KR20230033045A - An additive for improving the stability of hydrogen-silicon bond - Google Patents
An additive for improving the stability of hydrogen-silicon bond Download PDFInfo
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- 239000000654 additive Substances 0.000 title claims abstract description 31
- 230000000996 additive effect Effects 0.000 title claims abstract description 25
- 239000010703 silicon Substances 0.000 title claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 22
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 1
- 125000002843 carboxylic acid group Chemical group 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 150000003377 silicon compounds Chemical class 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000006884 silylation reaction Methods 0.000 description 2
- 229910007991 Si-N Inorganic materials 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- -1 Surfate Chemical compound 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical group 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/378—Thiols containing heterocyclic rings
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
Abstract
Description
본 발명은 이미다졸 계열의 수소-규소 결합의 안정성 개선을 위한 첨가제에 관한 것으로보다 구체적으로 산 조건 하에서 실리콘 화합물의 분자 내 수소-규소 결합의 안정성을 증가시킬 수 있는 첨가제에 관한 것이다.The present invention relates to an additive for improving the stability of an imidazole-based hydrogen-silicon bond, and more particularly, to an additive capable of increasing the stability of an intramolecular hydrogen-silicon bond of a silicon compound under an acidic condition.
수소-규소 결합을 갖는 실리콘 분자는 수소-규소화 반응을 통한 경화가 가능하여 다양한 구조의 유기 실리콘 화합물을 제조할 수 있는 가교제로서 활발히 연구 되고 있다. 수소-규소화 반응은 열에 의해 실리콘 경화물을 제조하는데 있어서 매우 간단하고 유용한 방법중의 하나이며, 적은 양의 촉매 하에 부산물이 적은 경화물을 제조할 수 있는 장점을 갖고 있다. 상기 반응은 백금과 같은 금속 촉매를 이용하여, 탄소-탄소 이중결합 (C=C)을 갖는 유기 화합물과 규소-수소 (수소-규소) 결합을 갖는 유기 화합물을 중합 반응 시켜 규소-탄소 (Si-C) 결합을 형성시키는 것이다.Silicon molecules having a hydrogen-silicon bond are actively studied as a cross-linking agent that can be cured through a hydrogen-siliconization reaction to prepare organic silicon compounds with various structures. The hydrogen-silylation reaction is one of the very simple and useful methods for preparing a cured silicone product by heat, and has the advantage of being able to produce a cured product with a small amount of by-products under a small amount of catalyst. In the above reaction, a silicon-carbon (Si- C) to form bonds.
이러한 반응을 통하여 원하는 작용기를 갖는 다양한 수소-규소 단량체를 합성할 수 있으며,가교결합을 통한 분자들의 네트워크 구조를 형성시킨 경화물을 제조하여 여러 소자에 응용할 수 있다.대표적인 중합 반응 기구인 라디칼 중합의 경우 개시제가 상대적으로 많이 필요하며, 반응에 따른 부산물이 발생하는 단점이 있다. 따라서 부산물이 발생하지 않고, 소량의 촉매 사용만으로도 충분한 경화를 진행시킬 수 있고, 추가적인 열처리 공정이 필요하지 않은 수소-규소화 반응기구 및 유기 수소-규소 화합물에 대한 연구가 활발히 진행되고 있다.Through this reaction, various hydrogen-silicon monomers having desired functional groups can be synthesized, and a cured product in which a network structure of molecules is formed through cross-linking can be prepared and applied to various devices. In this case, a relatively large amount of initiator is required, and there is a disadvantage in that by-products are generated according to the reaction. Therefore, studies on a hydrogen-silylation reaction mechanism and an organic hydrogen-silicon compound, which do not generate by-products, allow sufficient curing to proceed with only a small amount of catalyst, and do not require an additional heat treatment process, are being actively conducted.
한편, 산 조건 하에서 실리콘 화합물에 Si-H결합이 존재하는 경우, Si-H결합의 안정성은 매우 낮다. 그 이유는 산이 촉매 작용을 하여 Si-H결합을 깨기 때문이다. 당연히 pH가 낮아지면 낮아질수록 Si-H의 안정성은 더더욱 낮아지며 pH 가 0에 가까울수록 안정성이 0에 가까워진다. 또한 pH가 매우 높아진다면 base조건에 의하여 규소가 공격 당할 가능성이 커져 Si-H bonding이 깨질 위험 역시 존재한다. 이에 산 조건 하에서 실리콘 polymer를 합성하는 경우, 실리콘 화합물 내 Si-H 결합이 너무 쉽게 깨져 실리콘 화합물의 수율이 현저히 낮아지는 문제가 발생하였으며, 또한 side-product의 생성으로 인해 타겟 화합물의 정제가 매우 까다로워지는 단점이 발생하였다.(추가로 산 조건에서 시간이 지나면 Si-H의 존재가 사라지게 됨으로 안정성에서도 매우 큰 문제가 있다.)On the other hand, when a Si-H bond exists in a silicon compound under acid conditions, the stability of the Si-H bond is very low. The reason is that the acid catalyzes breaking the Si-H bond. Naturally, the lower the pH, the lower the stability of Si-H, and the closer the pH is to 0, the closer the stability is to 0. In addition, if the pH is very high, the possibility of silicon being attacked by the base condition increases, and there is also a risk of breaking the Si-H bonding. Therefore, when synthesizing a silicone polymer under acidic conditions, the Si-H bond in the silicone compound is too easily broken, resulting in a significantly lower yield of the silicone compound, and also, due to the generation of side-products, it is very difficult to purify the target compound. (In addition, there is a very big problem in stability as the existence of Si-H disappears over time in acid conditions.)
따라서, 산 조건 하에서 실리콘 화합물의 Si-H 결합의 안정성 개선을 위한 첨가제가 필요한 실정이다.Therefore, there is a need for an additive for improving the stability of the Si-H bond of a silicon compound under acid conditions.
본 발명은 상술한 문제를 해결하기 위하여, 수소-규소 결합을 갖는 실리콘 폴리머 및 monomer의 합성 시, 상기 수소-규소 결합의 안정성을 현저히 개선하기 위한 첨가제를 제공하는 것을 목적으로 한다.In order to solve the above problems, an object of the present invention is to provide an additive for significantly improving the stability of the hydrogen-silicon bond when synthesizing a silicon polymer and monomer having a hydrogen-silicon bond.
본 발명은 하기 화학식 1로 내지 화학식 4로 표시되는 화합물 중 1종 이상을 포함하는 첨가제를 제공한다:The present invention provides an additive comprising at least one of the compounds represented by Formula 1 to Formula 4:
[화학식 1][Formula 1]
상기 화학식 1에서, R1및 R2는X 및 Y는, 각각 독립적으로,In Formula 1, R 1 and R 2 are X and Y, each independently,
트라이플루오르메틸(CF3), 이산화질소(NO2), 에스테르(Ester), 아미드(Amide),황산염(Surfate), 인산염(Phosphate), 하이드록실(Hydroxyl), 또는 아민(Amine)이다.Trifluoromethyl (CF3), Nitrogen Dioxide (NO2), Ester, Amide, Surfate, Phosphate, Hydroxyl, or Amine.
본 발명은 산 조건에서의 결합유지가 어려운윤 수소-규소 결합(Si-H)을 효과적으로 보호 가능한 첨가제를 제공하는 것을 목적으로 한다.An object of the present invention is to provide an additive capable of effectively protecting the hydrogen-silicon bond (Si-H), which is difficult to maintain in acid conditions.
또한,본 발명은 상기 첨가제를 제공함으로써 산 조건하에서 타겟폴리머 or Monomer를 현저히 개선된 수율로 합성 가능하며,산 조건 하에서 합성의 기초가 되는 수소-규소 결합을 갖는 단량체를 효과적으로 보호 가능하며,합성된 폴리머 or monomer 구조 또한 보호 가능한 효과를 제공할 수 있다.In addition, the present invention can synthesize the target polymer or monomer with significantly improved yield under acidic conditions by providing the additive, and can effectively protect monomers having hydrogen-silicon bonds, which are the basis of synthesis under acidic conditions, and synthesized Polymer or monomer structures may also provide possible protective effects.
본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는 바, 특정 실시예들을 도면에 예시하고 본문에 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 개시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.Since the present invention may have various changes and various forms, specific embodiments are illustrated in the drawings and described in detail in the text. However, it should be understood that this is not intended to limit the present invention to the specific disclosed form, and includes all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.
본 출원에서, "포함하다" 또는 "가지다" 등의 용어는 명세서 상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부분품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다. 또한, 층, 막, 영역, 판 등의 부분이 다른 부분 "상에" 있다고 할 경우, 이는 다른 부분 "바로 위에" 있는 경우뿐만 아니라 그 중간에 또 다른 부분이 있는 경우도 포함한다. 반대로 층, 막, 영역, 판 등의 부분이 다른 부분 "하에" 있다고 할 경우, 이는 다른 부분 "바로 아래에" 있는 경우뿐만 아니라 그 중간에 또 다른 부분이 있는 경우도 포함한다. 또한, 본 출원에서 “상에” 배치된다고 하는 것은 상부뿐 아니라 하부에 배치되는 경우도 포함하는 것일 수 있다.In this application, the terms "include" or "have" are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that it does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof. In addition, when a part such as a layer, film, region, plate, etc. is said to be "on" another part, this includes not only the case where it is "directly on" the other part, but also the case where another part is present in the middle. Conversely, when a part such as a layer, film, region, plate, etc. is said to be "under" another part, this includes not only the case where it is "directly under" the other part, but also the case where there is another part in between. In addition, in the present application, being disposed “on” may include the case of being disposed not only on the upper part but also on the lower part.
본 발명은 하기 화학식 1 내지 화학식 4로 표시되는 화합물을 중 1종 이상을 포함하는 첨가제를 제공한다:The present invention provides an additive comprising at least one of the compounds represented by Formulas 1 to 4 below:
[화학식 1][Formula 1]
상기 화학식 1에서, X는, 각각 독립적으로, 수소(Hydrogen), C1-C10으로 이루어진 Alkyl기나 Cycloalkyl, 트라이플루오르메틸(CF3), 이산화질소(NO2), 에스테르(Ester), 아미드(Amide),황산염(Surfate), 인산염(Phosphate), 하이드록실(Hydroxyl), 또는 아민(Amine) 이다.In Formula 1, X is each independently hydrogen, an alkyl group consisting of C1-C10, a cycloalkyl, trifluoromethyl (CF3), nitrogen dioxide (NO2), an ester, an amide, a sulfate ( Surfate, Phosphate, Hydroxyl, or Amine.
예를 들어,상기 화학식 1은 하기 화학식 2내지 화학식 6 중 어느 하나5의 구조를 갖는 것이 바람직할 수 있다:For example, Formula 1 may preferably have a structure of any one of Formulas 2 to 6 below:
[화학식 2][Formula 2]
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
[화학식 6][Formula 6]
본 발명의 상기 첨가제는 산 조건 하 실리콘 화합물 및/또는 폴리머의 분자 내 수소-규소 결합의 안정성 증가용인것을 특징으로 한다.The additive of the present invention is characterized in that it is for increasing the stability of hydrogen-silicon bonds in molecules of silicone compounds and/or polymers under acid conditions.
[반응 메커니즘반응식 1][Reaction Mechanism Reaction Formula 1]
구체적인 예에서, 실리콘 화합물의 Si-H 결합에서 Delta- 인 H 가 본 발명에 따른 첨가제 쪽(피롤 쪽)에서 Delta+ 인 H 와 결합하여 전자 밀도 분포(Electron Density distribution)가 좋아질 수 있다.특히,본 발명에 따른 첨가제의 H 는 산성에 대한 양이온이 아닌 Delta+ 의 양이온이기 때문에 반응은 안하는 대신 Si-H 결합의 Delta- 의 전자밀도에 간섭하여 Si-H 의 염기도(Basicity)를 낮출 수 있다. Basicity를 낮출 경우 H+와의 반응 능력이 현저히 떨어진다. In a specific example, H of Delta- in the Si-H bond of the silicon compound is combined with H of Delta+ on the additive side (pyrrole side) according to the present invention, so that the electron density distribution can be improved. In particular, the present invention Since the H of the additive according to the invention is a cation of Delta+ rather than a cation for acidity, it does not react, but interferes with the electron density of Delta- of the Si-H bond to lower the basicity of Si-H. When the basicity is lowered, the ability to react with H+ is significantly reduced.
하나의 예에서,상기 산 조건이라 함은 pH 7 미만인 것을 의미할 수 있다.상기 산 조건은, pH를 7 미만으로 형성시키는 산이라면 제한 없이 포함될 수 있으나,보다 구체적으로,아세트산,트리플루오르아세트 산,황산,인산,질산,아질산,포름산,염산, 붕산 및 불산 또는 Carboxylic Acid 작용기를 가진 산에서 선택되는 1종 이상의 산을 포함하는 것이 바람직할 수 있다.In one example, the acid condition may mean a pH less than 7. The acid condition may include any acid that forms a pH less than 7 without limitation, but more specifically, acetic acid, trifluoroacetic acid , It may be preferable to include at least one acid selected from sulfuric acid, phosphoric acid, nitric acid, nitrous acid, formic acid, hydrochloric acid, boric acid, hydrofluoric acid, or acid having a Carboxylic Acid functional group.
본 발명의 상기 첨가제는 산 조건하에서 실리콘 화합물의 분자내 규소-질소 결합을 50% 이상 유지하는 것을 특징으로 한다.The additive of the present invention is characterized by maintaining 50% or more of the silicon-nitrogen bond in the molecule of the silicon compound under acid conditions.
실험예:산 조건 하(pH < 7) 에서 실리콘 화합물의 분자내 질소-규소(Nitrogen-Silicon) 결합의 안정성 유지 가능성 판단Experimental Example: Determining the possibility of maintaining the stability of nitrogen-silicon bonds in molecules of silicon compounds under acidic conditions (pH < 7)
실시예1 내지 5 Examples 1 to 5
산 조건 하 수소-규소에 대한 안정성을 부여하는 첨가제 및실리콘 화합물을 첨가하여 혼합 후 상온(Room temp.)에서 12 시간 방치하여 시간 별로 화합물 내의 수소-규소 결합 분해 여부를 확인 하였다. 각각의 산 조건,실리콘 화합물 및 첨가제는 아래의 표 1에 정리하였다.Additives and silicon compounds that give stability to hydrogen-silicon under acid conditions were added and mixed, and then left at room temperature for 12 hours to determine whether hydrogen-silicon bonds in the compound were decomposed over time. Each acid condition, silicone compound and additives are summarized in Table 1 below.
특정 함량에 대한 내용: 산 + 실리콘 화합물 (최소 100ppm)기준으로 첨가제는 최소 50 ppm에서 최대 500000ppm까지 첨가가 가능하다. 50 ppm 밑으로 내려 갈 경우 첨가제의 효능이 미미하게 되고 500000 ppm 넘어서는 500000ppm의 효능 대비 크게 영향이 없다. Information on specific content: Based on acid + silicone compound (minimum 100ppm), additives can be added from a minimum of 50 ppm to a maximum of 500000ppm. If it goes below 50 ppm, the effect of the additive becomes insignificant, and there is no significant effect compared to the efficacy of 500000 ppm over 500000 ppm.
[화학식 7][Formula 7]
[화학식 8][Formula 8]
[화학식 9][Formula 9]
[화학식 10][Formula 10]
[화학식 11][Formula 11]
비교예 1Comparative Example 1
산 조건 하 질소-규소에 대한 안정성을 부여하는 첨가제 없이, 질산 10%의 용액(Nitric acid 10% by volume)에, 하기 화학식 7 구조의 화합물 10g을 첨가하여 혼합 후 상온(Room temp.)에서 12 시간 방치하여 시간 별로 화합물 내의 수소-규소 결합 분해 여부를 확인 하였다. 10 g of a compound having the following formula (7) was added to a solution of 10% nitric acid (Nitric acid 10% by volume) without an additive providing stability to nitrogen-silicon under acid conditions, and mixed, followed by mixing at room temperature (Room temp.) for 12 By leaving it for a while, it was confirmed whether or not the hydrogen-silicon bond was decomposed in the compound on an hourly basis.
실험 결과Experiment result
산 조건 하(pH < 7) 에서 실리콘 화합물의 분자내수소-규소(Hydrogen-Silicon) 결합의 안정성 유지 가능성 판단하였다.보다 구체적으로,각각의 실시예 및 비교예의 혼합용액을 상온(Room temp.)에서 12 시간 방치하여,시간 별로 화합물 내의 질소-규소 결합 분해 여부를 확인하였다.그리고,그 결과는 표 2에 나타내었다.The possibility of maintaining the stability of the hydrogen-silicon bond in the molecule of the silicone compound under acidic conditions (pH < 7) was determined. More specifically, the mixed solutions of each Example and Comparative Example were tested at room temperature (Room temp.) was left for 12 hours, and whether nitrogen-silicon bonds were decomposed in the compound was checked for each hour. And, the results are shown in Table 2.
표 2는 시간별GC 로 Si-N분해여부를 보여주는 결과이다.Table 2 shows the results of Si-N decomposition by GC by time.
상기 표 2의 내용으로부터,본 발명의 첨가제를 포함할 경우,산 조건 하에서 실리콘 화합물의 분자내Si-H 결합이 분해되는 것을 방지하는 효과가 현저히 우수함을 확인하였다.From the contents of Table 2, it was confirmed that the inclusion of the additive of the present invention has a remarkably excellent effect of preventing the Si-H bond in the molecule of the silicon compound from being decomposed under acidic conditions.
Claims (10)
[화학식 1]
상기 화학식 1에서, X는, 각각 독립적으로, 수소(Hydrogen), C1-C10으로 이루워진 Alkyl기나 Cycloalkyl기, 트라이플루오르메틸(CF3), 이산화질소(NO2), 에스테르(Ester), 아미드(Amide),황산염(Surfate), 인산염(Phosphate), 하이드록실(Hydroxyl), 또는 아민(Amine) 이다.Additives containing at least one of the compounds represented by Formulas 1 to 4 below:
[Formula 1]
In Formula 1, X is each independently hydrogen, an alkyl group or cycloalkyl group consisting of C1-C10, trifluoromethyl (CF3), nitrogen dioxide (NO2), ester, amide, They are sulfate, phosphate, hydroxyl, or amine.
상기 첨가제는,산 조건 하에서 실리콘 화합물의 분자 내 수소-규소 결합의 안정성 증가용인 것인,첨가제.According to claim 1,
The additive is for increasing the stability of the hydrogen-silicon bond in the molecule of the silicone compound under acid conditions, Additives.
상기 화학식 1은 하기 화학식 2의 구조를 갖는 것인,첨가제:
[화학식 2]
Formula 1 has a structure of Formula 2 below, the additive:
[Formula 2]
상기 화학식 1은 하기 화학식 3의 구조를 갖는 것인,첨가제:
[화학식 3]
Formula 1 has a structure of Formula 3 below, the additive:
[Formula 3]
상기 화학식 1은 하기 화학식 4의 구조를 갖는 것인,첨가제:
[화학식 4]
Formula 1 has a structure of Formula 4 below, the additive:
[Formula 4]
상기 화학식 1은 하기 화학식 5의 구조를 갖는 것인,첨가제:
[화학식 5]
Formula 1 has a structure of Formula 5 below, the additive:
[Formula 5]
상기 화학식 1은 하기 화학식 6의 구조를 갖는 것인,첨가제:
[화학식 6]
Formula 1 has a structure of Formula 6 below, the additive:
[Formula 6]
상기 산 조건은 pH 7 미만인 것인,첨가제.According to claim 2,
The acid condition is that the pH is less than 7, additives.
상기 산 조건은 아세트산, 트리플루오르아세트 산, 황산, 인산, 질산, 아질산, 포름산, 염산, 붕산 및 불산그리고 carboxylic acid 그룹을 가진 산에서 선택되는 1종 이상의 산을 포함하는 것인, 첨가제.According to claim 2,
The acid condition comprises at least one acid selected from acetic acid, trifluoroacetic acid, sulfuric acid, phosphoric acid, nitric acid, nitrous acid, formic acid, hydrochloric acid, boric acid, hydrofluoric acid, and acids having a carboxylic acid group.
상기 첨가제는 산 조건하에서 실리콘 화합물의 분자내 수소-질소 결합을 50% 이상 유지하는 것을 특징으로 하는,첨가제.
According to claim 1,
The additive is characterized in that it maintains 50% or more of hydrogen-nitrogen bonds in the molecule of the silicone compound under acid conditions.
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