are condensed using a mixture of them as an acid component and glycols as an alcohol component. It can be produced by adding a copolymerizable vinyl monomer to a product. In this case, the copolymerizable vinyl monomers include styrene, α-methylstyrene, vinyltoluene,
Examples include vinyl acetate, methyl methacrylate, diallyl phthalate, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, vinyl acetate, acrylonitrile, 2-ethylhexyl (meth)acrylate, and ethyl (meth)acrylate. The above vinyl monomer not only crosslinks and cures the unsaturated polyester, but also improves the properties of the polymerized and cured product.
That is, it is desirable to use them in combination, taking into account the purpose of use, such as chemical resistance, weather resistance, and impact resistance. Further, the amount of the vinyl monomer used may be any amount based on the unsaturated polyester, but it is preferably about 50% or less in order to contain a large amount of water. In the present invention, the cement hydration supernatant liquid used as the aqueous phase can be prepared by, for example, mixing a certain amount of cement powder into a certain amount of water at room temperature, stirring the mixture, and then
Leave to stand for 16 hours, and the supernatant can be used. In this case, the mixing ratio of water and cement can be 0.03 to 200 parts of cement per 100 parts of water, but preferably 0.1 part or more of cement per 100 parts of water. Furthermore, the cement dispersion in the present invention can be prepared at room temperature as in the preparation of the cement hydration supernatant.
Mix a certain amount of cement powder with a certain amount of water, stir it, leave it as it is for a certain period of time (1 to 16 hours), then stir again and disperse it uniformly (because the ratio of water to cement is small, there is a risk that the cement will solidify during the process). (If necessary, stir continuously) This is used as a dispersion. In this case, the mixing ratio of water and cement can be 0.03 to 50 parts of cement to 100 parts of water.
It is desirable to use less than 10 parts of cement per 100 parts. In the above, it is desirable to increase or decrease the mixing ratio of water and cement as appropriate, taking into consideration the type of unsaturated polyester used as a starting material in the present invention, the stability of the emulsion, the effect on the cured product, etc. The cement used to prepare the cement hydration supernatant liquid and dispersion liquid used in the present invention includes:
Hydraulic cement, which has a chemical composition mainly consisting of lime, silica, alumina, iron oxide, and sulfuric anhydride with the addition of sulfuric acid, and can harden by reacting with water, i.e., ordinary Portland cement, Examples include alumina cement and bellows cement. The cement expansion agent used in the present invention may be present in the double emulsion, but is preferably added to the cement hydration supernatant or cement dispersion. Preferred cases will be explained below.
As cement expansion agents, (1) free lime (CaO);
Magnesia (MgO), which undergoes a digestive reaction with water and _{causes an} increase in volume. ₂ O ₃・
(3) CaO: Al _{2 O 3 : CaSO 4 is} prepared in a molar ratio of 3:1:3 to 4:1:3. , those calcined similar to Portland cement, which produce ettringite through a hydration reaction. In the case of calcium sulfoaluminate (CSA) based material (3) among the above expansion materials, the constituent components are SiO ₂ 1
~7%, _Al2O3 13~21 _% , _{Fe2O3 1} ~6%, CaO43
~48%, _So3 22~32%, _C4A3 (= _{SO3 )} 38~
41%, free− _CaSO4 30~40%, free−CaO3~20
%, and in order for C ₄ A ₃ to completely change to trisulfate (ettringite), CaSO ₄ ,
In addition to the need for CaO, Ca(OH) ₂ produced by hydration of the Portland cement used as the water phase is useful. At the beginning of hydration, the surface of C ₄ A ₃ particles is immediately surrounded by a hydrate film, through which a limited reaction takes place, which first forms monosulfate or its solid solution, which expands. Although SO ₄ ^-- and Ca ⁺⁺ ions diffuse from the liquid phase through this membrane, trisulfate is generated and irreversible expansion occurs. Therefore, hydration of C ₄ A ₃ proceeds as follows. C ₄ A ₃ +8Ca(OH) ₂ +30H ₂ O → (C ₃ A・CH ₁₂ −2C ₄ AH ₁₃ ) (C ₃ A・CH ₁₂ −2C ₄ AH ₁₃ ) +6Ca ⁺⁺ +8SO ₄ ^-- +55H ₂ O → 3C ₃ A・3CH ₃₂ The oil/water/oil or water/oil/water double emulsion in the present invention comprises an unsaturated polyester oil phase,
It can be obtained from a cement hydration supernatant liquid or a cement dispersion liquid to which a cement swelling agent has been added, but it can be formed using any method that can form a double emulsion from unsaturated polyester and cement hydration supernatant liquid, etc. It may be a method. A suitable method for forming a double emulsion includes, for example, adding a cement hydration supernatant or a cement dispersion containing a cement swelling agent little by little into an oil phase of an unsaturated polyester such as an unsaturated polyester containing a vinyl monomer, and stirring vigorously ( For example, a method of emulsifying at 700 to 3000 rpm) can be mentioned. Other emulsification methods include
Examples of the method include adding an oil phase to an aqueous phase, or mixing an oil phase and an aqueous phase and then vigorously stirring the mixture.
When forming a double emulsion, common surfactants and basic substances which can be polyester salts can also be added. The emulsion obtained according to the present invention is oil/
A water/oil (or water/oil/water) double emulsion,
In addition, there were large water particles ranging from several microns to several + microns in size. Furthermore, the emulsion obtained according to the present invention is extremely stable, with water not coagulating or separating even if left for a long time. Although the above-mentioned emulsion formation and stabilization mechanism is unknown, it is thought that the movement follows the compositional change and transition accompanying the cement hydration reaction.
Along with the hydration reaction of cement, a neutralization reaction between alkali components such as lime hydroxide and alkali sulfate in the liquid phase and unsaturated polyester occurs, and aluminate, gypsum,
It is thought that SiO ₂ , Al ₂ O ₃ and other trace amounts of dissolved inorganic components react to stabilize the oil-water interface and form an extremely complex emulsion. If desired, the emulsion obtained by the present invention may contain reinforcing materials such as inorganic fibers and organic fibers such as glass fiber, silica fiber, carbon fiber, and asbestos fiber, and fillers such as vermiculite, perlite, and iron sand. Other reinforcing additive components such as foaming agents, flame retardants, and colorants can be added. As the polymerization initiator used for curing the emulsion in the present invention, known radical polymerization initiators or redox polymerization initiators used for curing unsaturated polyesters can be used. For example, as a radical polymerization initiator, potassium persulfate, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, t-butyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, etc. are used as a redox polymerization initiator. Examples include benzoyl peroxide-dimethylaniline, methyl ethyl ketone peroxide-cobalt organic acid salt, and cumene hydroperoxide-cobalt organic acid salt (cobalt organic acid salts include cobalt naphthenate, cobalt octoate, etc.). The above polymerization initiator is used in an amount of 0.5 to 10 parts by weight per 100 parts by weight of the unsaturated polyester prepolymer.
In addition, the cobalt organic acid salt as a redox polymerization initiator is
It is used in an amount of 0.05 to 1 part by weight, but it is desirable to increase or decrease the amount as appropriate, taking into account the water content, curing conditions, properties of additives, influence on the cured product, etc. The hydrous polyester emulsion obtained according to the present invention is easily polymerized by the above-mentioned polymerization initiator at room temperature or under heating to give a cured hydrous resin product that is white and has a dry texture. The cured product contains almost all of the water contained during emulsification as minute droplets, and at the same time contains eluted components accompanying the cement hydration reaction,
It is characterized by containing large-volume crystals such as Ca(OH) ₂ and ettringite, and unlike conventional water-containing resins, it does not shrink or crack even if left in the air for a long period of time. In addition, dimensional stability, water retention, heat resistance, and mechanical strength are greatly improved. In particular, the improvement in mechanical strength is associated with the introduction of chemical prestress by cement expansion agents and the consolidation effect. That is, the cement hydration or dispersion liquid dispersed as minute droplets in the resin reacts with the cement expanding agent, and a large volume of cement bacillus and ettringiaite crystals, which have a large amount of water-insoluble bound water, interact with the resin. It precipitates and grows at the interface with the aqueous phase, giving a chemical prestress effect to the cured resin. i.e. ettringite crystal, Ca
Chemical prestress is later introduced into the cured resin matrix by the expanding force of (OH) ₂ crystals, etc., and when the resin is restrained by the resin matrix, a consolidation effect acts, making it possible to obtain a high-strength cured product. . The chemical reaction formula is shown below. 6CaO+Al ₂ O ₃ +3SO ₃ +32H ₂ O →3CaO・Al ₂ O ₃・3CaSO ₄・32H ₂ O 3CaO・Al ₂ O ₃ +3CaSO ₄ +32H ₂ O →3CaO・Al ₂ O ₃・3CaSO ₄・32H ₂ O CaO+H ₂ O→Ca(OH) ₂ 3CaO・3Al ₂ O ₃・CaSO ₄ +8CaSO ₄ +6CaO+96H ₂ O → 3 (3CaO・Al ₂ O ₃・3CaSO ₄・32H ₂ O) Ettringite crystal as shown in the above chemical reaction formula. Although large amounts of bound water are required for adequate growth, a large excess of water is conveniently dispersed in the hydrous polyester resin. Also, if the above reaction mechanism is utilized, for example, if an expanding cement dispersion is used as the cement dispersion when preparing an emulsion, only 3CaO・Al ₂ O ₃・mH ₂ O in the cement paste will participate in the reaction. In the initial stage, it does not expand much, and furthermore, because the dissolution rate of anhydrite is slow, it is possible to gradually form ettringite crystals over a long period of time. The reaction formula is shown below. 3CaO・Al ₂ O ₃・mH ₂ O+3CaSO ₄ +nH ₂ O →3CaO・Al ₂ O ₃・3CaSO ₄・32H ₂ O Next, the present invention will be explained in more detail with reference to Examples. It is not limited. Example 1 Unsaturated polyester [Sumiap, Sumitomo Chemical Co., Ltd.]
MG-1, oxidized 13, styrene content 40%] 100 parts (weight, same below) was stirred at a speed of 1200 rpm while 100 parts of Bortland cement hydration supernatant liquid (water 300%) manufactured by Nippon Cement Co., Ltd. 66 parts of cement is mixed into the
After stirring, the mixture was allowed to stand for 1 hour to obtain a supernatant liquid. ) was gradually added little by little to obtain a polyester emulsion. The emulsion obtained according to the present invention is oil/
It was a water/oil double emulsion. To 200 parts of the obtained emulsion, 1 part of methyl ethyl ketone peroxide and 0.5 part of cobalt naphthenate (Co6%) were added and poured into a triple mold of 4 x 4 x 16 cm. After curing at room temperature, it was taken out and placed in an air bath at 60°C. After being left for 4 hours, a hard water-containing polyester resin specimen with a completely dry feel was obtained. The hardness of this resin was 38 to 40 on the Barcol hardness scale. For comparison, Asano Gypcal [manufactured by Nippon Cement Co., Ltd.] 10 is used as a cement expansion material.
A water-containing polyester resin specimen was obtained in the same manner as above, except that the same amount was added to the cement hydration supernatant. The hardness of this resin was 40 to 41 on Barcol hardness. The two types of specimens obtained by the above
Compression and bending strengths were measured using a hydraulic universal testing machine in accordance with JIS R-5201. The results are shown in the table.

[Table] As can be seen from the results, the strength improved by 33% in compression and 15% in bending when compared to those without cement expansion agent added. Furthermore, when these two types of test specimens were left at room temperature for 5 months, it was found that both had excellent water retention properties with almost no change in weight. Examples 2 to 5

[Table] Product name of cement expanding agent Unsaturated polyester as starting material [Takeda Pharmaceutical
Polymer Co., Ltd. 6702, acid value 8.5, styrene content 40
%] was used, and the emulsion was treated in the same manner as in Example 1, except that the acid combination ratios were as shown in the table above.
After adding 0.5 parts of cobalt naphthenate (Co6%), the incineration ash was kneaded uniformly, packed in a 4 x 4 x 16 cm triple mold for mortar testing, and left at 60°C for 6 hours. A hydrous resin mortar specimen of No. 4 was obtained. For comparison, the same treatment as in Examples 2 and 4 was carried out except that a certain amount of Expan or Asanodypcal was added to the cement hydration supernatant liquid as a cement expansion agent.
Hydrous resin mortar specimens of Examples 3 and 5 were obtained. The compression and bending strengths of the four types of specimens obtained above were measured according to the method of Example 1. The results are summarized in a table. As can be seen by comparing Examples 2 and 4, the mechanical strength of hydrous resins generally decreases as the water content increases. In this case, when the moisture content increases by 50%, the compressive strength
25%, and a 15% decrease in bending strength. However, in Examples 3 and 5, in which Expan and Asanodypcal were added as cement expansion agents to the compositions of Examples 2 and 4, a significant improvement in strength was observed in both cases. Comparing Examples 2 and 3, the compressive strength is
65%, and bending strength increased by 41%. Also, when comparing Examples 4 and 5, the compressive strength was 99%, and the bending strength was 99%.
It has increased by 68%. In Example 3, large plate-like crystals of Ca are generated by hydration of the cement hydration liquid phase and liberated CaO in the aqueous phase dispersed as minute droplets in the resin.
This is thought to be caused by crystal growth of (OH) ₂ , precipitation/growth of Ettringit, and crystal pressure. On the other hand, in Example 5, the cement hydrated liquid phase reacts with anhydrous calcium sulfoaluminate (4CaO・3Al ₂ O ₃・SO ₃ ), gypsum (CaSO ₄ ), and calcium oxide,
A large amount of needle-like crystals of Ettringit and Ca(OH) ₂ precipitate.
It's because I grew up. Comparing Examples 3 and 5, even though Example 5 has a higher moisture content than Example 3, high strength can be obtained because Asano Zipcal has a larger volume of cement than Expan - BaCillus,
This is to precipitate a large amount of Ettringit. That is,
The prestressing effect of water particles in the cured product obtained by the present invention is due to the fact that the crystals formed are mainly Ca(OH) ₂ .
It depends on whether Ettringit is the subject. In any case, the water in the cured resin products obtained in Examples 2 and 4 was simply finely dispersed droplets, but in Examples 3 and 5, it changed to crystal water, so the water particles became fine bones. This is to create a structure that looks like it has been cured in a close-packed state. Examples 6-8

【table】

[Table] Examples 6, 7, and 8 were treated in the same manner as in Examples 2 and 3, except that Takeda Pharmaceutical Co., Ltd.'s Polymer 6702 was used as the unsaturated polyester resin and the compounding ratios were as shown in the table above. A hydrous resin mortar specimen was obtained. The three types of specimens obtained above were subjected to a wear resistance test in accordance with ASTMD-1242-56MethodA. The results are summarized in a table. Comparing Examples 6, 7, and 8, the wear amount was 0.61 mm when no EXPAN was added, 0.57 mm (7% reduction) when 15% EXPAN was added, and 0.57 mm (7% reduction) when 30% was added.
It has decreased to 0.46mm (25% decrease). - It can be seen that the addition of Expan greatly improves the wear resistance. Similar to the improvement in mechanical strength in Examples 3 and 5, this is due to the introduction of prestress and the consolidation effect accompanying the precipitation and growth of a large volume of Ca(OH) ₂ and Ettringit crystals. As explained in detail above, the cured hydrated polyester resin obtained by the present invention contains a large amount of water, maintains the excellent mechanical strength inherent to polyester resin, and has excellent water retention, dimensional stability, and heat resistance. , flame resistance is significantly improved. By applying these properties, we can create civil engineering and construction materials, polymer floor finishing materials,
It can be used for various purposes such as synthetic wood, flame retardant material, heat insulation material, and soundproofing material.

Claims (1)

[Claims] (1) Lime or magnesia in a ratio of 5 to 20 parts per 100 parts of unsaturated polyester resin in an oil/water/oil double emulsion obtained from an unsaturated polyester oil phase and a cement hydration supernatant; (2) Those whose main component is anhydrite that reacts with cement hydration supernatant to form ettringite crystals, and (3) CaO:
Al ₂ O ₃ :CaSO ₄ molar ratio 3:1:3 to 4:1:
A method for producing a water-containing polyester resin, which comprises crosslinking and curing a double emulsion in the presence of a cement expansion agent selected from those prepared and fired within the range of 3, which produces ettringite through a hydration reaction.