EA030417B1

EA030417B1 - Process for the preparation of a sulphur cement product and sulphur cement product prepared by this process

Info

Publication number: EA030417B1
Application number: EA201690313A
Authority: EA
Inventors: Ги Лоде Магда Мария Вербист; Корнелис Питер Хамелинк; Эдвард Росс Диксон; Арианне Элисабет Хоммес
Original assignee: Шелл Интернэшнл Рисерч Маатсхаппий Б.В.
Priority date: 2013-08-01
Filing date: 2014-07-31
Publication date: 2018-08-31
Also published as: EP3027577A1; EA030417B9; WO2015014953A1; EA201690313A1

Abstract

The invention relates to a process for the preparation of a sulphur cement product comprising admixing sulphur, particulate inorganic material and an oligomeric organosilane having one or more terminal groups of general formula (I)wherein Ris a linear or branched hydrocarbyl group having from 2-24 carbon atoms and Ris a linear or branched hydrocarbyl group having from 2-40 carbon atoms, wherein the particulate inorganic material is a filler or a sulphur cement aggregate and admixing all the components is carried out at a temperature at which the sulphur is molten to produce a molten sulphur cement product; and solidifying the molten sulphur cement product. The amount of the oligomeric organosilane which is admixed with sulphur and the particulate inorganic material is in the range of from 0.05 to 1 wt.% based of the weight of sulphur. The product prepared by said process is also disclosed.

Description

The invention relates to a method for producing a product from sulfur cement, comprising mixing sulfur, a dispersed inorganic material and an oligomeric organosilane containing one or more end groups described by the general formula (I)

I ^k2 \

I

030417 1

(I)

where K ¹ is a linear or branched hydrocarbyl group containing 2-24 carbon atoms, and K ² is a linear or branched hydrocarbyl group containing 2-40 carbon atoms, with the dispersed inorganic material being a filler or aggregate of sulfur cement and mixing all the components are carried out at a temperature at which sulfur melts to form a molten sulfur cement product; and solidification of the product from molten sulfur cement. The amount of oligomeric organosilane, which is mixed with sulfur and dispersed inorganic material, is in the range from 0.05 to 1 wt.% When calculating the mass of sulfur. Disclosed as a product obtained in this way.

030417

The technical field to which the invention relates.

The present invention provides a method for producing sulfur cement products. The invention also provides sulfur cement products, including sulfur cement, sulfur mortar and sulfur concrete. The invention also provides modified sulfur, which can be used in the production of sulfur cement products. The invention also provides a modified particulate inorganic material that can be used in the preparation of sulfur cement products.

The level of technology

Elemental sulfur or modified sulfur can be used to bind the aggregate and filler, which, in turn, leads to the manufacture of sulfur cement products, such as sulfur mortar and sulfur concrete. Sulfur concrete can be used in a wide range of precast concrete applications such as fortifications, paving slabs, road barriers and retaining walls.

Publication UO 2008 148804 describes the possibility of using polysulfide-containing organosilanes as stabilizers for the production of sulfur cement products, demonstrating improved water absorption properties. Sulfur cement products additionally have beneficial mechanical properties.

Additional stabilizers or coupling agents are described in publications \ EO 2011/000837 and \\ 'O / 2012 101127.

When used for the manufacture of sulfur cement, many organosilane coupling agents known in the prior art give ethanol or methanol as a by-product. Methanol and ethanol are volatile organic compounds (VOCs), and it is desirable to limit the number of VOC compounds that are released during the manufacture of sulfur cement products. The inventors sought to create a method of manufacturing products from sulfur cement, in which the formation of VOC compounds is reduced and in which products from sulfur cement retain satisfactory water absorption characteristics and mechanical properties.

Summary of Invention

As the inventors of the present invention have established, by using another type of organosilane in a method for producing sulfur cement products, reduced formation of VOC compounds can be achieved, but at the same time, sulfur cement products can be produced that demonstrate satisfactory water absorption characteristics and mechanical properties.

Accordingly, the invention provides a method for producing sulfur cement products, comprising the steps of:

(a) mix sulfur, dispersed inorganic material and oligomeric organosilane containing one or more end groups, described by the general formula (I)

(I)

where K ¹ is a linear or branched hydrocarbyl group containing 224 carbon atoms, and K ² is a linear or branched hydrocarbyl group containing 2-40 carbon atoms, the dispersed inorganic material being a filler or aggregate of sulfur cement and mixing all the components is carried out at the temperature at which sulfur melts to form a molten product from sulfur cement, and

(B) the molten sulfur cement product is cured.

In one further aspect, the present invention provides a sulfur cement product obtained by the above method, comprising sulfur and a reaction product between a particulate inorganic material and an oligomeric organosilane containing one or more end groups described by the general formula (I)

(one)

where K ¹ is a linear or branched hydrocarbyl group containing 224 carbon atoms, and K ² is a linear or branched hydrocarbyl group containing 2-40 carbon atoms.

In yet another additional aspect, the present invention provides modified sulfur,

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containing sulfur and oligomeric organosilane containing one or more end groups, described by the general formula (I)

(I)

where K ¹ is a linear or branched hydrocarbyl group containing 224 carbon atoms, and K ² is a linear or branched hydrocarbyl group containing 2-40 carbon atoms. Modified sulfur in a suitable case for use is used in the method for producing sulfur cement products of the invention.

In yet another additional aspect, the present invention provides a modified particulate inorganic material, which is a reaction product between a particulate inorganic material and an oligomeric organosilane containing one or more end groups described by the general formula (I)

(I)

where K ¹ is a linear or branched hydrocarbyl group containing 224 carbon atoms, and K ² is a linear or branched hydrocarbyl group containing 2-40 carbon atoms. The modified particulate inorganic material in a suitable case for use is used in the method for producing the sulfur cement products of the invention.

Detailed Description of the Invention

The term “sulfur cement product” refers to a composite containing sulfur, a filler and optionally a filler. Fillers and aggregates are dispersed inorganic materials. Fillers are characterized by an average particle size in the range from 0.1 μm to 0.1 mm. Fine aggregate is characterized by an average particle size in the range from 0.1 to 5 mm. Coarse aggregate is characterized by an average particle size in the range from 5 to 40 mm. Average particle sizes are based on arithmetic mean values. The sulfur cement of the invention contains sulfur and a filler, but not a filler. Sulfur mortar of the invention contains sulfur, a filler and fine aggregate, but does not contain coarse aggregate. The sulfur concrete of the invention contains sulfur, a filler, coarse aggregate and optionally fine aggregate.

The amounts of sulfur, filler and aggregate in the sulfur cement products of the invention can be chosen by experts in the relevant field of technology, taking into account the intended use of sulfur cement products. Specialists in the relevant field of technology will strive to ensure the inclusion of sufficient sulfur to bind the filler and aggregate, the inclusion of sufficient amounts of filler and aggregate to impart mechanical properties and to obtain from other components of the mixture, characterized by processability, suitable for use in the intended application. Sulfur cement preferably contains from 25 to 80 wt.% Sulfur and from 20 to 75 wt.% Filler. Sulfur mortar preferably contains from 5 to 40 wt.% Sulfur, from 45 to 90 wt.% Fine aggregate and from 1 to 10 wt.% Filler; more preferably from 5 to 30% by weight of sulfur, from 55 to 75% by weight of fine aggregate and from 3 to 8% by weight of filler. Sulfur concrete preferably contains from 5 to 40 wt.% Sulfur, from 25 to 50 wt.% Coarse aggregate, from 20 to 40 wt.% Fine aggregate, and from 1 to 10 wt.% Aggregate; more preferably from 5 to 30% by weight of sulfur, from 30 to 40% by weight of coarse aggregate, from 25 to 35% by weight of fine aggregate and from 3 to 8% by weight of filler.

The dispersed inorganic material can be any dispersed inorganic material known for use as a filler or aggregate of sulfur cement. Preferably, the dispersed inorganic material contains oxide or hydroxyl groups on its surface. Examples of dispersed inorganic materials suitable for use are silica, fly ash, limestone, quartz, iron oxide, aluminum oxide, titanium dioxide, carbon black, gypsum, talc or mica, sand, gravel, rock, or metal silicates. More preferably, the particulate inorganic material is silica or silicate. Examples of such silica or silicates are quartz, sand, and metal silicates (for example, mica).

In the process of the invention, sulfur, a dispersed inorganic material and an oligomeric organosilane are mixed, containing one or more terminal groups, described by the general formula (I)

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where K is a linear or branched hydrocarbyl group containing 224 carbon atoms, and K ² is a linear or branched hydrocarbyl group containing 2-40 carbon atoms.

Oligomeric organosilane in a suitable case for use is obtained when using the method, where the silane, described by formula (II), is introduced into the reaction with the polyhydroxy-containing compound, described by formula (III)

where X is a hydrolysable leaving group, preferably C _1-6 alkoxy, and most preferably ethoxy. In one particular embodiment, more than one silane can be used, for example two silanes can be used:

K ^2b

This will result in an oligomeric organosilane containing a mixture of groups K ^2a and

Organosilane is oligomeric in the sense that it will be obtained by reaction for several organosilane monomers. The structure of the oligomeric organosilane is preferably described by formula (IV)

where η is an integer. The oligomer will contain at least two end groups. At least one of the end groups, possibly more than one, will be described by formula (I).

K ¹ is a linear or branched hydrocarbyl group containing 2-24 carbon atoms. Preferably, K ¹ contains 2-16 carbon atoms, more preferably 2-8 carbon atoms. Preferred groups include 2-methylpropyl and 1-methyl-3,3-dimethylpropyl. Preferably, the carbon chain between the bound oxygen atoms is three carbon atoms long. K ^{1 is} preferably non-functionalized.

K ² is a linear or branched hydrocarbyl group containing 2-40 carbon atoms. Preferably, K ² contains 2-24 carbon atoms, more preferably 2-16 carbon atoms. K ² is optionally functionalized using one or more groups selected from thiol, thioester, alcohol, ester, carboxylic acid, carbonyl, amine, or amide groups. In one preferred embodiment, K ² is functionalized using a thiol or thioester group.

Suitable oligomeric organosilanes for use and methods for their preparation are described in publications J.) 2006/86375 and J.) 2008/21308. Oligomeric organosilanes are available from Moshepyu Reggoghapee Ma1ena1§ Shee. under the trade name ΝΧΤ * Ζ.

The sulfur cement products of the invention are suitably prepared using a process in which all components are mixed at a temperature at which the sulfur is melted, that is, usually at more than 120 ° C, preferably in the range from 120 to 150 ° C, more preferably in the range from 125 to 140 ° C. The mixture is preferably poured into the mold. After that, the product is solidified from sulfur cement by cooling to a temperature at which the sulfur hardens. After cooling, the sulfur cement product can be removed from the mold.

The amount of oligomeric organosilane, which is mixed with sulfur and dispersed inorganic material, is preferably in the range from 0.05 to 1 wt.% When calculating the mass of sulfur, preferably from 0.1 to 0.4 wt.%. In the case of using less than 0.05 wt.% Oligomeric organosilane, the modification may not provide sufficient improvement in water absorption and mechanical properties. The use of more than 1 wt.% Of oligomeric organosilane is usually optional, since all possible improvements in water absorption and mechanical properties will be

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achieved when using 1 wt.%.

In the case of mixing the oligomeric organosilane with the inorganic particulate material, there will be a reaction between the end groups of the oligomeric organosilane and the surface groups of the inorganic dispersed material. In the process, compounds having the formula HO-K? -OH will be obtained, and such compounds tend to exhibit boiling points that are high enough so that the compounds are not considered as LOS compounds.

In the method of the invention, a set of components may be submitted to the mixing stage in the form of a pre-composition or masterbatch. In one embodiment, the sulfur and oligomeric organosilane can be supplied as modified sulfur. Therefore, in one additional aspect, the present invention provides modified sulfur containing sulfur and an oligomeric organosilane containing one or more end groups described by the general formula (I)

(I)

where K ¹ is a linear or branched hydrocarbyl group containing 224 carbon atoms, and K ² is a linear or branched hydrocarbyl group containing 2-40 carbon atoms. The modified sulfur preferably contains less than 1% by weight of filler and less than 1% by weight of aggregate; and most preferably does not contain any filler and any aggregate. The modified sulfur preferably contains from 0.01 to 20 wt.% Oligomeric organosilane, more preferably from 0.01 to 10 wt.%, Most preferably from 0.01 to 1 wt.%, Where the levels of the mass percentage is obtained by mass modified sulfur. The modified sulfur preferably contains at least 80% by weight of sulfur. In one embodiment, the modified sulfur may contain higher amounts of oligomeric organosilane, for example, from 5 to 20 wt.%, And may also contain higher amounts of filler, for example, from 5 to 20 wt.%, Where the mass percentage levels are obtained by calculation on modified sulfur mass. In this embodiment, the modified sulfur is “concentrated” modified sulfur, and such “concentrated” modified sulfur can be used in small quantities to produce significant amounts of oligomeric organosilane.

In yet another embodiment, the particulate inorganic material and the oligomeric organosilane can be supplied in the form of a modified dispersed inorganic material. Therefore, in one additional aspect, the present invention provides a modified particulate inorganic material, which is a reaction product between a particulate inorganic material and an oligomeric organosilane containing one or more end groups described by the general formula (I)

I ^K2

I

(I)

where K ¹ is a linear or branched hydrocarbyl group containing 224 carbon atoms, and K ² is a linear or branched hydrocarbyl group containing 2-40 carbon atoms. The modified particulate inorganic material in a suitable case for use is obtained by combining the particulate inorganic material and from 0.001 to 5 wt.% Oligomeric organosilane, more preferably from 0.01 to 1 wt.%, Most preferably from 0.01 to 0.1 wt. .%, where the mass percentage levels are obtained by calculating the mass of the dispersed inorganic material.

Sulfur cement products obtained in accordance with the invention can be used in a wide range of applications. Sulfur concrete can be used in precast concrete applications such as fortifications, paving slabs, road barriers and retaining walls.

Examples

The invention is further illustrated using the following non-limiting examples.

Examples 1-6. Samples of sulfur mortar (fly ash / normal sand) were obtained using the following method.

Sulfur (25 (wt.% / Wt.%)), Preheated to about 65 ° C, and pre-heated

heated sand (150 ° C, 60 (wt.% / wt.%)) was stirred at 140 ° C until a homogeneous mixture. In some cases, 0.06 (wt% / wt%) bis (3-triethoxysilylpropyl) tetrasulfide (TESPT) was added to the mixture and continuously stirred for 5 minutes. After that, the appropriate amount of modifier ΝΧΤ Ζ 100 was added and stirred for another 5 min (see table). Then, preheated fly ash (150 ° C, 15 (wt% / wt%)) was added to the mixture and stirred for another 10 minutes. In conclusion, the mixture was poured into pre-heated (150 ° C) silicone molds with dimensions of 4 cm x 4 cm x 16 cm and allowed to cool to ambient temperature in a fume hood. The mortars were allowed to cure for at least 48 hours.

Organosilane modifier Comparative Example 1 Missing Comparative Example 2 0.06 wt.% Compound TESPT Example 1 0.06 wt.% Modifier ΝΧΤ 100 [1] Example 2 0.06 wt.% Compound TESPT 0.06 wt.% Modifier ΝΧΤ 100 [1] Example 3 0.06 wt.% Modifier ΝΧΤ 100 [2] Example 4 0.06 wt.% Compound TESPT 0.06 wt.% Modifier ΝΧΤ 100 [2] Example 5 0.06 wt.% Modifier ΝΧΤ 100 [3] Example 6 0.06 wt.% Compound TESPT 0.06 wt.% Modifier ΝΧΤ 100 [3]

The product ΝΧΤ Ζ 100 is an oligomeric organosilane available from Motepyuye RegGogtaps Milenapis 1ps. Three samples of organosilane were used: sample [1] corresponded to a fresh bottle of organosilane, sample [2] corresponded to a bottle of organosilane two weeks old, and sample [3] was exposed to atmospheric conditions in a hood overnight. Product ΝΧΤ Ζ 100 is susceptible to moisture absorption, as evidenced by a weight gain of 9.20% when exposed to atmospheric conditions overnight in a fume hood.

During all the experiments, there were no emissions of H ₂ 3 and 8 O ₂ detected with the use of portable detectors (the lower limit of detection was 0.2 ppm).

The durability of sulfur mortars was determined by measuring the retention of the flexural strength and water penetration after two months of immersion in water. The results are shown in FIG. 1 and 2. Sulfur mortar obtained in accordance with the method of the invention, have the best properties of maintaining the strength and penetration of water in comparison with the sulfur mortar, which does not contain organosilane (comparative example 1). They have similar, but slightly degraded properties of maintaining the strength and penetration of water in comparison with sulfur mortar, which contains organosilane TESPT (comparative example 2).

Example 7. Samples of sulfur mortar (fly ash / normal sand) were obtained using the following method.

Sulfur (25 (wt.% / Wt.%)), Preheated to approximately 65 ° C, and preheated sand (150 ° C, 60 (wt.% / Wt.%)) Was stirred at 140 ° C until receiving homogeneous mixture. After that, the appropriate amount of bis (3-triethoxysilylpropyl) tetrasulfide (TESPT) (0.06 wt.%) Or modifier ΝΧΤ Ζ 100 (0.02, 0.04, 0.06 or 0.12 wt.%) Was added and mixed for another 5 min. Then, preheated fly ash (150 ° C, 15 (wt.% / Wt.%)) Was added to the mixture and stirred for another 10 minutes. In conclusion, the mixture was poured into pre-heated (150 ° C) silicone molds with dimensions of 4 cm x 4 cm x 16 cm and allowed to cool to ambient temperature in a fume hood. The mortars were allowed to cure for at least 48 hours.

During all experiments, there were no emissions of H ₂ 3 and AO ₂ , detected using portable detectors (the lower detection limits are 1.6 ppm for H ₂ 3 and 2 ppm for 8 ₂ O) .

The durability of sulfur mortar was determined by measuring the penetration of water and maintaining the flexural strength after one month of immersion in water.

Samples containing the product ΝΧΤ Ζ 100, with all tested concentrations are characterized by significantly less water penetration and greater preservation of strength in comparison with the sample that does not contain any modifier. Water penetration and retention of strength for all samples based on the product ΝΧΤ are comparable to what occurs for a sample containing 0.06 wt.% TESPT compound.

Example 8. Samples of sulfur mortar (fly ash / normal sand) were obtained using the following method.

Sulfur (25 (wt.% / Wt.%)), Preheated to approximately 65 ° C, and preheated sand (150 ° C, 60 (wt.% / Wt.%)) Was stirred at 140 ° C until receiving homogeneous mixture. After this was added the proper amount of compound TESPT (0.06 wt.%) Or modifier

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ΝΧΤ Ζ 100 (0.02, 0.04, 0.06, or 0.12 wt.%) And stirred for another 5 minutes. Then, preheated fly ash (150 ° C, 15 (wt% / wt%)) was added to the mixture and stirred for another 10 minutes. In conclusion, the mixture was poured into pre-heated (150 ° C) silicone molds with dimensions of 4 cm x 4 cm x 16 cm and allowed to cool to ambient temperature in a fume hood. The mortars were allowed to cure for at least 48 hours.

During all experiments, there were no releases of Η ₂ δ and δθ ₂ detected with the use of portable detectors (the lower detection limits are 1.6 ppm for ₂ δ and 2 ppm for δ2θ).

The durability of sulfur mortars was determined by measuring the penetration of water and maintaining the flexural strength after immersion in water for approximately 8 months.

Samples containing 0.02% and 0.04% by weight of the product Ζ подобные 100 demonstrate similar performance characteristics from the point of view of water penetration compared to what occurs for a sample containing 0.06% by weight of TESPT compound. Also, their preservation of strength after almost 8 months of storage in water is quite large (83.5 and 107.2% for samples containing, respectively, 0.02 and 0.04 wt.% Product Ζ 100).

Claims

CLAIM

1. A method of obtaining a product from sulfur cement, including the stage at which carry out:

(a) mixing of sulfur, particulate inorganic material and oligomeric organosilane containing one or more end groups, described by the general formula (I)

I ^k2 \

I

ι ⁽¹⁾

where K ¹ is a linear or branched hydrocarbyl group containing 224 carbon atoms, and K ² is a linear or branched hydrocarbyl group containing 2-40 carbon atoms, the dispersed inorganic material being a filler or aggregate of sulfur cement and mixing all the components is carried out at the temperature at which sulfur melts to form a molten product from sulfur cement;

(B) solidification of the product from molten sulfur cement.

2. The method according to claim 1, in which the amount of oligomeric organosilane, which is mixed with sulfur and dispersed inorganic material in stage (a), is in the range from 0.05 to 1 wt.% When calculating the mass of sulfur.

3. The method according to claim 1 or 2, in which in step (a) the sulfur and the oligomeric organosilane are mixed, containing one or more end groups described by the general formula (I), to obtain a modified sulfur containing sulfur and the oligomeric organosilane containing one or several end groups described by the general formula (I), and then the modified sulfur is mixed with the particulate inorganic material.

4. The method according to claim 1 or 2, in which in step (a) the dispersed inorganic material and the oligomeric organosilane are mixed containing one or more end groups described by the general formula (I) to obtain a modified inorganic dispersed material, which is the reaction product between the dispersed inorganic material and the oligomeric organosilane containing one or more end groups described by the general formula (I), and then the modified dispersed inorganic material is mixed with sulfur.

5. Product from sulfur cement, obtained by the method according to claim 1 or 2.

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