JPS59126420A - Production of water-containing polyester resin - Google Patents

Abstract

PURPOSE:A specific multi-layer emulsion containing cement-swelling material is cured by crosslinking to produce a water-containing polyester resin with good dimensional stability and water retention as well as improved mechanical strength and abrasion resistance. CONSTITUTION:A supernatant of hydrated cement or cement dispersion containing a cement-swelling material such as free lime or magnesia, which reacts with water by slaking to expand its volume, is added in portion to an unsaturated polyester such as unsaturated polyester containing vinyl monomers, then they are thoroughly stirred to effect emulsification to an oil/water/oil or water/ oil/water multilayer emulsion. Then, the resultant emulsion is polymerized with a polymerization initiator such as benzoyl peroxide to produce the objective water-containing polyester resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a hydrous polyester resin. More specifically, in a method for producing a hydrous polyester resin by crosslinking and curing an unsaturated polyester oil phase and an oil/water/oil or water/oil/water double emulsion obtained from a cement irrigation supernatant or a cement dispersion, The present invention relates to a method characterized in that a cement expansion agent is present in the double emulsion.

Conventionally, a cured hydrous resin is known, which is obtained by forming an inverse i-mulsion (i.e., 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 a high lipophilicity of HLB 3 to 8 to the unsaturated polyester oil phase containing a vinyl monomer, specifically sorbitan monostearate, sorbitan instearate, sorbitan monooleate, and sorbitan. A method of forming a water-in-oil emulsion by adding a sorbitan derivative such as monopalmitate or a nonionic surfactant such as glycerin monostearate (Japanese Patent Application Laid-Open No. 17895/1989), vinyl monomers such as styrene, vinyl acetate, etc. and polyethylene. A method of forming a water-in-oil emulsion using a graft polymer with a hydrophilic polymer compound such as glycol, polyethylene oxide, or polypropylene oxide as an emulsifier (Bartl
, H, and W.

von Bonin, Makromol, Chem
-, 57, 74 (1962)); alternatively, basic substances that form salts with the terminal carboxyl groups of unsaturated polyester resins to obtain polyester salts, specifically triethanolamine, diethanolamine, triethylamine. Symmetrical or asymmetrical alkylamines such as, diamines such as methylenediamine and ethylenediamine, organic amines such as triaminotriethylamine, nitrogen-containing basic substances such as ammonia and hydrazine, sodium hydroxide,
There is a method of forming a water-in-oil emulsion using alkali metal hydroxides such as potassium hydroxide and lithium hydroxide, and alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide (Belgian patent 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.

Since the resin cured product obtained by the above method contains a large amount of water in the form of a dispersion, 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 its properties, numerous advantages have been reported.

The above-mentioned cured resin contains a large amount of water as a component, so the manufacturing cost is low, and its mechanical strength is high, so it can be used as structural materials, floor finishing materials, and secondary products. . 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,
It has the disadvantage that it cannot be used in items that require dimensional stability.

Also, the amount of moisture escaping is influenced by the external atmosphere.
In order to improve this drawback, for example, when forming a water-in-oil emulsion, an integral skin layer is applied to the surface of the cured product using a suitable resin such as unsaturated polyester resin.
Methods have been taken to increase water retention by adding water-soluble resins such as polyacrylamide, polyvinyl alcohol, and carboxymethyl cellulose to the aqueous phase.

However, sufficient effects have not been obtained.

In addition, when water is dispersed as fine droplets using the above-mentioned basic substance that can be used as a polyester salt as an emulsifier,
Above the critical base concentration (stable water-in-oil region), the viscosity of the inverse emulsion increases rapidly. It is also known that the higher the water content, the higher the viscosity.

Furthermore, when forming the emulsion, a stable relatively low viscosity oil/water/oil or water/
A double emulsion of oil/water is obtained, and a cured resin obtained by curing the emulsion contains water in the form of fine droplets and at the same time contains soluble and eluted components associated with cement water utilization reactions. , unlike conventional hydrous resins,
It is known that it does not shrink or crack even if left in the air for a long time, and has excellent stiffness, dimensional stability, and water retention (Japanese Patent Laid-Open No. 55-29552).

As a result of further research on the above method, it was found that by further adding a cement swelling agent to the above emulsion, it not only has the same advantages as above, but also significantly improves 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 oil/
Any unsaturated polyester that forms water/oil or water/oil/water double emulsions can be used. Suitable unsaturated polyesters include unsaturated polyesters containing vinyl monomers.

Although commercially available unsaturated polyesters containing vinyl monomers can be used, it is preferable to carry out a condensation reaction using α, β unsaturated dibasic acids or a mixture of them and saturated dibasic acids as an acid component and a glycol as an alcohol component. It can be produced by adding a copolymerizable vinyl monomer to

In this case, the copolymerizable vinyl monomers include styrene,
α-methylstyrene, vinyltoluene, vinyl acetate, methyl methacrylate, diallyl phthalate, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, vinyl acetate, acrylonitrile, 2-
Ethylhexyl (meth)acrylate, ethyl (meth)
Examples include acrylate.

It is desirable that the above vinyl monomers not only crosslink and cure the unsaturated polyester, but also be used in combination in consideration of the properties of the polymerized cured product, such as chemical resistance, weather resistance, impact resistance, etc. .

Further, the vinyl monomer may be used in 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, leaving it as it is for 1 to 16 hours, and then preparing the supernatant liquid. Can be used. In this case, the mixing ratio of water and cement is 0.03 to 2 parts per 100 parts of water.
00 parts, 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 by mixing a certain amount of cement powder into a certain amount of water at room temperature, stirring, and leaving it for a certain period of time (1 to 16 hours), as in the preparation of cement irrigation supernatant liquid. Stir again to uniformly disperse the mixture (continuously stir if the ratio of water to cement is small and there is a risk that the cement will solidify during the process), and use this as a dispersion liquid. In this case, the mixing ratio of water and cement can be 0.03 to 50 parts per 100 parts of water, but preferably 10 parts or less of cement per 100 parts of water. In addition, 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 chemical composition of the cement used to prepare the cement irrigation supernatant liquid and dispersion liquid used in the present invention is mainly composed of lime, silica, alumina, iron oxide, and sulfuric anhydride with the addition of Ceracola. , hydraulic cements that harden by reacting with water, i.e., ordinary Portland cement, alumina cement,
Bellows cement, etc. can be drilled.

The cement expansion agent used in the present invention may be present in the multiple emulsion, but it is preferably added to the cement water semen or cement dispersion. Preferred cases will be explained below. As a cement expanding agent, (
1) Free lime (CaO) and magnesia (Mr), which undergo a digestive reaction with water and increase in volume. (2) (Portland) Combines with 3CaO-AtzOa hydrate in cement to form ettringite crystals. (Rttringit
) (3CaO・Al-20s・3CaSO4・32
(3) CaO: kt203: CaSO4 was prepared in a molar ratio of 3:1:3 to 4:1:3 and calcined in the same manner as Portland cement. Examples include those that produce schedlingite through water utilization reactions.

In the case of (3) calcium sulfoalumina (C8A) type substance among the above expansion materials, the constituent components are 5i021~
7%, A-120313~21%, Fe2031~6%
, CaO43-48%, 5oa22-32%, C4A3
100 (5=SOa) 38-41%, free-CaSO
430-40%, free-CaO3-20%, in order for C4A5S to completely transform into trisulfate (ettringite), Ca5O4 and CaO are required, as well as the hydration of Portland cement used as the water phase. The generated Ca(OH)2 is useful. At the beginning of irrigation, C.
The surface of the 4A5S particles is immediately wrapped in a hydrate film,
Since a limited reaction takes place through this membrane, it first produces monosulfate or its solid solution, so it does not show swelling, but it is only when Bob-9Ca" ions diffuse from the liquid phase through this membrane that it forms trisulfate, which is irreversible. Therefore, C4A, 100 water uses proceed as follows.

CaA300+8Ca(OH)2+30H20-〉(C3
A-C100H12-2C4AH13) (C3A-C8H1
2-2C4AE1a)+6Ca"+8S○4--+55
H20-〉3C,A・3C100H32 The oil/water/oil or water/oil/water double emulsion in the present invention is composed of an unsaturated polyester oil phase and a cement water semen or cement dispersion to which a cement swelling agent has been added. However, any method that can form a double emulsion from unsaturated polyester and cement irrigation supernatant may be used. A suitable method for forming a double emulsion includes, for example, adding cement water semen or 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, , 700 to 3000 r, p, m) to emulsify. Other emulsification methods include adding an oil phase to an aqueous phase, or mixing an oil phase and an aqueous phase and then stirring vigorously. When forming a double emulsion,
It is also possible to add a basic substance that can be a surfactant or a polyester salt.

The emulsion obtained by the present invention is a multiple emulsion of oil/water/oil (or water/oil/water), ranging from several microns to several tens of microns.
The presence of large water particles.

Furthermore, the emulsion obtained by the present invention is extremely stable, with water not coagulating or separating even if left for a long time.

The above-mentioned emulsion generation and stabilization mechanism is unknown, but it is thought that the movement follows the compositional change and transition accompanying the cement water use 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 trace amounts of dissolved inorganic components such as aluminate, stone wax, 5i02, A220B and others react to form oil. - It is thought to stabilize the water interface and form a very complex emulsion.

The emulsion obtained according to the invention may optionally contain
For example, reinforcing materials such as inorganic and organic fibers such as glass fiber, silica fiber, carbon fiber, and asbestos fiber, fillers such as vermiculite, perlite, and iron sand, and auxiliary additions such as foaming agents, flame retardants, and coloring agents. Ingredients can be added.

As the polymerization initiator used for curing the emulsion in the present invention, a known radical polymerization initiator or redox polymerization initiator used for curing unsaturated polyester 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.
In addition, as a redox polymerization initiator, benzoyl peroxide-dimethylaniline, methyl ethyl ketone peroxide-cobalt organic acid salt, cumene hydroperoxide-cobalt organic acid salt (cobalt organic acid salts include cobalt naphthenate, cono(ruto-octoate, etc.) ) can be handled.

The above polymerization initiator is an unsaturated polyester prepolymer 10
It is used in an amount of 0.5 to 1 part ONN. In addition, the cobalt organic acid salt of the redox polymerization initiator is 0.05 to I
Although it is used in the amount of M, it is desirable to increase or decrease the amount as appropriate, taking into consideration the moisture 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 dry to the touch. The cured product contains almost all of the water contained during emulsification as minute droplets, and at the same time contains large-volume crystals such as Ca(OH)2, ettringite, etc. eluted components associated with cement water utilization reactions. Unlike conventional water-containing resins, it does not shrink or crack even when left in the air for long periods of time, and also has high dimensional stability, water retention, heat resistance, and mechanical strength. It has been improved. In particular, the improvement in mechanical strength is associated with the introduction of chemical prestress by cement expanders and the consolidation effect.

That is, the cement water or dispersion liquid dispersed as minute droplets in the resin reacts with the cement expanding agent, and a large volume of cement bacillus (Ba
cil'lus), ettringite crystals precipitate and grow at the interface between the resin and the aqueous phase, thereby imparting a chemical prestress effect to the cured resin product. In other words, due to the expansion force of ettringite crystals, Ca(OH)z crystals, etc., chemical prestress is later introduced into the hardened resin matrix, and when it is further restrained by the resin matrix, a consolidation effect acts, resulting in high strength. A cured product can be obtained. The chemical reaction formula is shown below.

6CaO+kL203+ 3SO3+ 32H20-1→3CaO・AA20a 3CaSO4・32H203
CaOAt-zos + 3CaSO4+ 32H20
-1--→ 3CaO-A7!4os ・3CaSO4
・32H20CaO+H20-)Ca(OH)z 3Ca0・3At203・CaSO4+8CaS04+
6CaO+96H2〇-1→3(3CaO-AL203
・3CaSo4・32H20) As shown in the chemical reaction formula above, a large amount of bound water is required to sufficiently grow ettringite crystals, but conveniently, a large excess of water is dispersed in the hydrous polyester resin. .

Moreover, if the above reaction mechanism is utilized, for example, when preparing an emulsion, expanded cement (Expan
If a dispersion is used, only 3CaO-A7203-mH20 in the cement paste will participate in the reaction, so it will not expand much at the beginning, and since the dissolution rate of anhydrous ceracola is slow, ettringite crystals will gradually form over a long period of time. You can also do that. The reaction formula is shown below.

3CaO・At203・mH2O+3CaS○4+nH
zO-)3CaOAt20s 3CaSO4・32Hz
Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these seven examples.

Example 1゜Unsaturated polyester [Sumitomo Chemical ■Smiatube MG-1,
Oxidation 13-, containing fL/7 i 40 X] 1100
1.20 Or, p, m.

While stirring at a speed of
After stirring, the mixture was left to stand for 1 hour to obtain a supernatant. ) was gradually added little by little to obtain a polyester emulsion.

The emulsion obtained according to the invention was an oil/water/oil double emulsion. To 200 parts of the obtained emulsion were added 1 part of methyl ethyl ketone peroxide and 5 parts of Cobal Nanthenate (006%) O, 4X4X16c.
After pouring into a triple Fn form and curing at room temperature, it was taken out and left in an air bath at 60° C. for 4 hours to obtain a hard hydrous polyester resin specimen that felt completely dry. The hardness of this resin was 38 to 4o on the Barcol hardness tester. For comparison, 88,310 parts of Asano Gypcal [Nippon Cement] was used as a cement expansion material on a cement water conduit, and the Barcol hardness was 40 to 41. The two types of specimens obtained above were tested in accordance with JIS R-5201,
Compression and bending strength were measured using a hydraulic universal testing machine.

The results are shown in the table.

As can be seen from the results, the strength was improved by 15% in compression and 33X1 bending when the cement expansion agent was added compared to when it was not added. In addition, these two types of specimens were kept at room temperature.
After being left for 5 months, it was found that there was almost no change in weight and that they had excellent water retention.

Examples 2 to 5 Note 1) The bulk specific gravity of incinerated ash is approximately 0.2, which is equal to that of pearlite #1.

Note 2) Expan is Onoda Cement @ Asanojipcal is the trade name of Nippon Cement Co., Ltd.'s cement expansion material. Unsaturated polyester [Takeda Pharmaceutical ■Polymer 6702. 1 part of methyl ethyl ketone peroxide and cobalt naphthenate were added to the emulsion obtained by processing in the same manner as in Example 1, except that the mixture ratio was as shown in the table above. (C
.

After adding 0.5 part of 6%), knead the incineration ash uniformly and place it in a 4x4x1171 double mold for mortar testing.
After standing at 0°C for 6 hours, a specimen of Example 2°40 hydrous resin mortar was obtained.

For comparison, hydrated resin mortar specimens of Examples 3 and 5 were obtained by processing in the same manner as in Examples 2 and 4, except that a certain amount of Expan or Asano Dipcal was added to the cement hydration semen as a cement expansion agent. .

The four types of specimens obtained above were compressed according to the method of Example 1, and the bending strength was measured.

The results are summarized in 2.

As can be seen by comparing Example 2.4, the mechanical strength of hydrous resins generally decreases as the water content increases. In this case, when the water content increases by 50%, the compressive strength decreases by 25% and the bending strength decreases by 15X.

However, Examples 3 and 5 in which Expan and Asanogypcal were added as cement expansion agents to the composition of Example 2.4.
In both cases, a significant improvement in strength can be seen. Example 2.
When comparing Example 3, the compressive strength is increased by 65% and the bending strength is increased by 41%, and when comparing Example 4.5, the compressive strength is increased by 99%.
%, the song's intensity has increased by 68%. In Example 3, large plate-shaped crystals of Ca were generated by watering the cement hydrated 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 Rttringit, and crystal pressure. On the other hand, in Example 5, the cement irrigation liquid phase and anhydrous calcium sul7o aluminate (4Ca0 ・3AI, 20s ・5O3
), reacts with gypsum (CaSO4) and calcium oxide, forming Ettringit needle crystals and Ca(OH)r7)
'This is due to a large amount of precipitation and growth. Comparing Examples 3 and 5, Example 5 has a higher moisture content than Example 3, but Azano dypcal has a higher strength than Example 3. Azano dypcal has a larger volume cement than Expan - Bacillus, Ett.
This is to precipitate a large amount of ringit. That is, the prestressing effect of water particles in the cured product obtained in the present invention depends on whether the generated crystals are mainly Ca(OH)2 or not.
It depends on whether t is the main character. It depends on the situation. 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 to 8゜--Processed in the same manner as in Examples 2 and 3, except that Takeda Pharmaceutical @φNelimar 6702 was used as the unsaturated polyester resin and the compounding ratio was changed as shown in the table above, and Example 6, 7.8
A hydrous resin mortar specimen was obtained. Regarding the three types of specimens obtained above, ASTM D-1242-4
A wear resistance test was conducted according to 6MethodA. The results were summarized in a piece of clothing. Comparing Examples 6 and 7.8, the wear amount was 0.61 am when no Expan was added, and 0.57 'am (7% reduction) when 15% Expan was added.
, when 30% was added, the value decreased to 46my1 (25% wave). - It can be seen that the addition of Expan significantly improves the abrasion resistance. This shows that the mechanical strength of Examples 3 and 5 was improved, and the large volume of Ca(OH)2, Et
This is caused by the prestressing effect and the casing effect caused by the precipitation and growth of tringit 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, heat resistance, and flame resistance. performance has been significantly improved. Applying these properties to civil engineering construction materials and polymer coatings
Floor finishes can be used for a variety of purposes, including lumber, synthetic wood, flame retardant, heat insulation, and soundproofing.

Claims (1)

[Claims] Unsaturated polyester oil phase and oil/water/oil or water/oil/ obtained from cement hydrated semen or cement dispersion.
A method for producing a water-containing polyester resin by cross-linking and curing a double emulsion of water, characterized in that a cement expanding agent is present in the double emulsion.