KR101160422B1 - Modified sulfur polymer and concrete composition comprising the same - Google Patents

Modified sulfur polymer and concrete composition comprising the same Download PDF

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KR101160422B1
KR101160422B1 KR1020100114356A KR20100114356A KR101160422B1 KR 101160422 B1 KR101160422 B1 KR 101160422B1 KR 1020100114356 A KR1020100114356 A KR 1020100114356A KR 20100114356 A KR20100114356 A KR 20100114356A KR 101160422 B1 KR101160422 B1 KR 101160422B1
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South Korea
Prior art keywords
sulfur polymer
formula
weight
sulfur
modified sulfur
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KR1020100114356A
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Korean (ko)
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KR20120053202A (en
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김재현
김혜령
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지에스칼텍스 주식회사
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Priority to PCT/KR2011/002314 priority patent/WO2012067314A1/en
Priority to CN201180055674.6A priority patent/CN103221457B/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/025—Preparatory processes
    • C08G75/0263—Preparatory processes using elemental sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers

Abstract

The present invention provides a modified sulfur polymer synthesized by polymerizing a phenol compound or a thioester compound with sulfur and dicyclopentadiene.
According to the present invention, it is possible to obtain a modified sulfur polymer having excellent long-term storage properties and workability, and excellent mechanical strength such as bending strength and compressive strength.

Description

Modified sulfur polymer and concrete composition containing same {MODIFIED SULFUR POLYMER AND CONCRETE COMPOSITION COMPRISING THE SAME}

The present technology relates to sulfur polymer cement (SPC) related technology, specifically, a technology related to a modified sulfur polymer that can replace conventional cement and improve long-term storage and workability.

Recently, researches using sulfur to replace cement have been actively conducted. In particular, techniques are known which can ensure excellent strength by modifying sulfur to synthesize it as a polymer.

As such, the sulfur polymer is a material obtained by mixing sulfur with specific monomers as a sulfur modifier and polymerizing the sulfur polymer. The sulfur polymer may be used in asphalt and the like, and may also be used in concrete compositions by mixing aggregates and other fillers.

On the other hand, as a method of synthesizing a sulfur polymer, a method of reforming sulfur by mixing sulfur with dicyclopentadiene (DCPD) and then cooling it is known. However, in the case of using an excessive sulfur modifier to enhance strength, this method is known. There is a problem to be improved in terms of physical properties such as workability deterioration and bending strength.

To date, as described above, a method for synthesizing a sulfur polymer using DCPD is known, and additional compounds for replacing or supplementing DCPD are not widely known. In addition, in order to enhance the strength, when a sulfur modifier is used in synthesizing the sulfur polymer, there is a problem in that the viscosity of the sulfur polymer is increased and workability is extremely lowered. There is a need for technology that can be improved.

An object of the present invention is to provide a modified sulfur polymer which is excellent in flexural strength and compressive strength and at the same time improves long-term storage and workability. Moreover, this invention makes it the subject to provide the concrete composition manufactured using the said modified sulfur polymer and excellent in strength.

The present invention to solve the above problems, 100 parts by weight of sulfur, 1 to 10 parts by weight of dicyclopentadiene (DCPD); And 0.05 to 3 parts by weight,

Figure 112010075056547-pat00001
It provides a modified sulfur polymer synthesized by polymerizing with an aryl compound having 8 to 75 carbon atoms containing a group or a compound represented by the formula (1).

(Wherein, R 1 and R 2 are the same or different and each independently represent an alkyl group having 1 to 18 carbon atoms.)

Figure 112010075056547-pat00002

(Wherein

R 3 is

Figure 112010075056547-pat00003
X is an integer from 0 to 4,

R 4 is an alkyl group having 1 to 20 carbon atoms.)

The aryl compound may be a compound represented by the following Chemical Formulas 2 to 6.

Figure 112010075056547-pat00004

Figure 112010075056547-pat00005

Figure 112010075056547-pat00006

Figure 112010075056547-pat00007

Figure 112010075056547-pat00008

The compound of Chemical Formula 1 may be a compound represented by the following Chemical Formulas 7 to 9.

Figure 112010075056547-pat00009

Figure 112010075056547-pat00010

Figure 112010075056547-pat00011

The present invention provides a modified sulfur polymer having a viscosity of 600 cps or less after five days storage at 130 ° C. temperature.

In addition, the present invention 100 parts by weight of the modified sulfur polymer; And it provides a concrete composition comprising 200 to 600 parts by weight of aggregate.

According to the present invention, it is possible to obtain a modified sulfur polymer having excellent long-term storage properties and workability, and excellent mechanical strength such as bending strength and compressive strength.

1 is a graph showing the viscosity change according to the storage date of the modified sulfur polymer according to an embodiment of the present invention.

Modified sulfur polymer according to an embodiment of the present invention, 100 parts by weight of sulfur, 1 to 10 parts by weight of dicyclopentadiene (DCPD); And 0.05 to 3 parts by weight,

Figure 112010075056547-pat00012
It may be synthesized by polymerizing with an aryl compound having 8 to 75 carbon atoms containing a group or a compound represented by the following formula (1).

[Formula 1]

Figure 112010075056547-pat00013

In the above formula, R 1 and R 2 are the same or different and each independently represent an alkyl group having 1 to 18 carbon atoms. More preferably, R 1 and R 2 may be an alkyl group having 4 to 18 carbon atoms, and most preferably, a tert-butyl group.

.

Figure 112010075056547-pat00014
Specific examples of the tris (3,5-di-tert-butyl-4-hydroxyphenyl) group may be mentioned.

In the above formula, R 3 is

Figure 112010075056547-pat00015
X is an integer of 0-4, More preferably, x is an integer of 1-2.

R 4 is an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 12 to 20 carbon atoms, and most preferably an alkyl group having 12 to 18 carbon atoms.

The sulfur is the first powdery sulfur, S 8 may be used as the sulfur. The sulfur is melted during the reaction to participate in the synthesis of the sulfur polymer as molten sulfur. When the content of the DCPD is less than 1 part by weight, the polymerization of the sulfur polymer may be weakened, and thus the mechanical strength of the sulfur polymer may be lowered. Can be drastically reduced. In particular, when the percentage content in the sulfur polymer of the DCPD is 2.0 to 3.5% by weight, it is very advantageous in terms of strength and shelf life of the sulfur polymer.

Specifically, the aryl compound is a compound represented by the following Chemical Formulas 2 to 6.

[Formula 2]

Figure 112010075056547-pat00016

(3)

Figure 112010075056547-pat00017

[Formula 4]

Figure 112010075056547-pat00018

[Chemical Formula 5]

Figure 112010075056547-pat00019

[Formula 6]

Figure 112010075056547-pat00020

The compound of Formula 1 is specifically a compound of Formulas 7 to 9.

[Formula 7]

Figure 112010075056547-pat00021

[Formula 8]

Figure 112010075056547-pat00022

[Chemical Formula 9]

Figure 112010075056547-pat00023

The synthesis may be performed for 1 to 3 hours at a temperature of 130 ℃ to 150 ℃.

 The modified sulfur polymer according to one embodiment of the present invention has a viscosity of 600 cp or less after 5 days storage at 130 ℃ temperature.

When synthesizing the modified sulfur polymer, a radical reaction between sulfur and a modifier by polymerizing a phenolic compound or a thioester compound represented by Formula 1 together with sulfur and dicyclopentadiene, more specifically, an aryl compound having 8 to 75 carbon atoms. By controlling the viscosity it is possible to maintain a low viscosity.

The modified sulfur polymer may be mixed with aggregate and other fillers and used as a concrete composition. Concrete composition according to an embodiment of the present invention 100 parts by weight of the modified sulfur polymer; And 200 to 600 parts by weight of aggregate.

In addition, the concrete composition may further include a filler to further improve the strength of the concrete. Glass fibers and the like may be used as the filler.

Hereinafter, the above-described modified sulfur polymer and concrete composition will be described in more detail. However, the technical spirit of the present invention is not limited by the following examples.

Example

Example  One

3 kg of sulfur was added to a 5 L reactor made of stainless steel and dissolved in an oven at 140 ° C. for 3 hours. To synthesize sulfur polymer (SPC), 4 parts by weight of DCPD was added dropwise to the reactor with respect to 100 parts by weight of sulfur to the reactor and stirred for 2 hours, followed by 2,6-di-t-butyl-p-cresol (2,6 -di-t-butyl-p-cresol) was added dropwise to the reactor and stirred for 30 minutes. The reaction proceeded under a temperature of 145 ° C. After completion of the reaction, the mixture was stirred for 5 days at 130 ° C. and the viscosity was measured.

Example  2

Octadecyl 3,5-di-t-butyl-4-hydroxy hydrocinnamate instead of 2,6-di-t-butyl-p-cresol It carried out similarly to Example 1 except using 1 weight part.

Example  3

Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane instead of 2,6-di-t-butyl-p-cresol Except for using 1 part by weight of (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane) it was carried out in the same manner as in Example 1.

Example  4

The same procedure as in Example 1 was conducted except that 1 part by weight of distearyl thiodipropionate was used instead of 2,6-di-t-butyl-p-cresol.

Example  5

Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate instead of 2,6-di-t-butyl-p-cresol (Tris (3,5-di-tert-butyl-4 -hydroxybenzyl) isocyanurate) was carried out in the same manner as in Example 1 except for using 1 part by weight.

Example  6

1,3,5-trimethyl 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (1,3 instead of 2,6-di-t-butyl-p-cresol Example 1, except that 1 part by weight of, 5-Trimethyl-2,4,6-tris (3,5-di- tert- butyl-4-hydroxybenzyl) benzene) was used.

Example  7

The same procedure as in Example 1 was conducted except that 1 part by weight of Di Myristryl Thiodipropionate was used instead of 2,6-di-t-butyl-p-cresol.

Example  8

The same procedure as in Example 1 was conducted except that 1 part by weight of dilauryl thiodipropionate was used instead of 2,6-di-t-butyl-p-cresol.

Comparative example

3 kg of sulfur was added to a 5 L reactor made of stainless steel and dissolved in an oven at 140 ° C. for 3 hours. In order to synthesize sulfur polymer (SPC), 4 parts by weight of DCPD was added dropwise to the reactor with respect to 100 parts by weight of sulfur to the reactor and stirred for 2 hours. The reaction proceeded under a temperature of 145 ° C. After completion of the reaction, the mixture was stirred for 5 days at 130 ° C. and the viscosity was measured.

Viscosity Measurement Results

In Comparative Examples and Examples 1 to 4, the viscosity was measured at 130 ° C. for 0 to 5 days after the synthesis of the sulfur polymer, and the results of viscosity measurements are shown in Table 1 below. 1 is a graph showing the viscosity change according to the storage date of the sulfur polymer according to Comparative Examples and Examples 1 to 4.

0 days 1 day 2 days 3 days 5 days Comparative example 76 549 840 890 1135 Example  One 71 300 407 427 599 Example  2 74 548 509 466 440 Example  3 115 449 621 509 469 Example  4 73 677 674 502 570

Unit: cp (centi-poise)

Referring to Table 1 and Figure 1, after 5 days storage at 130 ℃ temperature can be confirmed that the viscosity of the modified sulfur polymer according to an embodiment of the present invention is less than 600 cp.

Claims (5)

100 parts by weight of sulfur,
1 to 10 parts by weight of dicyclopentadiene (DCPD); And
0.05 to 3 parts by weight,
Figure 112010075056547-pat00024
A modified sulfur polymer synthesized by polymerization with an aryl compound having 8 to 75 carbon atoms containing a group or a compound represented by the following formula (1).
(Wherein, R 1 and R 2 are the same or different and each independently represent an alkyl group having 1 to 18 carbon atoms.)
[Formula 1]
Figure 112010075056547-pat00025

Wherein R 3 is
Figure 112010075056547-pat00026
X is an integer from 0 to 4,
R 4 is an alkyl group having 1 to 20 carbon atoms.)
The method of claim 1,
The aryl compound is a compound represented by the formula 2 to 6, modified sulfur polymer.
(2)
Figure 112010075056547-pat00027

(3)
Figure 112010075056547-pat00028

[Chemical Formula 4]
Figure 112010075056547-pat00029

[Chemical Formula 5]
Figure 112010075056547-pat00030

[Formula 6]
Figure 112010075056547-pat00031

 The method of claim 1,
The compound of Formula 1 is a modified sulfur polymer, which is a compound represented by the formula (7-9).
[Formula 7]
Figure 112010075056547-pat00032

[Chemical Formula 8]
Figure 112010075056547-pat00033

[Chemical Formula 9]
Figure 112010075056547-pat00034

 The method of claim 1,
Modified sulfur polymer having a viscosity of 600 cps or less after 5 days storage at 130 ° C.
100 parts by weight of the modified sulfur polymer according to any one of claims 1 to 4; And
Concrete composition comprising 200 to 600 parts by weight of aggregate.
KR1020100114356A 2010-11-17 2010-11-17 Modified sulfur polymer and concrete composition comprising the same KR101160422B1 (en)

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PCT/KR2011/002314 WO2012067314A1 (en) 2010-11-17 2011-04-04 Reformulated sulfuric polymer and concrete composition containing same
CN201180055674.6A CN103221457B (en) 2010-11-17 2011-04-04 Reformulated sulfuric polymer and concrete composition containing same

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Publication number Priority date Publication date Assignee Title
KR20220040241A (en) 2020-09-23 2022-03-30 이희재 Method For Manufacturing Polysulfide For Preparing Concrete Composition

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EP2896644A1 (en) * 2014-01-20 2015-07-22 Construction Research & Technology GmbH Sulfur-based polymers
CN104844772B (en) * 2015-04-28 2017-11-10 中科院广州化学有限公司 It is a kind of that there is soluble elemental sulfur/alicyclic olefin copolymer and preparation method thereof
MX2022012785A (en) 2020-04-13 2023-03-01 Sileto Pesquisa E Desenvolvimento S A Polymer composite, use of said composite to prepare articles, method for preparing said composite and articles including said composite.

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US4190460A (en) 1978-04-03 1980-02-26 Suntech, Inc. Sulfur plasticization with olefins
US4290816A (en) 1979-01-29 1981-09-22 Southwest Research Institute Sulfur compounds and method of making same
JP2002060491A (en) 2000-08-16 2002-02-26 Nippon Mitsubishi Oil Corp Method for manufacturing sulfur binder, sulfur binder, and method for manufacturing sulfur composition
JP4166702B2 (en) 2002-03-08 2008-10-15 新日本石油株式会社 Method for producing modified sulfur-containing binder and method for producing modified sulfur-containing material

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US4219364A (en) * 1978-12-13 1980-08-26 Chevron Research Company Sulfur foam process and product
KR20040072278A (en) * 2003-02-10 2004-08-18 에스케이 주식회사 Sulfur polymer concrete pipe and manufacturing method thereof
JP4033894B2 (en) * 2005-11-14 2008-01-16 新日本石油株式会社 Modified sulfur-containing binder and method for producing modified sulfur-containing material
EP2362862A4 (en) * 2008-10-15 2014-08-20 Mun-Son Choe Modified sulfur binder and the fabrication method thereof, hydraulic modified sulfur material composition and the fabrication method thereof or combustible modified sulfur material composition and the fabrication method thereof containing the modified sulfur binder
CN101736911A (en) * 2009-12-31 2010-06-16 王丹 External protection or repair method for concrete

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Publication number Priority date Publication date Assignee Title
US4190460A (en) 1978-04-03 1980-02-26 Suntech, Inc. Sulfur plasticization with olefins
US4290816A (en) 1979-01-29 1981-09-22 Southwest Research Institute Sulfur compounds and method of making same
JP2002060491A (en) 2000-08-16 2002-02-26 Nippon Mitsubishi Oil Corp Method for manufacturing sulfur binder, sulfur binder, and method for manufacturing sulfur composition
JP4166702B2 (en) 2002-03-08 2008-10-15 新日本石油株式会社 Method for producing modified sulfur-containing binder and method for producing modified sulfur-containing material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20220040241A (en) 2020-09-23 2022-03-30 이희재 Method For Manufacturing Polysulfide For Preparing Concrete Composition

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KR20120053202A (en) 2012-05-25
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