WO2012067314A1 - Reformulated sulfuric polymer and concrete composition containing same - Google Patents

Reformulated sulfuric polymer and concrete composition containing same Download PDF

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WO2012067314A1
WO2012067314A1 PCT/KR2011/002314 KR2011002314W WO2012067314A1 WO 2012067314 A1 WO2012067314 A1 WO 2012067314A1 KR 2011002314 W KR2011002314 W KR 2011002314W WO 2012067314 A1 WO2012067314 A1 WO 2012067314A1
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sulfur polymer
sulfur
parts
concrete composition
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PCT/KR2011/002314
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French (fr)
Korean (ko)
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김재현
김혜령
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지에스칼텍스 주식회사
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Priority to CN201180055674.6A priority Critical patent/CN103221457B/en
Publication of WO2012067314A1 publication Critical patent/WO2012067314A1/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

Definitions

  • 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.
  • SPC sulfur polymer cement
  • 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.
  • 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, It provides a modified sulfur polymer synthesized by polymerization with an aryl compound having 8 to 75 carbon atoms or a compound represented by the following formula (1) containing a group.
  • DCPD dicyclopentadiene
  • R 1 and R 2 are the same or different and each independently represent an alkyl group having 1 to 18 carbon atoms.
  • R 3 is 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.
  • the compound of Chemical Formula 1 may be a compound represented by the following Chemical Formulas 7 to 9.
  • the present invention provides a modified sulfur polymer having a viscosity of 600 cps or less after five days storage at 130 ° C. temperature.
  • 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.
  • the concrete composition according to one side of the present invention can be used to manufacture at least one of sewer pipes, manholes, bricks, tiles, railway sleepers, piles and artificial reefs.
  • 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 100 parts by weight of sulfur, 1 to 10 parts by weight of dicyclopentadiene (DCPD); And 0.05 to 3 parts by weight, 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).
  • 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.
  • R 3 is 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.
  • 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.
  • 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.
  • the aryl compound is a compound represented by the following Chemical Formulas 2 to 6.
  • the compound of Formula 1 is specifically a compound of Formulas 7 to 9.
  • the synthesis may be performed for 1 to 3 hours at a temperature of 130 °C to 150 °C.
  • 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 °C temperature.
  • 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.
  • the concrete composition may further include a filler to further improve the strength of the concrete.
  • a filler to further improve the strength of the concrete. Glass fibers and the like may be used as the filler.
  • the concrete composition can be used to produce sewer pipes, manholes, bricks, tiles, railway sleepers, piles or artificial reefs.
  • the concrete composition may be used as a finished product or directly poured in the field. That is, since the concrete composition includes a modified sulfur polymer having excellent long-term storage properties and workability but excellent mechanical strength such as bending strength and compressive strength, the concrete composition may be used for such a purpose.
  • Example 2 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.
  • 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 2 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 2 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.
  • the viscosity of the modified sulfur polymer according to an embodiment of the present invention is less than 600 cp.

Abstract

The present invention provides a reformulated sulfuric polymer which is synthesized by polymerizing a phenol-based compound or a thioester-based compound with sulfur and dicyclopentadiene. According to the present invention, the reformulated sulfuric polymer having superior long-term storability and workability, and also having superior mechanical strength such as bending strength and compressive strength, can be obtained.

Description

개질 유황 폴리머 및 이를 포함하는 콘크리트 조성물Modified sulfur polymer and concrete composition comprising the same
본 기술은 유황 폴리머 시멘트(SPC) 관련 기술로서 구체적으로는 종래의 시멘트를 대체할 수 있고 장기저장성 및 작업성이 향상된 개질 유황 폴리머에 관한 기술이다.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.
최근 시멘트를 대체하기 위하여 유황을 사용하는 연구가 활발히 진행되고 있다. 특히, 유황을 개질하여 폴리머로서 합성함으로써 우수한 강도를 확보할 수 있는 기술들이 알려져 있다. 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.
이처럼, 유황 폴리머란 유황을 유황 개질제로서의 특정 모노머들과 혼합하여 폴리머화한 소재이며, 상기 유황 폴리머는 아스팔트 등에 사용될 수 있으며, 나아가 골재 및 기타 충진제 등을 혼합하여 콘크리트 조성물에 이용될 수 있다. 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.
한편, 유황 폴리머를 합성하는 방법으로서는, 유황을 디싸이클로펜타디엔(DCPD)과 혼합하여 반응 시킨 후 냉각함으로써 유황을 개질하는 방법이 알려져 있으나, 이 방법은 강도 강화를 위하여 과량의 유황 개질제를 사용할 경우 작업성이 저하되는 문제 및 휨 강도 등 물성 면에서 개선해야 할 문제점이 있다. 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.
현재까지는 전술한 바와 같이 DCPD를 이용한 유황 폴리머의 합성 방법이 알려져 있으며 DCPD를 대체하거나 DCPD를 보완하기 위한 추가 화합물 등에 대해서는 널리 알려져 있지 않다. 또한, 일반적으로 강도를 강화하기 위하여 유황 폴리머 합성시 유황 개질제를 많이 사용할 경우 유황 폴리머의 점성이 높아져 작업성이 극히 저하되는 문제점이 있어, 점도를 저점도로 일정하게 조절하면서 동시에 유황 폴리머의 강도 특성을 개선할 수 있는 기술이 요구되고 있다.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.
본 발명은 휨강도 및 압축강도가 우수하고 동시에 장기저장성 및 작업성이 향상된 개질 유황 폴리머를 제공하는 것을 그 과제로 한다. 또한, 본 발명은 상기 개질 유황 폴리머를 이용하여 제조되고, 강도가 우수한 콘크리트 조성물을 제공하는 것을 그 과제로 한다.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.
상기 과제를 해결하기 위하여 본 발명은, 100 중량부의 유황을, 1 내지 10 중량부의 디싸이클로펜타디엔(DCPD); 및 0.05 내지 3 중량부의,
Figure PCTKR2011002314-appb-I000001
기를 포함하는 탄소수 8 내지 75의 아릴 화합물 또는 하기 화학식 1로 표시되는 화합물과 중합하여 합성된 개질 유황 폴리머를 제공한다. 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 PCTKR2011002314-appb-I000001
It provides a modified sulfur polymer synthesized by polymerization with an aryl compound having 8 to 75 carbon atoms or a compound represented by the following formula (1) containing a group.
(상기 식에서, R1 및 R2 는 동일하거나 상이하고, 각각 독립적으로 탄소수 1 내지 18의 알킬기이다.)(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 PCTKR2011002314-appb-I000002
Figure PCTKR2011002314-appb-I000002
(상기 식에서, (Wherein
R3은
Figure PCTKR2011002314-appb-I000003
이고, x는 0 내지 4의 정수이며,R 3 is
Figure PCTKR2011002314-appb-I000003
X is an integer from 0 to 4,
R4 는 탄소수 1 내지 20의 알킬기이다.)R 4 is an alkyl group having 1 to 20 carbon atoms.)
상기 아릴 화합물은 하기 화학식 2 내지 6으로 표시되는 화합물일 수 있다. The aryl compound may be a compound represented by the following Chemical Formulas 2 to 6.
Figure PCTKR2011002314-appb-I000004
Figure PCTKR2011002314-appb-I000004
Figure PCTKR2011002314-appb-I000005
Figure PCTKR2011002314-appb-I000005
Figure PCTKR2011002314-appb-I000006
Figure PCTKR2011002314-appb-I000006
상기 화학식 1의 화합물은 하기 화학식 7 내지 9 로 표시되는 화합물일 수 있다.The compound of Chemical Formula 1 may be a compound represented by the following Chemical Formulas 7 to 9.
Figure PCTKR2011002314-appb-I000007
Figure PCTKR2011002314-appb-I000007
본 발명은 130℃ 온도에서 5일 저장 후 점성이 600 cp이하인 개질 유황 폴리머를 제공한다.The present invention provides a modified sulfur polymer having a viscosity of 600 cps or less after five days storage at 130 ° C. temperature.
또한, 본 발명은 상기 개질 유황 폴리머 100 중량부; 및 골재 200 내지 600 중량부를 포함하는 콘크리트 조성물을 제공한다.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.
나아가, 본 발명의 일 측에 따른 콘크리트 조성물은, 하수관, 맨홀, 벽돌, 타일, 철도 침목, 말뚝(pile) 및 인공어초 중 적어도 어느 하나를 제조하는 데에 사용될 수 있다.Furthermore, the concrete composition according to one side of the present invention can be used to manufacture at least one of sewer pipes, manholes, bricks, tiles, railway sleepers, piles and artificial reefs.
본 발명에 따르면, 장기 저장성 및 작업성이 우수하면서도 휨강도 및 압축강도 등의 기계적 강도가 우수한 개질 유황 폴리머를 확보할 수 있다.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.
도 1은 본 발명의 일 실시예에 따른 개질 유황 폴리머의 보관일자에 따른 점도 변화를 도시한 그래프이다.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.
본 발명의 일 실시예에 따른 개질 유황 폴리머는, 100 중량부의 유황을, 1 내지 10 중량부의 디싸이클로펜타디엔(DCPD); 및 0.05 내지 3 중량부의,
Figure PCTKR2011002314-appb-I000008
기를 포함하는 탄소수 8 내지 75의 아릴 화합물 또는 하기 화학식 1로 표시되는 화합물과 중합하여 합성될 수 있다.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 PCTKR2011002314-appb-I000008
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).
Figure PCTKR2011002314-appb-I000009
Figure PCTKR2011002314-appb-I000009
상기 식에서, R1 및 R2 는 동일하거나 상이하고, 각각 독립적으로 탄소수 1 내지 18의 알킬기이다. 보다 바람직하게는, 상기 R1 및 R2는 탄소수 4 내지 18의 알킬기이며, 가장 바람직하게는, 터셔리 부틸(tert-butyl)기 일 수 있다In 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 PCTKR2011002314-appb-I000010
의 구체적인 예로는 트리스(3,5-디-tert-부틸-4-하이드록시페닐)기를 들 수 있다.
Figure PCTKR2011002314-appb-I000010
Specific examples of the tris (3,5-di-tert-butyl-4-hydroxyphenyl) group may be mentioned.
또한, 상기 식에서, R3은
Figure PCTKR2011002314-appb-I000011
이고, x는 0 내지 4의 정수이며, 보다 바람직하게는, x는 1 내지 2의 정수이다.In the above formula, R 3 is
Figure PCTKR2011002314-appb-I000011
X is an integer of 0-4, More preferably, x is an integer of 1-2.
R4 은 탄소수 1 내지 20의 알킬기이고, 바람직하게는, 탄소수 12 내지 20의 알킬기이며, 가장 바람직하게는 탄소수 12 내지 18의 알킬기이다.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.
상기 유황은 최초 분말 상의 유황으로서, 상기 유황으로서는 S8이 사용될 수 있다. 상기 유황은 반응 시 용융되어 용융 유황(molten sulfur)으로서 유황 폴리머의 합성 반응에 참여하게 된다. 상기 DCPD의 함량이 1 중량부 미만이면 유황 폴리머의 폴리머화가 약화되어 유황 폴리머의 기계적 강도가 저하될 수 있으며 유황 폴리머의 함량이 10 중량부를 초과하면 유황 폴리머의 점성이 높아져, 보관 안정성 및 작업성이 급격히 저하될 수 있다. 특히, 상기 DCPD의 유황 폴리머 내 백분율 함량이 2.0 내지 3.5 중량%인 경우가 유황 폴리머의 강도 및 저장성 면에서 매우 유리하다.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.
상기 아릴 화합물은 구체적으로는 하기 화학식 2 내지 6의 화합물이다.Specifically, the aryl compound is a compound represented by the following Chemical Formulas 2 to 6.
Figure PCTKR2011002314-appb-I000012
Figure PCTKR2011002314-appb-I000012
Figure PCTKR2011002314-appb-I000013
Figure PCTKR2011002314-appb-I000013
Figure PCTKR2011002314-appb-I000014
Figure PCTKR2011002314-appb-I000014
상기 화학식 1의 화합물은 구체적으로 하기 화학식 7 내지 9의 화합물이다.The compound of Formula 1 is specifically a compound of Formulas 7 to 9.
Figure PCTKR2011002314-appb-I000015
Figure PCTKR2011002314-appb-I000015
상기 합성은 130℃ 내지 150℃의 온도 하에서, 1 내지 3시간 동안 이루어질 수 있다. The synthesis may be performed for 1 to 3 hours at a temperature of 130 ℃ to 150 ℃.
본 발명의 일 실시예에 따른 개질 유황 폴리머는 130℃ 온도에서 5일 저장 후 점성이 600 cp이하이다. 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.
상기 개질 유황 폴리머를 합성할 때 탄소수 8 내지 75의 아릴 화합물 보다 구체적으로는 페놀계 화합물 또는 화학식1로 표시되는 티오에스테르계 화합물을 유황 및 디싸이클로펜타디엔과 함께 중합함으로써 유황과 개질제 간의 라디컬 반응을 제어하여 점도를 저점도로 유지할 수 있게 된다.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.
상기 개질 유황 폴리머는 골재 및 기타 충진제 등과 혼합되어 콘크리트 조성물로 사용될 수 있다. 본 발명의 일 실시예에 따른 콘크리트 조성물은 상기 개질 유황 폴리머 100 중량부; 및 골재 200 내지 600 중량부를 포함한다.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.
또한, 상기 콘크리트 조성물은 콘크리트의 강도를 보다 개선하기 위하여 충진제를 더 포함할 수 있다. 상기 충진제로서는 유리 섬유 등이 사용될 수 있다.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.
나아가, 상기 콘크리트 조성물은 하수관, 맨홀, 벽돌, 타일, 철도 침목, 말뚝(pile) 또는 인공어초를 제조하는 데에 사용될 수 있다. 이때, 상기 콘크리트 조성물은 완성된 제품으로 또는 현장에서 직접 타설되어 사용될 수 있다. 즉, 상기 콘크리트 조성물은, 장기 저장성 및 작업성이 우수하면서도 휨강도 및 압축강도 등의 기계적 강도가 우수한 개질 유황 폴리머를 포함하기 때문에, 상기와 같은 용도로 사용될 수 있다.Furthermore, the concrete composition can be used to produce sewer pipes, manholes, bricks, tiles, railway sleepers, piles or artificial reefs. At this time, the concrete composition may be used as a finished product or directly poured in the field. That is, since the concrete composition includes a modified sulfur polymer having excellent long-term storage properties and workability but excellent mechanical strength such as bending strength and compressive strength, the concrete composition may be used for such a purpose.
이하 실시예들을 통하여 전술한 개질 유황 폴리머 및 콘크리트 조성물을 더욱 상세하게 설명하도록 한다. 그러나 하기 실시예들에 의하여 본 발명의 기술 사상이 한정되는 것은 아니다.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.
실시예Example
실시예 1Example 1
스테인레스 스틸 재질의 5L 반응기에 유황 3kg을 첨가하고 140℃의 오븐에서 3시간 동안 녹였다. 유황 폴리머(SPC)를 합성하기 위하여 상기 반응기에 유황 100 중량부에 대하여 DCPD 4 중량부를 반응기에 적가하고 2시간 동안 교반한 후, 2,6-디-t-부틸-p-크레졸(2,6-di-t-butyl-p-cresol) 1 중량부를 반응기에 적가하고 30분 동안 교반 하였다. 상기 반응은 145℃의 온도 하에서 진행되었다. 반응 완료 후, 5일 동안 130℃ 온도 하에서 교반시키며 점도를 측정하였다.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.
실시예 2Example 2
2,6-디-t-부틸-p-크레졸 대신 옥타데실 3,5-디-t-부틸-4-하이드록시 하이드로신나메이트(Octadecyl 3,5-di-t-butyl-4-hydroxy Hydrocinnamate) 1 중량부를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 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.
실시예 3Example 3
2,6-디-t-부틸-p-크레졸 대신 테트라키스[메틸렌-3-(3,5-디-tert-부틸-4-하이드록시페닐)프로피오네이트]메탄(Tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane) 1 중량부를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다.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.
실시예 4Example 4
2,6-디-t-부틸-p-크레졸 대신 디스테아릴 티오디프로피오네이트(distearyl thiodipropionate) 1 중량부를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다.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.
실시예 5Example 5
2,6-디-t-부틸-p-크레졸 대신 트리스(3,5-디-tert-부틸-4-하이드록시벤질)이소시아누레이트(Tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate) 1 중량부를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다.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.
실시예 6Example 6
2,6-디-t-부틸-p-크레졸 대신 1,3,5-트리메틸 2,4,6-트리스(3,5-디-tert-부틸-4-하이드록시벤질)벤젠(1,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene) 1 중량부를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다.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.
실시예 7Example 7
2,6-디-t-부틸-p-크레졸 대신 디미리스트릴 티오디프로피오네이트(Di Myristryl Thiodipropionate) 1 중량부를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다.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.
실시예 8Example 8
2,6-디-t-부틸-p-크레졸 대신 디라우릴 티오디프로피오네이트(Dilauryl thiodipropionate) 1 중량부를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다.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.
비교예Comparative example
스테인레스 스틸 재질의 5L 반응기에 유황 3kg을 첨가하고 140℃의 오븐에서 3시간 동안 녹였다. 유황 폴리머(SPC)를 합성하기 위하여 상기 반응기에 유황 100중량부에 대하여 DCPD 4 중량부를 반응기에 적가하고 2시간 동안 교반 하였다. 상기 반응은 145℃의 온도 하에서 진행되었다. 반응 완료 후, 5일 동안 130℃ 온도 하에서 교반시키며 점도를 측정하였다.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.
점도 측정 결과Viscosity Measurement Results
상기 비교예 및 실시예 1 내지 4에 있어서, 유황 폴리머 합성 후 0 내지 5일 동안 130℃ 온도하에서 교반시키며 점도를 측정한 결과를 하기 표 1에 도시하였다. 도 1은 비교예 및 실시예 1 내지 4에 따른 유황 폴리머의 보관일자에 따른 점도 변화를 도시한 그래프이다.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.
Figure PCTKR2011002314-appb-I000016
Figure PCTKR2011002314-appb-I000016
상기 표 1 및 도 1을 참조하면, 130℃ 온도하에서 5일 보관 후에 본 발명의 실시예에 따른 개질 유황 폴리머의 점도는 600 cp이하인 것을 확인할 수 있다. 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 (6)

100 중량부의 유황을,100 parts by weight of sulfur,
1 내지 10 중량부의 디싸이클로펜타디엔(DCPD); 및 1 to 10 parts by weight of dicyclopentadiene (DCPD); And
0.05 내지 3 중량부의,
Figure PCTKR2011002314-appb-I000017
기를 포함하는 탄소수 8 내지 75의 아릴 화합물 또는 하기 화학식 1로 표시되는 화합물과 중합하여 합성된 개질 유황 폴리머. 0.05 to 3 parts by weight,
Figure PCTKR2011002314-appb-I000017
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).
(상기 식에서, R1 및 R2 는 동일하거나 상이하고, 각각 독립적으로 탄소수 1 내지 18의 알킬기이다.)(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 PCTKR2011002314-appb-I000018
Figure PCTKR2011002314-appb-I000018
(상기 식에서, R3은
Figure PCTKR2011002314-appb-I000019
이고, x는 0 내지 4의 정수이며,Wherein R 3 is
Figure PCTKR2011002314-appb-I000019
X is an integer from 0 to 4,
R4 은 탄소수 1 내지 20의 알킬기이다.)R 4 is an alkyl group having 1 to 20 carbon atoms.)
제1항에 있어서,The method of claim 1,
상기 아릴 화합물은 하기 화학식 2 내지 6으로 표시되는 화합물인, 개질 유황 폴리머. The aryl compound is a compound represented by the formula 2 to 6, modified sulfur polymer.
Figure PCTKR2011002314-appb-I000020
Figure PCTKR2011002314-appb-I000021
Figure PCTKR2011002314-appb-I000020
Figure PCTKR2011002314-appb-I000021
Figure PCTKR2011002314-appb-I000022
Figure PCTKR2011002314-appb-I000022
제1항에 있어서,The method of claim 1,
상기 화학식 1의 화합물은 하기 화학식 7 내지 9로 표시되는 화합물인, 개질 유황 폴리머.The compound of Formula 1 is a modified sulfur polymer, which is a compound represented by the formula (7-9).
Figure PCTKR2011002314-appb-I000023
Figure PCTKR2011002314-appb-I000023
제1항에 있어서,The method of claim 1,
130 ℃ 온도에서 5일 저장 후 점성이 600 cp이하인, 개질 유황 폴리머.Modified sulfur polymer having a viscosity of 600 cps or less after 5 days storage at 130 ° C.
제1항 내지 제4항 중 어느 한 항 기재의 개질 유황 폴리머 100 중량부; 및100 parts by weight of the modified sulfur polymer according to any one of claims 1 to 4; And
골재 200 내지 600 중량부를 포함하는 콘크리트 조성물.Concrete composition comprising 200 to 600 parts by weight of aggregate.
제5항에 있어서,The method of claim 5,
상기 콘크리트 조성물은, 하수관, 맨홀, 벽돌, 타일, 철도 침목, 말뚝(pile) 및 인공어초 중 적어도 어느 하나를 제조하는 데에 사용되는 콘크리트 조성물.The concrete composition is a concrete composition used to manufacture at least one of sewer pipes, manholes, bricks, tiles, railway sleepers, piles and artificial reefs.
PCT/KR2011/002314 2010-11-17 2011-04-04 Reformulated sulfuric polymer and concrete composition containing same WO2012067314A1 (en)

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