KR102396554B1 - Radical based mechanochromic monomers and self-reporting polymers - Google Patents
Radical based mechanochromic monomers and self-reporting polymers Download PDFInfo
- Publication number
- KR102396554B1 KR102396554B1 KR1020200032976A KR20200032976A KR102396554B1 KR 102396554 B1 KR102396554 B1 KR 102396554B1 KR 1020200032976 A KR1020200032976 A KR 1020200032976A KR 20200032976 A KR20200032976 A KR 20200032976A KR 102396554 B1 KR102396554 B1 KR 102396554B1
- Authority
- KR
- South Korea
- Prior art keywords
- mechanochromic
- monomer
- polymer
- range
- formula
- Prior art date
Links
- 239000000178 monomer Substances 0.000 title claims abstract description 98
- 229920000642 polymer Polymers 0.000 title claims description 67
- -1 vinyl acryl group Chemical group 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 30
- 238000006116 polymerization reaction Methods 0.000 claims description 24
- 239000000853 adhesive Substances 0.000 claims description 18
- 230000001070 adhesive effect Effects 0.000 claims description 18
- 125000000524 functional group Chemical group 0.000 claims description 10
- 239000003973 paint Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 3
- 238000003825 pressing Methods 0.000 abstract description 18
- 238000005452 bending Methods 0.000 abstract description 7
- 239000002861 polymer material Substances 0.000 abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 230000000638 stimulation Effects 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- YBFPOZNRCXKQHW-UHFFFAOYSA-N 2,3-bis[4-(6-hydroxyhexoxy)phenyl]-2,3-bis(4-methoxyphenyl)butanedinitrile Chemical compound COC1=CC=C(C(C(C(C=C2)=CC=C2OC)(C(C=C2)=CC=C2OCCCCCCO)C#N)(C(C=C2)=CC=C2OCCCCCCO)C#N)C=C1 YBFPOZNRCXKQHW-UHFFFAOYSA-N 0.000 description 2
- LEGOFBYSYBUOSV-UHFFFAOYSA-N 2-(4-hydroxyphenyl)-2-(4-methoxyphenyl)acetonitrile Chemical compound OC1=CC=C(C=C1)C(C#N)C1=CC=C(C=C1)OC LEGOFBYSYBUOSV-UHFFFAOYSA-N 0.000 description 2
- WLDAAMXETLHTER-UHFFFAOYSA-N 2-hydroxy-2-(4-methoxyphenyl)acetonitrile Chemical compound COC1=CC=C(C(O)C#N)C=C1 WLDAAMXETLHTER-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- PZYHLENTJZMOQC-UHFFFAOYSA-N 1-bromohexan-1-ol Chemical compound CCCCCC(O)Br PZYHLENTJZMOQC-UHFFFAOYSA-N 0.000 description 1
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002520 smart material Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/19—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and carboxyl groups, other than cyano groups, bound to the same saturated acyclic carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/11—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same saturated acyclic carbon skeleton
- C07C255/14—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same saturated acyclic carbon skeleton containing cyano groups and esterified hydroxy groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Biochemistry (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Abstract
본 발명은 눌림, 휨, 찢김, 인장등 기계적 자극에 의해 색이 변화하는 라디칼계 메카노크로믹 단량체에 관한 것으로, 본 발명에 의한 단량체로부터 제조된 고분자를 활용하여 물리적 자극 감응형 센서, 자가보고 스마트 고분자 소재 등으로 유용하게 사용될 수 있다.The present invention relates to a radical-based mechanochromic monomer that changes color by mechanical stimuli such as pressing, bending, tearing, and tension. It can be usefully used as a smart polymer material and the like.
Description
본 발명은 눌림, 휨, 찢김, 인장등 기계적 자극에 의해 색이 변화하는 라디칼계 메카노크로믹 단량체 및 이를 포함하는 스마트 고분자에 관한 것이다.The present invention relates to a radical-based mechanochromic monomer that changes color by mechanical stimuli such as pressing, bending, tearing, and tension, and a smart polymer including the same.
메카노크로믹 화합물은 기계적인 자극에 의해 색이 변화하는 물질로 눌림, 휨, 찢김, 당겨짐 등의 다양한 물리적 자극에 의해 화학결합이 끊어지거나, 분자들이 뭉쳐지거나 혹은 뭉쳐진 분자들이 풀어지거나, 결정상의 층상구조 등이 변하면서 색의 변화가 나타나는 화합물이다.A mechanochromic compound is a material that changes color by mechanical stimulation. Chemical bonds are broken by various physical stimuli such as pressing, bending, tearing, and pulling, or molecules are agglomerated or the aggregated molecules are released, or crystal phase It is a compound that changes color as the layer structure changes.
기계적인 자극에 의해 색이 변화하는 특성은 센서로 응용이 가능한데, 고분자 소재에 적용시 물리적 자극에 의해 자가보고(self-reporting) 특성을 갖는 스마트 소재를 기대할 수 있다.The property of changing color due to mechanical stimulation can be applied as a sensor, and when applied to polymer materials, smart materials with self-reporting properties can be expected by physical stimulation.
종래 기술에 대해 언급하면,Referring to the prior art,
특허문헌 1(JP 2016-210991)과 비특허문헌 1(Chem. Commun., 2017, 53, 11885) 등에는 하기 스킴 1 내지 3으로 제조되는 TASN(Tetraarylsuccinonitrile)-centered polystyrene을 제조하고, 이렇게 제조된 TASN(Tetraarylsuccinonitrile)-centered polystyrene, PS-TASN-PS이 grinding 등의 물리적 자극에 의해 색과 형광이 변화할 수 있음을 개시하고 있다(비특허문헌 1의 Fig.3a 등 참조).In Patent Document 1 (JP 2016-210991) and Non-Patent Document 1 (Chem. Commun., 2017, 53, 11885), TASN (Tetraarylsuccinonitrile)-centered polystyrene prepared by the following schemes 1 to 3 is prepared, and thus prepared It is disclosed that the color and fluorescence of TASN (Tetraarylsuccinonitrile)-centered polystyrene and PS-TASN-PS can be changed by physical stimuli such as grinding (see Fig. 3a of Non-Patent Document 1, etc.).
[스킴 1, TASN-diol 제조스킴][Scheme 1, TASN-diol manufacturing scheme]
[스킴 2, TASN-diol로부터 TASN-dialkyne 제조스킴][Scheme 2, TASN-dialkyne manufacturing scheme from TASN-diol]
[스킴 3, TASN-dialkyne로부터 PS-TASN-PS 제조스킴][Scheme 3, PS-TASN-PS manufacturing scheme from TASN-dialkyne]
한편, 본 발명은 기계적인 힘에 의해 화학결합이 끊어져 라디칼이 생성되고 이로부터 무색에서 색이 발현되는 메카노크로믹 분자에 고분자화 가능한 반응성기를 도입하여, 외부에서 가해지는 힘에 의해 변형이 발생할 시 자가보고할 수 있는 접착제, 페인트, 기판등으로 응용하고자 하였으며, 앞서 언급한 특허문헌 1(JP 2016-210991)과 비특허문헌 1(Chem. Commun., 2017, 53, 11885) 내용과는 하기에 개진한 차별성이 있다.On the other hand, the present invention introduces a polymerizable reactive group into a mechanochromic molecule that is colorless to colorless from which a chemical bond is broken by a mechanical force to generate a radical, and deformation may occur due to external force. It was intended to be applied to adhesives, paints, substrates, etc. that can be self-reported, and the contents of Patent Document 1 (JP 2016-210991) and Non-Patent Document 1 (Chem. There is a distinction made in
먼저, 본 발명은 메카노크로믹 단량체 말단에 광가교성 관능기를 도입함에 따라, 50-400 nm 파장 영역의 자외선을 간단히 조사하여, 광 가교를 통해 자극 반응형 자가보고 고분자의 제조가 가능한 반면,First, the present invention introduces a photo-crosslinkable functional group at the end of the mechanochromic monomer, by simply irradiating ultraviolet light in a wavelength region of 50-400 nm, thereby making it possible to prepare a stimulus-responsive self-reporting polymer through photocrosslinking,
앞서 언급한 특허문헌 1(JP 2016-210991)과 비특허문헌 1(Chem. Commun., 2017, 53, 11885)은 자외선 조사를 통한 광 가교가 아닌, C≡C 결합과 N3의 click reaction을 복잡하게 수행하여야만 자극 반응형 자가보고 고분자 제조가 가능한 단점이 있다.The aforementioned Patent Document 1 (JP 2016-210991) and Non-Patent Document 1 (Chem. Commun., 2017, 53, 11885) show a click reaction of C≡C bond and N 3 rather than photocrosslinking through ultraviolet irradiation. There is a disadvantage that it is possible to manufacture a stimulus-responsive self-reporting polymer only when it is performed in a complicated manner.
또한, 특허문헌 1(JP 2016-210991)과 비특허문헌 1(Chem. Commun., 2017, 53, 11885)에서 개시하고 있는 상기 TASN-diol 단량체는 3개의 탄소 사슬이 링커로 존재하는 치환체가 치환되어 있으므로, 단량체에 치환된 치환체의 구조에 있어서도, 본 발명과 상이하다.In addition, in the TASN-diol monomer disclosed in Patent Document 1 (JP 2016-210991) and Non-Patent Document 1 (Chem. Commun., 2017, 53, 11885), a substituent having three carbon chains as a linker is substituted Therefore, it is different from the present invention also in the structure of the substituent substituted for the monomer.
나아가, 특허문헌 1(JP 2016-210991)과 비특허문헌 1(Chem. Commun., 2017, 53, 11885)은 상기 TASN-dialkyne 단량체와 하기 화학식으로 표시되는 PS-N3(ω-아자이드-말단 폴리스티렌)을 화학적으로 반응시켜 고분자를 제조하므로, 최종 제조되는 자극 반응형 자가보고 고분자 구조 자체도, 본 발명과 상이하다.Furthermore, Patent Document 1 (JP 2016-210991) and Non-Patent Document 1 (Chem. Commun., 2017, 53, 11885) include the TASN-dialkyne monomer and PS-N 3 (ω-azide- Since the polymer is prepared by chemically reacting the terminal polystyrene), the structure of the stimuli-responsive self-reporting polymer itself is also different from the present invention.
[PS-N3(ω-아자이드-말단 폴리스티렌) 구조][PS-N 3 (ω-azide-terminated polystyrene) structure]
즉, 본 발명은 종래에 시도하지 않았던 메카노크로믹 단량체에 광가교성 관능기를 도입할 경우, 간단한 광 조사를 통해 고분자 제조가 가능하고, 이렇게 제조된 고분자가 눌림, 휨, 찢김, 인장등 기계적 자극에 의해 색과 형광이 용이하게 변화하므로, 물리적 자극 반응형 자가보고 고분자 소재, 이를 포함하는 접착제, 페인트, 또는 물리적 자극 응답형 센서 등으로 유용하게 사용될 수 있음을 입증하고 본 발명을 완성하였다.That is, in the present invention, when a photocrosslinkable functional group is introduced into a mechanochromic monomer, which has not been attempted before, a polymer can be prepared through simple light irradiation, and the polymer thus prepared is subjected to mechanical stimulation such as compression, bending, tearing, and tension. Since the color and fluorescence are easily changed by , it has been proved that it can be usefully used as a physical stimulus responsive self-reporting polymer material, an adhesive, paint, or a physical stimulus responsive sensor including the same, and completed the present invention.
본 발명의 일 측면에서의 목적은, 눌림, 휨, 찢김, 인장 등 기계적 자극에 의해 색이 변화하여 자가 보고할 수 있는 고분자 소재의 제조가 가능한 메카노크로믹 단량체를 제공하는 것이다.It is an object of one aspect of the present invention to provide a mechanochromic monomer capable of producing a self-reporting polymer material that changes color by mechanical stimuli such as pressing, bending, tearing, and tension.
본 발명의 다른 일 측면에서의 목적은, 상기 메카노크로믹 단량체에 광 조사를 통한 광 가교로 제조되는 고분자를 제공하는 것이다.Another object of the present invention is to provide a polymer prepared by photocrosslinking through light irradiation to the mechanochromic monomer.
본 발명의 다른 일 측면에서의 목적은, 상기 메카노크로믹 단량체 및 바이닐 아크릴기를 가지는 단량체의 중합에 의해 제조되는 고분자를 제공하는 것이다.Another object of the present invention is to provide a polymer prepared by polymerization of the mechanochromic monomer and a monomer having a vinyl acryl group.
본 발명의 또 다른 일 측면에서의 목적은, 상기 메카노크로믹 단량체에 광 조사를 통한 광 가교로 제조되는 고분자, 또는 상기 메카노크로믹 단량체 및 바이닐 아크릴기를 가지는 단량체의 중합에 의해 제조되는 고분자를 포함하는, 자가 보고 가능한 접착제 조성물을 제공하는 것이다.Another object of the present invention is a polymer prepared by photocrosslinking through light irradiation to the mechanochromic monomer, or a polymer prepared by polymerization of the mechanochromic monomer and a monomer having a vinyl acryl group. It is to provide a self-reportable adhesive composition comprising a.
본 발명의 다른 일 측면에서의 목적은, 상기 메카노크로믹 단량체에 광 조사를 통한 광 가교로 제조되는 고분자, 또는 상기 메카노크로믹 단량체 및 바이닐 아크릴기를 가지는 단량체의 중합에 의해 제조되는 고분자를 포함하는, 자가 보고 가능한 페인트 조성물을 제공하는 것이다.An object of another aspect of the present invention is a polymer prepared by photocrosslinking through light irradiation to the mechanochromic monomer, or a polymer prepared by polymerization of the mechanochromic monomer and a monomer having a vinyl acryl group. It is to provide a self-reportable paint composition comprising.
본 발명의 또 다른 일 측면에서의 목적은, 상기 메카노크로믹 단량체에 광 조사를 통한 광 가교로 제조되는 고분자, 또는 상기 메카노크로믹 단량체 및 바이닐 아크릴기를 가지는 단량체의 중합에 의해 제조되는 고분자를 포함하는, 물리적 자극 반응형 자가보고 고분자 조성물을 제공하는 것이다.Another object of the present invention is a polymer prepared by photocrosslinking through light irradiation to the mechanochromic monomer, or a polymer prepared by polymerization of the mechanochromic monomer and a monomer having a vinyl acryl group. It is to provide a self-reporting polymer composition containing a physical stimulus responsive.
본 발명의 다른 일 측면에서의 목적은, 상기 메카노크로믹 단량체에 광 조사를 통한 광 가교로 제조되는 고분자, 또는 상기 메카노크로믹 단량체 및 바이닐 아크릴기를 가지는 단량체의 중합에 의해 제조되는 고분자를 포함하는, 물리적 자극 응답형 센서를 제공하는 것이다.An object of another aspect of the present invention is a polymer prepared by photocrosslinking through light irradiation to the mechanochromic monomer, or a polymer prepared by polymerization of the mechanochromic monomer and a monomer having a vinyl acryl group. It is to provide a physical stimulus responsive sensor, including.
상기 목적을 달성하기 위하여,In order to achieve the above object,
본 발명의 일 측면은,One aspect of the present invention is
하기 화학식 1로 표시되는 메카노크로믹 단량체를 제공한다.It provides a mechanochromic monomer represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
A는 -O-, -NH-, 또는 -S-이고,A is -O-, -NH-, or -S-,
B는 비치환 또는 하나 이상의 플루오로로 치환된 직쇄 또는 분지쇄의 C1-20알킬이고,B is straight or branched C 1-20 alkyl unsubstituted or substituted with one or more fluoro;
n은 2 내지 20의 정수이고; 및n is an integer from 2 to 20; and
X는 분자 내에 라디칼 중합성의 이중결합을 하나 이상 포함하는 광가교성 관능기이다.X is a photocrosslinkable functional group including at least one radically polymerizable double bond in the molecule.
본 발명의 다른 일 측면은,Another aspect of the present invention is
상기 화학식 1로 표시되는 메카노크로믹 단량체에 광 조사를 통한 광 가교로 제조되는 고분자를 제공한다.To provide a polymer prepared by light crosslinking through light irradiation to the mechanochromic monomer represented by Formula 1 above.
본 발명의 또 다른 일 측면은,Another aspect of the present invention is
상기 화학식 1로 표시되는 메카노크로믹 단량체 및 바이닐 아크릴기를 가지는 단량체의 중합에 의해 제조되는 고분자를 제공한다.Provided is a polymer prepared by polymerization of a mechanochromic monomer represented by Formula 1 and a monomer having a vinyl acryl group.
본 발명의 다른 일 측면은, Another aspect of the present invention is
상기 화학식 1로 표시되는 메카노크로믹 단량체에 광 조사를 통한 광 가교로 제조되는 고분자, 또는 상기 화학식 1로 표시되는 메카노크로믹 단량체 및 바이닐 아크릴기를 가지는 단량체의 중합에 의해 제조되는 고분자를 포함하는 접착제 조성물을 제공한다.A polymer prepared by photocrosslinking through light irradiation to the mechanochromic monomer represented by Formula 1, or a polymer prepared by polymerization of the mechanochromic monomer represented by Formula 1 and a monomer having a vinyl acryl group An adhesive composition is provided.
본 발명의 또 다른 일 측면은,Another aspect of the present invention is
상기 화학식 1로 표시되는 메카노크로믹 단량체에 광 조사를 통한 광 가교로 제조되는 고분자, 또는 상기 화학식 1로 표시되는 메카노크로믹 단량체 및 바이닐 아크릴기를 가지는 단량체의 중합에 의해 제조되는 고분자를 포함하는 페인트 조성물을 제공한다.A polymer prepared by photocrosslinking through light irradiation to the mechanochromic monomer represented by Formula 1, or a polymer prepared by polymerization of the mechanochromic monomer represented by Formula 1 and a monomer having a vinyl acryl group A paint composition is provided.
본 발명의 다른 일 측면은,Another aspect of the present invention is
상기 화학식 1로 표시되는 메카노크로믹 단량체에 광 조사를 통한 광 가교로 제조되는 고분자, 또는 상기 화학식 1로 표시되는 메카노크로믹 단량체 및 바이닐 아크릴기를 가지는 단량체의 중합에 의해 제조되는 고분자를 포함하는 물리적 자극 반응형 자가보고 고분자 조성물을 제공한다.A polymer prepared by photocrosslinking through light irradiation to the mechanochromic monomer represented by Formula 1, or a polymer prepared by polymerization of the mechanochromic monomer represented by Formula 1 and a monomer having a vinyl acryl group Provided is a self-reporting polymer composition that responds to physical stimuli.
본 발명의 또 다른 일 측면은,Another aspect of the present invention is
상기 화학식 1로 표시되는 메카노크로믹 단량체에 광 조사를 통한 광 가교로 제조되는 고분자, 또는 상기 화학식 1로 표시되는 메카노크로믹 단량체 및 바이닐 아크릴기를 가지는 단량체의 중합에 의해 제조되는 고분자를 포함하는 물리적 자극 응답형 센서를 제공한다.A polymer prepared by photocrosslinking through light irradiation to the mechanochromic monomer represented by Formula 1, or a polymer prepared by polymerization of the mechanochromic monomer represented by Formula 1 and a monomer having a vinyl acryl group A physical stimulus-response sensor is provided.
본 발명의 일 측면에서 제공하는 라디칼계 메카노크로믹 단량체는 눌림, 휨, 찢김, 인장등 기계적 자극에 의해 색이 변화하여 센서, 자가보고 스마트 고분자 소재로 유용하게 사용될 수 있다.The radical-based mechanochromic monomer provided in one aspect of the present invention can be usefully used as a sensor and a self-reporting smart polymer material because the color changes due to mechanical stimuli such as pressing, bending, tearing, and tension.
도 1은 <실시예 1>에서 제조한 (((1,2-디시아노-1,2-비스(4-메톡시페닐)에탄-1,2-디일)비스(4,1-페닐렌))비스(옥시))비스(헥산-6,1-디일)비스(2-메틸아크릴레이트), 즉, 메카노크로믹 단량체의 NMR 구조분석 결과를 나타내는 도면이다.
도 2는 <실시예 2>에서 제조한 자가보고 고분자 분말을 얇게 편 후 핀셋으로 누르기, 약수저로 누르기, 망치로 때리기 등의 기계적 자극을 가한 후 육안으로 봤을 때의 색변화와, 자외선 램프를 비췄을 때의 색변화를 관찰한 결과를 나타내는 도면이다.
도 3은 <실시예 3>에서 제조한 메카노크로믹 단량체를 포함하는 자외선 경화형 접착제 조성물을 경화시키고 핀셋으로 누르기, 약수저로 누르기, 망치로 때리기 등의 기계적 자극을 가한 후 육안으로 봤을 때의 색변화와, 자외선 램프를 비췄을 때의 색변화를 관찰한 결과를 나타내는 도면이다.1 is (((1,2-dicyano-1,2-bis(4-methoxyphenyl)ethane-1,2-diyl)bis(4,1-phenylene) prepared in <Example 1> )bis(oxy))bis(hexane-6,1-diyl)bis(2-methylacrylate), that is, a diagram showing the results of NMR structural analysis of a mechanochromic monomer.
Figure 2 shows the color change and UV lamp when the self-reported polymer powder prepared in <Example 2> is thinly flattened and then subjected to mechanical stimulation such as pressing with tweezers, pressing with a spoon, or hitting with a hammer. It is a diagram showing the result of observing the color change when illuminated.
3 is a view of the UV curable adhesive composition containing the mechanochromic monomer prepared in <Example 3> after curing the UV curable adhesive composition and applying mechanical stimulation such as pressing with tweezers, pressing with a spoon, and hitting with a hammer. It is a diagram showing the result of observing color change and color change when irradiated with an ultraviolet lamp.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
한편, 본 발명의 실시 형태는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 이하 설명하는 실시 형태로 한정되는 것은 아니다. 또한, 본 발명의 실시 형태는 당해 기술분야에서 평균적인 지식을 가진 자에게 본 발명을 더욱 완전하게 설명하기 위해서 제공되는 것이다.On the other hand, the embodiment of the present invention can be modified in various other forms, the scope of the present invention is not limited to the embodiments described below. In addition, the embodiments of the present invention are provided in order to more completely explain the present invention to those of ordinary skill in the art.
나아가, 명세서 전체에서 어떤 구성요소를 "포함"한다는 것은 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있다는 것을 의미한다.Furthermore, in the entire specification, "including" a certain element means that other elements may be further included, rather than excluding other elements, unless otherwise stated.
본 발명의 일 측면은,One aspect of the present invention is
하기 화학식 1로 표시되는 메카노크로믹 단량체를 제공한다.It provides a mechanochromic monomer represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
A는 -O-, -NH-, 또는 -S-이고,A is -O-, -NH-, or -S-,
B는 비치환 또는 하나 이상의 플루오로로 치환된 직쇄 또는 분지쇄의 C1-20알킬이고,B is straight or branched C 1-20 alkyl unsubstituted or substituted with one or more fluoro;
n은 2 내지 20의 정수이고; 및n is an integer from 2 to 20; and
X는 분자 내에 라디칼 중합성의 이중결합을 하나 이상 포함하는 광가교성 관능기이다.X is a photocrosslinkable functional group including at least one radically polymerizable double bond in the molecule.
다른 일 측면에서,In another aspect,
A는 -O-, 또는 -NH-이고,A is -O-, or -NH-,
B는 비치환 또는 하나 이상의 플루오로로 치환된 직쇄 또는 분지쇄의 C1-15알킬이고,B is straight-chain or branched C 1-15 alkyl unsubstituted or substituted with one or more fluoro;
n은 2 내지 15의 정수이고; 및n is an integer from 2 to 15; and
X는 분자 내에 라디칼 중합성의 이중결합을 하나 이상 포함하는 광가교성 관능기일 수 있다.X may be a photocrosslinkable functional group including at least one radically polymerizable double bond in the molecule.
또 다른 일 측면에서,In another aspect,
A는 -O-, 또는 -NH-이고,A is -O-, or -NH-,
B는 비치환 또는 하나 이상의 플루오로로 치환된 직쇄 또는 분지쇄의 C1-10알킬이고,B is straight or branched C 1-10 alkyl unsubstituted or substituted with one or more fluoro;
n은 2 내지 10의 정수이고; 및n is an integer from 2 to 10; and
X는 분자 내에 라디칼 중합성의 이중결합을 하나 이상 포함하는 광가교성 관능기일 수 있다.X may be a photocrosslinkable functional group including at least one radically polymerizable double bond in the molecule.
다른 일 측면에서,In another aspect,
A는 -O-이고,A is -O-,
B는 비치환 또는 하나 이상의 플루오로로 치환된 직쇄 또는 분지쇄의 C1-5알킬이고,B is straight-chain or branched C 1-5 alkyl unsubstituted or substituted with one or more fluoro;
n은 4 내지 8의 정수이고; 및n is an integer from 4 to 8; and
X는 분자 내에 라디칼 중합성의 이중결합을 하나 이상 포함하는 광가교성 관능기일 수 있다.X may be a photocrosslinkable functional group including at least one radically polymerizable double bond in the molecule.
또 다른 일 측면에서,In another aspect,
A는 -O-이고,A is -O-,
B는 직쇄 또는 분지쇄의 C1-3알킬이고,B is a straight-chain or branched C 1-3 alkyl,
n은 5 내지 7의 정수이고; 및n is an integer from 5 to 7; and
X는 분자 내에 라디칼 중합성의 이중결합을 하나 이상 포함하는 광가교성 관능기일 수 있다.X may be a photocrosslinkable functional group including at least one radically polymerizable double bond in the molecule.
다른 일 측면에서,In another aspect,
상기 -A-X는,The -A-X is,
또 다른 일 측면에서,In another aspect,
상기 화학식 1로 표시되는 메카노크로믹 단량체는,The mechanochromic monomer represented by Formula 1 is,
하기 화학식 2로 표시되는 메카노크로믹 단량체인 것이 바람직하다.It is preferably a mechanochromic monomer represented by the following formula (2).
[화학식 2][Formula 2]
본 발명의 일 측면에서 제공하는 라디칼계 메카노크로믹 단량체는 눌림, 휨, 찢김, 인장등 기계적 자극에 의해 색이 변화하여 센서, 자가보고 스마트 고분자 소재로 유용하게 사용될 수 있다.The radical-based mechanochromic monomer provided in one aspect of the present invention can be usefully used as a sensor and a self-reporting smart polymer material because the color changes due to mechanical stimuli such as pressing, bending, tearing, and tension.
또한, 본 발명의 다른 일 측면은,In addition, another aspect of the present invention,
상기 화학식 1로 표시되는 메카노크로믹 단량체에 광 조사를 통한 광 가교로 제조되는 고분자를 제공한다.To provide a polymer prepared by light crosslinking through light irradiation to the mechanochromic monomer represented by Formula 1 above.
이때, 상기 광은 라디칼 중합성의 이중결합을 하나 이상 포함하는 광가교성 관능기의 가교를 유도할 수 있는 광이라면 특별한 제한 없이 사용할 수 있으며, 몇 가지 구체예를 들면 50-400 nm 파장 영역의 자외선, 100-400 nm 파장 영역의 자외선, 150-400 nm 파장 영역의 자외선, 200-400 nm 파장 영역의 자외선, 250-400 nm 파장 영역의 자외선, 300-400 nm 파장 영역의 자외선, 350-400 nm 파장 영역의 자외선 등을 사용할 수 있다.In this case, the light can be used without any particular limitation as long as it can induce crosslinking of a photocrosslinkable functional group containing one or more radically polymerizable double bonds. -400 nm wavelength range ultraviolet, 150-400 nm wavelength range UV light, 200-400 nm wavelength range UV light, 250-400 nm wavelength range UV light, 300-400 nm wavelength range UV light, 350-400 nm wavelength range of ultraviolet light, etc. can be used.
나아가, 본 발명의 또 다른 일 측면은,Furthermore, another aspect of the present invention is
상기 화학식 1로 표시되는 메카노크로믹 단량체; 및Mechanochromic monomer represented by Formula 1; and
바이닐 아크릴기를 가지는 단량체;의 중합에 의해 제조되는 고분자를 제공한다.It provides a polymer prepared by polymerization of a monomer having a vinyl acryl group.
이때, 상기 고분자는,In this case, the polymer is
상기 화학식 1로 표시되는 메카노크로믹 단량체 내 X의 이중결합과,A double bond of X in the mechanochromic monomer represented by Formula 1,
상기 바이닐 아크릴기를 가지는 단량체 내 바이닐기가 서로 중합 반응되어 형성되는 고분자일 수 있다.It may be a polymer formed by polymerization of vinyl groups in the monomer having the vinyl acryl group.
상기 바이닐 아크릴기를 가지는 단량체로는 메틸메타아크릴레이트 등을 사용할 수 있다. 상기 화학식 1로 표시되는 메카노크로믹 단량체와 바이닐 아크릴기를 가지는 단량체의 혼합 몰 비율(mole ratio)은 1:10 내지 30 범위일 수 있고, 1:12 내지 30 범위일 수 있고, 1:14 내지 30 범위일 수 있고, 1:16 내지 30 범위일 수 있고, 1:18 내지 30 범위일 수 있고, 1:10 내지 28 범위일 수 있고, 1:10 내지 26 범위일 수 있고, 1:10 내지 24 범위일 수 있고, 1:10 내지 22 범위일 수 있고, 1:10 내지 20 범위일 수 있고, 1:12 내지 28 범위일 수 있고, 1:14 내지 26 범위일 수 있고, 1:16 내지 24 범위일 수 있고, 1:18 내지 22 범위일 수 있고, 1:18 내지 20 범위일 수 있고, 1:19 범위일 수 있다.As the monomer having the vinyl acryl group, methyl methacrylate may be used. The mixing mole ratio of the mechanochromic monomer represented by Formula 1 and the monomer having a vinyl acryl group may be in the range of 1:10 to 30, may be in the range of 1:12 to 30, and may be in the range of 1:14 to It may be in the range of 30, it may be in the range of 1:16 to 30, it may be in the range of 1:18 to 30, it may be in the range of 1:10 to 28, it may be in the range of 1:10 to 26, it may be in the range of 1:10 to It can range from 24, it can be from 1:10 to 22, it can be from 1:10 to 20, it can be from 1:12 to 28, it can be from 1:14 to 26, it can be from 1:16 to It may be in the range of 24, it may be in the range of 1:18 to 22, it may be in the range of 1:18 to 20, and it may be in the range of 1:19.
상기 화학식 1로 표시되는 메카노크로믹 단량체 및 바이닐 아크릴기를 가지는 단량체의 중합 반응은 N-메틸-2-피롤리돈(N-methyl-2-pyrrolidone, NMP) 등의 용매와 질소 분위기 하에서 교반하여 수행될 수 있다.The polymerization reaction of the mechanochromic monomer represented by Formula 1 and the monomer having a vinyl acryl group is performed by stirring with a solvent such as N-methyl-2-pyrrolidone (NMP) under a nitrogen atmosphere. can be performed.
상기 교반 온도는 몇 가지 구체예로 40 내지 120℃ 범위일 수 있고, 50 내지 120℃ 범위일 수 있고, 60 내지 120℃ 범위일 수 있고, 70 내지 120℃ 범위일 수 있고, 75 내지 120℃ 범위일 수 있고, 40 내지 110℃ 범위일 수 있고, 40 내지 100℃ 범위일 수 있고, 40 내지 90℃ 범위일 수 있고, 40 내지 95℃ 범위일 수 있고, 50 내지 110℃ 범위일 수 있고, 60 내지 100℃ 범위일 수 있고, 70 내지 90℃ 범위일 수 있고, 75 내지 85℃ 범위일 수 있고, 90℃일 수 있다.The stirring temperature may range from 40 to 120 °C, from 50 to 120 °C, from 60 to 120 °C, from 70 to 120 °C, from 75 to 120 °C, in some embodiments. may be in the range of 40 to 110 °C, may be in the range of 40 to 100 °C, may be in the range of 40 to 90 °C, may be in the range of 40 to 95 °C, may be in the range of 50 to 110 °C, may be in the range of 60 It can be in the range of 100°C, it can be in the range of 70-90°C, it can be in the range of 75-85°C, and it can be 90°C.
상기 교반 시간은 몇 가지 구체예로 36 내지 60시간 범위일 수 있고, 38 내지 60시간 범위일 수 있고, 40 내지 60시간 범위일 수 있고, 42 내지 60시간 범위일 수 있고, 44 내지 60시간 범위일 수 있고, 46 내지 60시간 범위일 수 있고, 47 내지 60시간 범위일 수 있고, 36 내지 58시간 범위일 수 있고, 36 내지 56시간 범위일 수 있고, 36 내지 54시간 범위일 수 있고, 36 내지 52시간 범위일 수 있고, 36 내지 50시간 범위일 수 있고, 36 내지 49시간 범위일 수 있고, 38 내지 58시간 범위일 수 있고, 40 내지 56시간 범위일 수 있고, 42 내지 54시간 범위일 수 있고, 44 내지 52시간 범위일 수 있고, 46 내지 50시간 범위일 수 있고, 47 내지 49시간 범위일 수 있고, 48시간일 수 있다.The stirring time may be in the range of 36 to 60 hours, in some embodiments, in the range of 38 to 60 hours, in the range of 40 to 60 hours, in the range of 42 to 60 hours, in the range of 44 to 60 hours. may be in the range of 46 to 60 hours, may be in the range of 47 to 60 hours, may be in the range of 36 to 58 hours, may be in the range of 36 to 56 hours, may be in the range of 36 to 54 hours, 36 It may be in the range of from to 52 hours, it may be in the range of 36 to 50 hours, it may be in the range of 36 to 49 hours, it may be in the range of 38 to 58 hours, it may be in the range of 40 to 56 hours, it may be in the range of 42 to 54 hours. It may be in the range of 44 to 52 hours, may be in the range of 46 to 50 hours, may be in the range of 47 to 49 hours, and may be in the range of 48 hours.
상기 화학식 1로 표시되는 메카노크로믹 단량체 및 바이닐 아크릴기를 가지는 단량체의 중합 반응 후, 반응 혼합물을 과량의 메탄올에 침전시켜 반응을 종료하고 필터 후, 소량의 N-메틸-2-피롤리돈에 녹인 후 과량의 메탄올에 재침전 후 필터할 수 있다. 이후, 3회 이상 과량의 메탄올을 이용해서 세척하여 상기 화학식 1로 표시되는 메카노크로믹 단량체 및 바이닐 아크릴기를 가지는 단량체가 중합되어 제조된 고체 고분자를 제조할 수 있다.After the polymerization reaction of the mechanochromic monomer represented by Formula 1 and the monomer having a vinyl acryl group, the reaction mixture is precipitated in excess methanol to terminate the reaction, filtered, and added to a small amount of N-methyl-2-pyrrolidone After dissolving, it can be filtered after reprecipitation in excess methanol. Thereafter, the solid polymer prepared by polymerization of the mechanochromic monomer represented by Formula 1 and the monomer having a vinyl acryl group by washing with excess methanol three or more times may be prepared.
또한, 본 발명의 다른 일 측면은, In addition, another aspect of the present invention,
상기 화학식 1로 표시되는 메카노크로믹 단량체에 광 조사를 통한 광 가교로 제조되는 고분자, 또는 상기 화학식 1로 표시되는 메카노크로믹 단량체 및 바이닐 아크릴기를 가지는 단량체의 중합에 의해 제조되는 고분자를 포함하는 접착제 조성물을 제공한다.A polymer prepared by photocrosslinking through light irradiation to the mechanochromic monomer represented by Formula 1, or a polymer prepared by polymerization of the mechanochromic monomer represented by Formula 1 and a monomer having a vinyl acryl group An adhesive composition is provided.
상기 접착제 조성물에서, 상기 화학식 1로 표시되는 메카노크로믹 단량체에 광 조사를 통한 광 가교로 제조되는 고분자, 또는 상기 화학식 1로 표시되는 메카노크로믹 단량체 및 바이닐 아크릴기를 가지는 단량체의 중합에 의해 제조되는 고분자는, 상기 접착제 조성물 총 100 중량% 중에서, 0.1 내지 30 중량% 범위로 포함될 수 있고, 0.3 내지 30 중량% 범위로 포함될 수 있고, 0.5 내지 30 중량% 범위로 포함될 수 있고, 0.1 내지 28 중량% 범위로 포함될 수 있고, 0.1 내지 26 중량% 범위로 포함될 수 있고, 0.1 내지 24 중량% 범위로 포함될 수 있고, 0.1 내지 22 중량% 범위로 포함될 수 있고, 0.1 내지 20 중량% 범위로 포함될 수 있고, 0.1 내지 18 중량% 범위로 포함될 수 있고, 0.1 내지 16 중량% 범위로 포함될 수 있고, 0.1 내지 14 중량% 범위로 포함될 수 있고, 0.1 내지 12 중량% 범위로 포함될 수 있고, 0.1 내지 10 중량% 범위로 포함될 수 있고, 0.1 내지 8 중량% 범위로 포함될 수 있고, 0.1 내지 6 중량% 범위로 포함될 수 있고, 0.1 내지 4 중량% 범위로 포함될 수 있고, 0.3 내지 5 중량% 범위로 포함될 수 있고, 0.5 내지 3 중량% 범위 등으로 포함될 수 있으나, 물리적 자극에 대한 응답을 충분히 유도할 수 있는 함량이라면 제한 없이 접착제 조성물에 포함시킬 수 있다.In the adhesive composition, a polymer prepared by photocrosslinking through light irradiation to the mechanochromic monomer represented by Formula 1, or by polymerization of the mechanochromic monomer represented by Formula 1 and a monomer having a vinyl acryl group The polymer to be prepared may be included in the range of 0.1 to 30% by weight, in the range of 0.3 to 30% by weight, in the range of 0.5 to 30% by weight, and in the range of 0.1 to 28 of the total 100% by weight of the adhesive composition. It may be included in the range of weight %, may be included in the range of 0.1 to 26 weight%, may be included in the range of 0.1 to 24% by weight, may be included in the range of 0.1 to 22% by weight, may be included in the range of 0.1 to 20% by weight and may be included in the range of 0.1 to 18% by weight, may be included in the range of 0.1 to 16% by weight, may be included in the range of 0.1 to 14% by weight, may be included in the range of 0.1 to 12% by weight, may be included in the range of 0.1 to 10% by weight %, may be included in the range of 0.1 to 8% by weight, may be included in the range of 0.1 to 6% by weight, may be included in the range of 0.1 to 4% by weight, may be included in the range of 0.3 to 5% by weight, , but may be included in the range of 0.5 to 3% by weight, etc., as long as the content can sufficiently induce a response to a physical stimulus, it may be included in the adhesive composition without limitation.
나아가, 본 발명의 또 다른 일 측면은,Furthermore, another aspect of the present invention is
상기 화학식 1로 표시되는 메카노크로믹 단량체에 광 조사를 통한 광 가교로 제조되는 고분자, 또는 상기 화학식 1로 표시되는 메카노크로믹 단량체 및 바이닐 아크릴기를 가지는 단량체의 중합에 의해 제조되는 고분자를 포함하는 페인트 조성물을 제공한다.A polymer prepared by photocrosslinking through light irradiation to the mechanochromic monomer represented by Formula 1, or a polymer prepared by polymerization of the mechanochromic monomer represented by Formula 1 and a monomer having a vinyl acryl group A paint composition is provided.
상기 페인트 조성물에서, 상기 화학식 1로 표시되는 메카노크로믹 단량체에 광 조사를 통한 광 가교로 제조되는 고분자, 또는 상기 화학식 1로 표시되는 메카노크로믹 단량체 및 바이닐 아크릴기를 가지는 단량체의 중합에 의해 제조되는 고분자는, 상기 페인트 조성물 총 100 중량% 중에서, 0.1 내지 30 중량% 범위로 포함될 수 있고, 0.3 내지 30 중량% 범위로 포함될 수 있고, 0.5 내지 30 중량% 범위로 포함될 수 있고, 0.1 내지 28 중량% 범위로 포함될 수 있고, 0.1 내지 26 중량% 범위로 포함될 수 있고, 0.1 내지 24 중량% 범위로 포함될 수 있고, 0.1 내지 22 중량% 범위로 포함될 수 있고, 0.1 내지 20 중량% 범위로 포함될 수 있고, 0.1 내지 18 중량% 범위로 포함될 수 있고, 0.1 내지 16 중량% 범위로 포함될 수 있고, 0.1 내지 14 중량% 범위로 포함될 수 있고, 0.1 내지 12 중량% 범위로 포함될 수 있고, 0.1 내지 10 중량% 범위로 포함될 수 있고, 0.1 내지 8 중량% 범위로 포함될 수 있고, 0.1 내지 6 중량% 범위로 포함될 수 있고, 0.1 내지 4 중량% 범위로 포함될 수 있고, 0.3 내지 5 중량% 범위로 포함될 수 있고, 0.5 내지 3 중량% 범위 등으로 포함될 수 있으나, 물리적 자극에 대한 응답을 충분히 유도할 수 있는 함량이라면 제한 없이 페인트 조성물에 포함시킬 수 있다.In the paint composition, a polymer prepared by photocrosslinking through light irradiation to the mechanochromic monomer represented by Formula 1, or by polymerization of the mechanochromic monomer represented by Formula 1 and a monomer having a vinyl acryl group The polymer to be prepared may be included in the range of 0.1 to 30% by weight, in the range of 0.3 to 30% by weight, in the range of 0.5 to 30% by weight, and in the range of 0.1 to 28, among 100% by weight of the total weight of the paint composition It may be included in the range of weight %, may be included in the range of 0.1 to 26 weight%, may be included in the range of 0.1 to 24% by weight, may be included in the range of 0.1 to 22% by weight, may be included in the range of 0.1 to 20% by weight and may be included in the range of 0.1 to 18% by weight, may be included in the range of 0.1 to 16% by weight, may be included in the range of 0.1 to 14% by weight, may be included in the range of 0.1 to 12% by weight, may be included in the range of 0.1 to 10% by weight %, may be included in the range of 0.1 to 8% by weight, may be included in the range of 0.1 to 6% by weight, may be included in the range of 0.1 to 4% by weight, may be included in the range of 0.3 to 5% by weight, , may be included in the range of 0.5 to 3% by weight, etc., but may be included in the paint composition without limitation as long as the content can sufficiently induce a response to a physical stimulus.
또한, 본 발명의 다른 일 측면은,In addition, another aspect of the present invention,
상기 화학식 1로 표시되는 메카노크로믹 단량체에 광 조사를 통한 광 가교로 제조되는 고분자, 또는 상기 화학식 1로 표시되는 메카노크로믹 단량체 및 바이닐 아크릴기를 가지는 단량체의 중합에 의해 제조되는 고분자를 포함하는 물리적 자극 반응형 자가보고 고분자 조성물을 제공한다.A polymer prepared by photocrosslinking through light irradiation to the mechanochromic monomer represented by Formula 1, or a polymer prepared by polymerization of the mechanochromic monomer represented by Formula 1 and a monomer having a vinyl acryl group Provided is a self-reporting polymer composition that responds to physical stimuli.
나아가, 본 발명의 또 다른 일 측면은,Furthermore, another aspect of the present invention is
상기 화학식 1로 표시되는 메카노크로믹 단량체에 광 조사를 통한 광 가교로 제조되는 고분자, 또는 상기 화학식 1로 표시되는 메카노크로믹 단량체 및 바이닐 아크릴기를 가지는 단량체의 중합에 의해 제조되는 고분자를 포함하는 물리적 자극 응답형 센서를 제공한다.A polymer prepared by photocrosslinking through light irradiation to the mechanochromic monomer represented by Formula 1, or a polymer prepared by polymerization of the mechanochromic monomer represented by Formula 1 and a monomer having a vinyl acryl group A physical stimulus-response sensor is provided.
본 발명에 따른 단량체는 광가교에 의해, 혹은 다른 광반응형 단량체와 고분자화 반응을 통해 기계적 자극에 의해 색이 변화하는 자가보고 고분자 소재로 유용하게 사용될 수 있으며, 이는 후술하는 실시예 및 실험예에 의해 직접적으로 뒷받침된다.The monomer according to the present invention can be usefully used as a self-reporting polymer material whose color changes due to mechanical stimulation through photocrosslinking or polymerization with other photoreactive monomers, which will be described later in Examples and Experimental Examples is supported directly by
이하, 본 발명을 실시예 및 실험예를 통해 상세히 설명한다.Hereinafter, the present invention will be described in detail through Examples and Experimental Examples.
단, 후술하는 실시예 및 실험예는 본 발명을 일 측면에서 구체적으로 예시하는 것일 뿐, 본 발명이 이에 한정되는 것은 아니다.However, the Examples and Experimental Examples described below are merely illustrative of the present invention in detail in one aspect, and the present invention is not limited thereto.
<실시예 1> (((1,2-디시아노-1,2-비스(4-메톡시페닐)에탄-1,2-디일)비스(4,1-페닐렌))비스(옥시))비스(헥산-6,1-디일)비스(2-메틸아크릴레이트) 제조<Example 1> (((1,2-dicyano-1,2-bis(4-methoxyphenyl)ethane-1,2-diyl)bis(4,1-phenylene))bis(oxy)) Preparation of bis(hexane-6,1-diyl)bis(2-methylacrylate)
단계 1: 2-히드록시-2-(4-메톡시페닐)아세토니트릴 제조Step 1: Preparation of 2-hydroxy-2-(4-methoxyphenyl)acetonitrile
반응 용기에 포타슘시아니드 57.37 g (881mmol) 을 증류수 180 mL, 초산에틸 200 mL에 녹이고 소듐비설피트 91.68 g (881 mmol) 을 첨가한 후, p-아니살데하이드(p-anisaldehyde) 17.89 mL (147mmol) 을 천천히 적가하고, 상온에서 20시간 동안 교반하였다. 반응 혼합물을 초산에틸과 증류수로 추출하고, 용매를 모두 증발시킨 후, 톨루엔/헥산 = 5:1(v/v) 로 잔여물을 제거하여 하얀색의 고체 (16.8 g, 70%) 를 수득하였다.In a reaction vessel, 57.37 g (881 mmol) of potassium cyanide was dissolved in 180 mL of distilled water and 200 mL of ethyl acetate, and 91.68 g (881 mmol) of sodium bisulfite was added thereto, and then 17.89 mL (147 mmol) of p -anisaldehyde. ) was slowly added dropwise, and stirred at room temperature for 20 hours. The reaction mixture was extracted with ethyl acetate and distilled water, and all solvents were evaporated, and the residue was removed with toluene/hexane = 5:1 (v/v) to obtain a white solid (16.8 g, 70%).
1H NMR (500 MHz, CDCl3) δ 7.49 - 7.44 (m, 2H), 6.98 - 6.94 (m, 2H), 5.49 (s, 1H), 3.84 (s, 3H). 1 H NMR (500 MHz, CDCl 3 ) δ 7.49 - 7.44 (m, 2H), 6.98 - 6.94 (m, 2H), 5.49 (s, 1H), 3.84 (s, 3H).
단계 2: 2-(4-히드록시페닐)-2-(4-메톡시페닐)아세토니트릴 제조Step 2: Preparation of 2-(4-hydroxyphenyl)-2-(4-methoxyphenyl)acetonitrile
2-히드록시-2-(4-메톡시페닐)아세토니트릴 10.0 g (61.3 mmol) 을 반응 용기에 넣고 35% 황산 47.7 mL (367.8 mmol), 페놀 13.87g (147.4 mmol) 을 첨가한 후, 50℃ 에서 20시간 이상 동안 교반하였다. 상온으로 냉각 후, 반응 혼합물 중 고체만 걸러 초산에틸과 증류수로 추출하고, 용매를 모두 증발시킨 후, 소량의 테트라하이드로퓨란에 용해시킨 후, 증류수에서 재침전시켜 여과시킨 후, 진공 건조하여 하얀색 고체 (13.64g, 93%) 를 수득하였다.2-hydroxy-2-(4-methoxyphenyl)acetonitrile 10.0 g (61.3 mmol) was placed in a reaction vessel, 47.7 mL (367.8 mmol) of 35% sulfuric acid, and 13.87 g (147.4 mmol) of phenol were added, followed by 50 The mixture was stirred at ℃ for 20 hours or more. After cooling to room temperature, only solids in the reaction mixture were filtered, extracted with ethyl acetate and distilled water, all solvents evaporated, dissolved in a small amount of tetrahydrofuran, reprecipitated in distilled water, filtered, vacuum dried, and white solids (13.64 g, 93%) was obtained.
1H NMR (500 MHz, Chloroform-d) δ 7.25 - 7.21 (m, 2H), 7.21 - 7.16 (m, 2H), 6.91 - 6.86 (m, 2H), 6.84 - 6.79 (m, 2H), 5.04 (s, 1H), 3.80 (s, 3H). 1 H NMR (500 MHz, Chloroform- d ) δ 7.25 - 7.21 (m, 2H), 7.21 - 7.16 (m, 2H), 6.91 - 6.86 (m, 2H), 6.84 - 6.79 (m, 2H), 5.04 ( s, 1H), 3.80 (s, 3H).
단계 3: 2-(4-((6-히드록시헥실)옥시)페닐)-1-(4-메톡시페닐)아세토니트릴 제조Step 3: Preparation of 2-(4-((6-hydroxyhexyl)oxy)phenyl)-1-(4-methoxyphenyl)acetonitrile
2-(4-히드록시페닐)-2-(4-메톡시페닐)아세토니트릴 2.0 g (8.36 mmol) 을 반응 용기에 넣고 디메틸포름아미드 64 mL에 녹이고 포타슘카보나트 2.89 g (20.9 mmol) 을 첨가하고, 100 ℃ 에서 1.5시간 동안 교반하였다. 브로모헥사놀 2.28 mL (16.72 mmol) 을 천천히 적가한 후, 100 ℃ 에서 20시간 이상동안 교반하였다. 반응 혼합물을 초산에틸과 증류수로 추출하고, 용매를 모두 증발시킨 후, 컬럼 크로마토그래피 (헥산/초산에틸 = 4:1(v/v)) 로 분리하여 주황색의 액체 (1.77 g, 62%) 를 수득하였다.2.0 g (8.36 mmol) of 2-(4-hydroxyphenyl)-2-(4-methoxyphenyl)acetonitrile was dissolved in 64 mL of dimethylformamide, and 2.89 g (20.9 mmol) of potassium carbonate was added. and stirred at 100 °C for 1.5 hours. 2.28 mL (16.72 mmol) of bromohexanol was slowly added dropwise, followed by stirring at 100° C. for 20 hours or more. The reaction mixture was extracted with ethyl acetate and distilled water, and all solvents were evaporated, and then separated by column chromatography (hexane/ethyl acetate = 4:1 (v/v)) to give an orange liquid (1.77 g, 62%). obtained.
1H NMR (500 MHz, Chloroform-d) δ 7.25 - 7.20 (m, 4H), 6.89 - 6.84 (m, 4H), 5.04 (s, 1H), 3.94 (t, J = 6.5 Hz, 2H), 3.80 (s, 3H), 3.66 (td, J = 6.4, 4.7 Hz, 2H), 2.05 (s, 2H), 1.78 (dt, J = 8.0, 6.6 Hz, 2H), 1.63 - 1.58 (m, 2H), 1.51 - 1.47 (m, 2H), 1.47 - 1.42 (m, 2H). 1 H NMR (500 MHz, Chloroform- d ) δ 7.25 - 7.20 (m, 4H), 6.89 - 6.84 (m, 4H), 5.04 (s, 1H), 3.94 (t, J = 6.5 Hz, 2H), 3.80 (s, 3H), 3.66 (td, J = 6.4, 4.7 Hz, 2H), 2.05 (s, 2H), 1.78 (dt, J = 8.0, 6.6 Hz, 2H), 1.63 - 1.58 (m, 2H), 1.51 - 1.47 (m, 2H), 1.47 - 1.42 (m, 2H).
단계 4: 2,3-비스(4-((6-히드록시헥실)옥시)페닐)-2,3-비스(4-메톡시페닐)석시노니트릴 제조Step 4: Preparation of 2,3-bis(4-((6-hydroxyhexyl)oxy)phenyl)-2,3-bis(4-methoxyphenyl)succinonitrile
2-(4-((6-히드록시헥실)옥시)페닐)-1-(4-메톡시페닐)아세토니트릴 2.0 g (5.89 mmol) 을 반응 용기에 넣고 메탄올 52 mL에 녹인다. 포타슘시아니드 2.13 g (6.46 mmol) 을 5몰 소듐히드록시드 22 mL에 용해시킨 후 천천히 적가하고, 상온에서 5분 동안 교반하였다. 반응 혼합물을 이염화메탄과 증류수로 추출하고, 용매를 모두 증발시킨 후, 컬럼 크로마토그래피 (초산에틸/이염화메탄 = 1:1(v/v)) 로 분리하여 주황색의 액체 (0.93g, 47%) 를 수득하였다.2.0 g (5.89 mmol) of 2-(4-((6-hydroxyhexyl)oxy)phenyl)-1-(4-methoxyphenyl)acetonitrile was placed in a reaction vessel, and dissolved in 52 mL of methanol. After dissolving 2.13 g (6.46 mmol) of potassium cyanide in 22 mL of 5 mol sodium hydroxide, it was slowly added dropwise, followed by stirring at room temperature for 5 minutes. The reaction mixture was extracted with methane dichloride and distilled water, and all solvents were evaporated, and then separated by column chromatography (ethyl acetate/methane dichloride = 1:1 (v/v)) as an orange liquid (0.93 g, 47 %) was obtained.
1H NMR (500 MHz, Chloroform-d) δ 7.19 (dtd, J = 8.9, 4.7, 2.2 Hz, 8H), 6.80 - 6.74 (m, 8H), 3.95 (t, J = 6.5 Hz, 4H), 3.81 (s, 6H), 3.69 (t, J = 6.7 Hz, 4H), 1.85 - 1.78 (m, 4H), 1.66 - 1.61 (m, 4H), 1.55 - 1.50 (m, 4H), 1.49 - 1.45 (m, 4H). 1 H NMR (500 MHz, Chloroform- d ) δ 7.19 (dtd, J = 8.9, 4.7, 2.2 Hz, 8H), 6.80 - 6.74 (m, 8H), 3.95 (t, J = 6.5 Hz, 4H), 3.81 (s, 6H), 3.69 (t, J = 6.7 Hz, 4H), 1.85 - 1.78 (m, 4H), 1.66 - 1.61 (m, 4H), 1.55 - 1.50 (m, 4H), 1.49 - 1.45 (m , 4H).
단계 5: (((1,2-디시아노-1,2-비스(4-메톡시페닐)에탄-1,2-디일)비스(4,1-페닐렌))비스(옥시))비스(헥산-6,1-디일)비스(2-메틸아크릴레이트) 제조Step 5: (((1,2-dicyano-1,2-bis(4-methoxyphenyl)ethane-1,2-diyl)bis(4,1-phenylene))bis(oxy))bis( Preparation of hexane-6,1-diyl)bis(2-methylacrylate)
2,3-비스(4-((6-히드록시헥실)옥시)페닐)-2,3-비스(4-메톡시페닐)석시노니트릴 0.91 g (1.48 mmol) 을 반응 용기에 넣고 이염화메탄 10 mL, 트리에틸아민 0.93 mL, 디메틸아미노피리딘 0.016 g (0.148 mmol) 을 첨가하였다. 산소를 제거하고 질소분위기 하에서 메타크릴로일클로라이드 0.58 mL (5.92 mmol) 을 천천히 적가하고, 상온에서 3시간 이상동안 교반하였다. 반응 혼합물을 이염화메탄과 증류수로 추출하고, 용매를 모두 증발시킨 후, 컬럼 크로마토그래피 (헥산/초산에틸 = 5:1 (v/v)) 로 분리하여 노랑색의 액체 (0.2 g, 33%) 를 수득하였다.0.91 g (1.48 mmol) of 2,3-bis(4-((6-hydroxyhexyl)oxy)phenyl)-2,3-bis(4-methoxyphenyl)succinonitrile was placed in a reaction vessel, and methane dichloride 10 mL, 0.93 mL of triethylamine, 0.016 g (0.148 mmol) of dimethylaminopyridine were added. After oxygen was removed, 0.58 mL (5.92 mmol) of methacryloyl chloride was slowly added dropwise under a nitrogen atmosphere, and the mixture was stirred at room temperature for at least 3 hours. The reaction mixture was extracted with methane dichloride and distilled water, all solvents were evaporated, and then separated by column chromatography (hexane/ethyl acetate = 5:1 (v/v)) as a yellow liquid (0.2 g, 33%) was obtained.
1H NMR (500 MHz, Chloroform-d) δ 7.19 (tdd, J = 6.7, 4.0, 2.1 Hz, 8H), 6.80 - 6.74 (m, 8H), 6.12 (dq, J = 2.0, 1.0 Hz, 2H), 5.57 (p, J = 1.6 Hz, 2H), 4.18 (t, J = 6.6 Hz, 4H), 3.95 (t, J = 6.4 Hz, 4H), 3.81 (s, 6H), 1.97 (t, J = 1.3 Hz, 6H), 1.85 - 1.78 (m, 4H), 1.74 (p, J = 6.8 Hz, 4H), 1.56 - 1.51 (m, 4H), 1.51 - 1.47 (m, 4H). 1 H NMR (500 MHz, Chloroform- d ) δ 7.19 (tdd, J = 6.7, 4.0, 2.1 Hz, 8H), 6.80 - 6.74 (m, 8H), 6.12 (dq, J = 2.0, 1.0 Hz, 2H) , 5.57 (p, J = 1.6 Hz, 2H), 4.18 (t, J = 6.6 Hz, 4H), 3.95 (t, J = 6.4 Hz, 4H), 3.81 (s, 6H), 1.97 (t, J = 1.3 Hz, 6H), 1.85 - 1.78 (m, 4H), 1.74 (p, J = 6.8 Hz, 4H), 1.56 - 1.51 (m, 4H), 1.51 - 1.47 (m, 4H).
<실시예 1>에서 제조한 (((1,2-디시아노-1,2-비스(4-메톡시페닐)에탄-1,2-디일)비스(4,1-페닐렌))비스(옥시))비스(헥산-6,1-디일)비스(2-메틸아크릴레이트), 즉, 메카노크로믹 단량체의 NMR 구조분석 결과를 도 1에 나타내었다.Prepared in <Example 1> (((1,2-dicyano-1,2-bis(4-methoxyphenyl)ethane-1,2-diyl)bis(4,1-phenylene))bis( The results of NMR structural analysis of oxy)) bis (hexane-6,1-diyl) bis (2-methyl acrylate), that is, mechanochromic monomer, are shown in FIG. 1 .
<실시예 2> 자가보고 고분자 제조<Example 2> Preparation of self-reporting polymer
상기 <실시예 1>에서 제조한 (((1,2-디시아노-1,2-비스(4-메톡시페닐)에탄-1,2-디일)비스(4,1-페닐렌))비스(옥시))비스(헥산-6,1-디일)비스(2-메틸아크릴레이트), 즉, 메카노크로믹 단량체에 자외선 (365 nm)을 조사를 통한 경화를 유도하여 자가보고 고분자를 분말 형태로 제조하였다.(((1,2-dicyano-1,2-bis(4-methoxyphenyl)ethane-1,2-diyl)bis(4,1-phenylene))bis prepared in <Example 1> (oxy))bis(hexane-6,1-diyl)bis(2-methylacrylate), that is, self-reporting polymer in powder form by inducing curing through irradiation with ultraviolet (365 nm) to mechanochromic monomer was prepared with
최종 제조된 자가보고 고분자의 대략적인 구조는 하기와 같다.The approximate structure of the finally prepared self-reporting polymer is as follows.
[자가보고 고분자 구조][Self-reported polymer structure]
<실시예 3> 메카노크로믹 단량체를 포함하는 자외선 경화형 접착제 조성물 제조<Example 3> Preparation of UV-curable adhesive composition containing mechanochromic monomer
(((1,2-디시아노-1,2-비스(4-메톡시페닐)에탄-1,2-디일)비스(4,1-페닐렌))비스(옥시))비스(헥산-6,1-디일)비스(2-메틸아크릴레이트), 즉, 메카노크로믹 단량체를 함량별로 상용 자외선 경화형 레진 (머크)과 혼합한 후 1분 동안 실온에서 교반하였다. 혼합한 조성물을 유기기판이나 플라스틱 기판위에 코팅 한 후 10 내지 50 J의 자외선 (365 nm)을 조사하여 경화하였다.(((1,2-dicyano-1,2-bis(4-methoxyphenyl)ethane-1,2-diyl)bis(4,1-phenylene))bis(oxy))bis(hexane-6 ,1-diyl)bis(2-methylacrylate), that is, mechanochromic monomer was mixed with a commercial UV-curable resin (Merck) by content, followed by stirring at room temperature for 1 minute. After coating the mixed composition on an organic or plastic substrate, it was cured by irradiating UV rays (365 nm) of 10 to 50 J.
<실험예 1> 자가보고 고분자의 기계적 자극에 의한 변색특성 평가<Experimental Example 1> Evaluation of discoloration characteristics due to mechanical stimulation of self-reported polymers
상기 <실시예 2>에서 제조한 자가보고 고분자 분말을 대상으로 하기와 같은 실험을 수행하였다.The following experiment was performed on the self-reported polymer powder prepared in <Example 2>.
보다 구체적으로, 상기 <실시예 2>에서 제조한 자가보고 고분자 분말을 얇게 편 후 핀셋으로 누르기, 약수저로 누르기, 망치로 때리기 등의 기계적 자극을 가한 후 육안으로 봤을 때의 색변화와, 자외선 램프를 비췄을 때의 색변화를 관찰하였다.More specifically, after applying a mechanical stimulus such as pressing with tweezers, pressing with a spatula, or hitting with a hammer after thinly flattening the self-reported polymer powder prepared in <Example 2>, the color change and ultraviolet rays when viewed with the naked eye The color change when the lamp was illuminated was observed.
그 결과를 도 2에 나타내었다.The results are shown in FIG. 2 .
도 2는 <실시예 2>에서 제조한 자가보고 고분자 분말을 얇게 편 후 핀셋으로 누르기, 약수저로 누르기, 망치로 때리기 등의 기계적 자극을 가한 후 육안으로 봤을 때의 색변화와, 자외선 램프를 비췄을 때의 색변화를 관찰한 결과를 나타내는 도면이다.Figure 2 shows the color change and UV lamp when the self-reported polymer powder prepared in <Example 2> is thinly flattened and then subjected to mechanical stimulation such as pressing with tweezers, pressing with a spatula, or hitting with a hammer. It is a diagram showing the result of observing the color change when illuminated.
도 2에 나타난 바와 같이,As shown in Figure 2,
기계적 자극에 의해 육안으로 봤을 때는 붉은색으로 색이 나타나며, 자외선 램프 조사시에 형광이 나타남을 확인 할 수 있다.It can be seen that the color appears red when viewed with the naked eye due to mechanical stimulation, and fluorescence appears when irradiated with an ultraviolet lamp.
<실험예 2> 자외선 경화형 접착제 조성물의 기계적 자극에 의한 변색특성 평가<Experimental Example 2> Evaluation of discoloration characteristics due to mechanical stimulation of UV-curable adhesive composition
상기 <실시예 3>에서 제조한 메카노크로믹 단량체를 포함하는 자외선 경화형 접착제 조성물을 대상으로 하기와 같은 실험을 수행하였다.The following experiment was performed on the UV curable adhesive composition containing the mechanochromic monomer prepared in <Example 3>.
보다 구체적으로, 상기 <실시예 3>에서 제조한 메카노크로믹 단량체를 포함하는 자외선 경화형 접착제 조성물에 자외선 (365 nm)을 조사한 후 경화시킨 후,More specifically, after curing after irradiating ultraviolet rays (365 nm) to the ultraviolet curable adhesive composition containing the mechanochromic monomer prepared in <Example 3>,
핀셋으로 누르기, 약수저로 누르기, 망치로 때리기 등의 기계적 자극을 가한 후 육안으로 봤을 때의 색변화와, 자외선 램프를 비췄을 때의 색변화를 관찰하였다.After applying mechanical stimuli such as pressing with tweezers, pressing with a spoon, or hitting with a hammer, the color change when viewed with the naked eye and color change when illuminated with an ultraviolet lamp were observed.
그 결과를 도 3에 나타내었다.The results are shown in FIG. 3 .
도 3은 <실시예 3>에서 제조한 메카노크로믹 단량체를 포함하는 자외선 경화형 접착제 조성물을 경화시키고 핀셋으로 누르기, 약수저로 누르기, 망치로 때리기 등의 기계적 자극을 가한 후 육안으로 봤을 때의 색변화와, 자외선 램프를 비췄을 때의 색변화를 관찰한 결과를 나타내는 도면이다.3 is a view of the UV curable adhesive composition containing the mechanochromic monomer prepared in <Example 3> after curing the UV curable adhesive composition and applying mechanical stimulation such as pressing with tweezers, pressing with a spoon, and hitting with a hammer. It is a diagram showing the result of observing the color change and the color change when irradiated with an ultraviolet lamp.
도 3에서 0.5 wt%, 1wt%는, 접착제 조성물 총 100 wt% 중, 메카노크로믹 단량체가 0.5 wt%, 1wt% 만큼 포함된 경우를 의미한다.In FIG. 3, 0.5 wt% and 1 wt% means a case in which 0.5 wt% or 1 wt% of the mechanochromic monomer is included among 100 wt% of the total adhesive composition.
도 3에 나타난 바와 같이,As shown in Figure 3,
기계적 자극에 의해 육안으로 봤을 때는 붉은색으로 색이 나타나며, 자외선 램프 조사시에 형광이 나타남을 확인 할 수 있다.It can be seen that the color appears red when viewed with the naked eye due to mechanical stimulation, and fluorescence appears when irradiated with an ultraviolet lamp.
Claims (15)
[화학식 1]
상기 화학식 1에서,
A는 -O-, -NH-, 또는 -S-이고,
B는 비치환 또는 하나 이상의 플루오로로 치환된 직쇄 또는 분지쇄의 C1-20알킬이고,
n은 2 내지 20의 정수이고; 및
X는 분자 내에 라디칼 중합성의 이중결합을 하나 이상 포함하는 광가교성 관능기이고,
상기 -A-X는,
A mechanochromic monomer represented by the following formula (1):
[Formula 1]
In Formula 1,
A is -O-, -NH-, or -S-,
B is straight or branched C 1-20 alkyl unsubstituted or substituted with one or more fluoro;
n is an integer from 2 to 20; and
X is a photocrosslinkable functional group containing at least one radically polymerizable double bond in the molecule,
The -AX is,
상기 화학식 1로 표시되는 메카노크로믹 단량체는,
하기 화학식 2로 표시되는 메카노크로믹 단량체인 것을 특징으로 하는 메카노크로믹 단량체:
[화학식 2]
The method of claim 1,
The mechanochromic monomer represented by Formula 1 is,
A mechanochromic monomer, characterized in that it is a mechanochromic monomer represented by the following formula (2):
[Formula 2]
광 조사를 통한 광 가교로 제조되는 고분자.
To the mechanochromic monomer represented by Formula 1 of claim 1,
A polymer produced by photocrosslinking through light irradiation.
상기 광은 50-400 nm 파장 영역의 자외선인 것을 특징으로 하는 고분자.
9. The method of claim 8,
The light is a polymer, characterized in that the 50-400 nm wavelength region ultraviolet.
바이닐 아크릴기를 가지는 단량체;의 중합에 의해 제조되는 고분자.
A mechanochromic monomer represented by Formula 1 of claim 1; and
A polymer produced by polymerization of a monomer having a vinyl acryl group.
상기 고분자는,
제1항의 화학식 1로 표시되는 메카노크로믹 단량체 내 X의 이중결합과, 상기 바이닐 아크릴기를 가지는 단량체 내 바이닐기가 중합 반응되어 형성되는 것을 특징으로 하는 고분자.
11. The method of claim 10,
The polymer is
A polymer characterized in that it is formed by a polymerization reaction between the double bond of X in the mechanochromic monomer represented by Formula 1 of claim 1 and the vinyl group in the monomer having the vinyl acryl group.
An adhesive composition comprising the polymer of claim 8 or 10.
A paint composition comprising the polymer of claim 8 or 10.
A physical stimulus responsive self-reporting polymer composition comprising the polymer of claim 8 or 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020200032976A KR102396554B1 (en) | 2020-03-18 | 2020-03-18 | Radical based mechanochromic monomers and self-reporting polymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020200032976A KR102396554B1 (en) | 2020-03-18 | 2020-03-18 | Radical based mechanochromic monomers and self-reporting polymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20210116869A KR20210116869A (en) | 2021-09-28 |
| KR102396554B1 true KR102396554B1 (en) | 2022-05-10 |
Family
ID=77923138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020200032976A KR102396554B1 (en) | 2020-03-18 | 2020-03-18 | Radical based mechanochromic monomers and self-reporting polymers |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR102396554B1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20230033902A (en) | 2021-09-02 | 2023-03-09 | 주식회사 엘지에너지솔루션 | Battery cell and battery module including the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016066656A (en) | 2014-09-24 | 2016-04-28 | 株式会社トクヤマ | Composition for imprint |
| JP2016210991A (en) * | 2015-05-11 | 2016-12-15 | 国立大学法人東京工業大学 | Mechanochromic compound and mechanochromic material comprising the same |
| CN110835530A (en) | 2018-08-15 | 2020-02-25 | 北京化工大学 | Reversible light modulation and control fluorescent liquid crystal nano particle and reversible light modulation and control color fluorescent ink |
-
2020
- 2020-03-18 KR KR1020200032976A patent/KR102396554B1/en active IP Right Grant
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016066656A (en) | 2014-09-24 | 2016-04-28 | 株式会社トクヤマ | Composition for imprint |
| JP2016210991A (en) * | 2015-05-11 | 2016-12-15 | 国立大学法人東京工業大学 | Mechanochromic compound and mechanochromic material comprising the same |
| CN110835530A (en) | 2018-08-15 | 2020-02-25 | 北京化工大学 | Reversible light modulation and control fluorescent liquid crystal nano particle and reversible light modulation and control color fluorescent ink |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20210116869A (en) | 2021-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109476774B (en) | Polymeric materials using controlled free radical initiators and methods of making | |
| Temel et al. | Synthesis and characterization of one-component polymeric photoinitiator by simultaneous double click reactions and its use in photoinduced free radical polymerization | |
| JP5187825B2 (en) | Hyperbranched polymer and method for producing the same | |
| Nakabayashi et al. | RAFT polymerization of S-vinyl sulfide derivatives and synthesis of block copolymers having two distinct optoelectronic functionalities | |
| EP2065408A1 (en) | Hyperbranched polymer and process for production thereof | |
| TW201736333A (en) | Preparing method of (meth)acrylate group-containing benzophenone for optical adhesive use and optical adhesive composition | |
| KR102396554B1 (en) | Radical based mechanochromic monomers and self-reporting polymers | |
| JP5578512B2 (en) | Novel (meth) acrylate compound and method for producing the same | |
| KR101294367B1 (en) | Adhesive material, adhesive composition including the same and method for curing the adhesive composition | |
| Palanisamy et al. | Tetrafunctional acrylates based on β-hydroxy alkyl amides as crosslinkers for UV curable coatings | |
| DE69815404T2 (en) | BROWNED MATERIALS | |
| TWI542603B (en) | Adhesive composition coating (meth)acrylic ester copolymer, maunfacturing method of it, and method of control physical property thereof | |
| US11028294B2 (en) | Acrylate-cyanoacrylate monomers | |
| CN110028629B (en) | Preparation method of longifolene-based acrylate modified waterborne polyurethane | |
| JP6381140B2 (en) | Composition, curable composition, method for producing the same, and cured product | |
| KR101965194B1 (en) | Fluoro monomer and oligomer compounds, photopolymerized composition, and hydrophobic film using the same | |
| Podkościelna | Synthesis, spectroscopic and thermal characterization of the new photoluminescent monomer: 2, 7-di (methacyloyloxy) naphthalene and its copolymerization with selected vinyl monomers | |
| KR101066943B1 (en) | Aqueous suspension of cardanol polymer and preparation method thereof | |
| Schenzel | Advanced debonding on demand systems for dental adhesives | |
| JP6524768B2 (en) | Oligofluor orange (meth) acrylate, (meth) acrylate resin composition, optical member and lens | |
| CN110452327B (en) | Fluorescent polymer shape memory material and preparation method thereof | |
| US6486344B1 (en) | Polymer coatings with improved adhesion properties on metallic surfaces | |
| EP4011864A1 (en) | Photobase generator, compound, photoreactive composition, and reaction product | |
| EP4067453A1 (en) | Photobase generator, compound, photoreactive composition, and reaction product | |
| JP2001039956A (en) | New ester compound having isocyanuric acid ring and its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |