KR20230080099A - Method of manufacturing the high-substituted carboxymethyl cellulose - Google Patents
Method of manufacturing the high-substituted carboxymethyl cellulose Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 229920002134 Carboxymethyl cellulose Polymers 0.000 title claims description 57
- 235000010948 carboxy methyl cellulose Nutrition 0.000 title claims description 56
- 239000001768 carboxy methyl cellulose Substances 0.000 title claims description 52
- 239000008112 carboxymethyl-cellulose Substances 0.000 title claims description 52
- 238000006467 substitution reaction Methods 0.000 claims abstract description 53
- 230000021962 pH elevation Effects 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 75
- 239000000376 reactant Substances 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 230000035484 reaction time Effects 0.000 claims description 21
- 229920002678 cellulose Polymers 0.000 claims description 12
- 239000001913 cellulose Substances 0.000 claims description 12
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 5
- 229940106681 chloroacetic acid Drugs 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 40
- 238000000034 method Methods 0.000 abstract description 9
- 230000003247 decreasing effect Effects 0.000 abstract description 2
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 48
- QMGYPNKICQJHLN-UHFFFAOYSA-M Carboxymethylcellulose cellulose carboxymethyl ether Chemical compound [Na+].CC([O-])=O.OCC(O)C(O)C(O)C(O)C=O QMGYPNKICQJHLN-UHFFFAOYSA-M 0.000 description 13
- 238000003756 stirring Methods 0.000 description 6
- 239000008186 active pharmaceutical agent Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 4
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 4
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 3
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 3
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 3
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 3
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 3
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- WWSJZGAPAVMETJ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-ethoxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OCC WWSJZGAPAVMETJ-UHFFFAOYSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000021164 cell adhesion Effects 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 239000011153 ceramic matrix composite Substances 0.000 description 1
- 238000012710 chemistry, manufacturing and control Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
- C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
- C08B11/22—Isolation
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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Abstract
본 발명은 CMC의 제조방법에 관한 것이다.
본 발명에 의한 CMC의 제조방법은, 알칼리화 단계와 카르복시메틸화 단계를 반복하여 진행하고, 반복하여 진행하는 과정에서 상기 알칼리화 단계와 상기 카르복시메틸화 단계의 반응조건을 다르게 진행할 수 있으며, 그 이후 세척, 중화, 여과, 건조 단계를 진행할 수 있다.
본 발명에 따른 CMC의 제조방법은 고치환도의 CMC를 얻을 수 있을 뿐만 아니라, 반응 조건을 변화시킴에 따라서 점도 감소 없이 고치환도의 고점도 CMC를 제조할 수 있다. The present invention relates to a method for preparing CMC.
In the method for producing CMC according to the present invention, the alkalinization step and the carboxymethylation step are repeatedly performed, and in the process of repeating the alkalinization step and the carboxymethylation step, the reaction conditions may be different, and then washing and neutralization are performed. , filtration, and drying steps may be performed.
The method for producing CMC according to the present invention can not only obtain CMC with high substitution degree, but also prepare high viscosity CMC with high substitution degree without decreasing the viscosity by changing the reaction conditions.
Description
본 발명은 고치환도 카르복시메틸 셀룰로오스의 제조방법에 관한 것으로서, 더욱 상세하게는 최종 제품의 점도를 약화시키지 않으면서도 고치환도를 얻을 수 있는 고치환도 카르복시메틸 셀룰로오스의 제조방법에 관한 것이다. The present invention relates to a method for producing high substitution degree carboxymethyl cellulose, and more particularly, to a method for producing high substitution degree carboxymethyl cellulose capable of obtaining high substitution degree without weakening the viscosity of a final product.
일반적으로 카르복시메틸셀룰로오스 (Carboxymethyl cellulose: CMC)는 셀룰로오스의 하이드록시기 (-OH)를 친수성인 카르복시메틸기 (-CH2COONa)로 치환시켜 수용성을 부가한 것으로, 일반의 수용성 고분자와 같이 흡습성을 나타낸다.In general, carboxymethyl cellulose (CMC) is obtained by substituting the hydroxyl group (-OH) of cellulose with a hydrophilic carboxymethyl group (-CH 2 COONa) to add water solubility, and exhibits hygroscopicity like general water-soluble polymers. .
셀룰로오스는 무수글루코오스 단위체 (Anhydroglucose unit)가 서로 연결되어 이루어진 긴 사슬형의 고분자 물질이다. 각각의 글루코오스는 반응할 수 있는 활성화 부분으로 세 개의 하이드록시기를 가지고 있으며, 이 중 1급 하이드록시기 (-CH2OH)의 활성도가 가장 높다.Cellulose is a long-chain polymeric material composed of anhydroglucose units connected to each other. Each glucose has three hydroxyl groups as active moieties that can react, and among them, the primary hydroxyl group (-CH 2 OH) has the highest activity.
무수 글루코오스 단위체 한 개에 대해 치환된 카르복시메틸기의 평균수를 치환도 (Degree of substitution, 이하 'DS'라고 칭한다)라 하며, 세 개의 하이드록시기 전부가 카르복시메틸기로 치환되었을 때, DS 3.0의 CMC 제조가 가능해진다. 셀룰로오스부터 얻어진 CMC에서 DS는 CMC의 특성을 결정하는 중요한 지표가 되고 있다. The average number of carboxymethyl groups substituted for one anhydroglucose unit is called the degree of substitution (hereinafter referred to as 'DS'), and when all three hydroxyl groups are substituted with carboxymethyl groups, CMC production of DS 3.0 becomes possible In CMC obtained from cellulose, DS has become an important index to determine the properties of CMC.
CMC는 주원료인 셀룰로오스에 수산화나트륨을 반응시켜 셀룰로오스를 활성화시키고, 여기에 클로로아세트산을 반응시켜 셀룰로오스의 하이드록시기를 카르복시메틸기로 치환시켜 만들어진 음이온성의 수용성 고분자이다. 각 단계의 반응시간, 반응온도, 반응물 투입량 및 반응물의 농도 등에 따라 DS가 달라진다. CMC is an anionic water-soluble polymer made by reacting sodium hydroxide with cellulose, the main raw material, to activate cellulose, and then reacting with chloroacetic acid to replace the hydroxy group of cellulose with carboxymethyl group. DS varies depending on the reaction time, reaction temperature, reactant input amount, and reactant concentration in each step.
그러나, 고치환도 CMC를 제조할 수 있는 최적의 반응온도와 반응시간이 한정적이며, 실험변수 조건의 변화에 따라 물리적 특성이 급변하기 때문에 사용처에서 요구하는 점도를 유지하면서 고치환도의 CMC를 제조하는 것은 쉽지 않다는 문제가 있다.However, the optimal reaction temperature and reaction time for producing CMC with high substitution degree are limited, and physical properties change rapidly according to changes in experimental variable conditions. The problem is that it is not easy.
종래의 기술로서는 다음과 같은 사례가 대표적인 것으로 여겨진다. As a conventional technique, the following cases are considered representative.
본 발명의 목적은 상술한 문제를 해결하기 위한 것으로, 알칼리화 단계와 카르복시메틸화 단계의 반복을 통해 고치환도 CMC의 제조방법을 제공하는 것이다.An object of the present invention is to solve the above-mentioned problems, and to provide a method for producing CMC with a high degree of substitution through repetition of an alkalization step and a carboxymethylation step.
본 발명의 다른 목적은 반응 사이클 2회 이상에서의 반응 조건 (반응시간, 반응물 투입량 등)의 변화를 통해 점도 감소현상 없는 고치환도 CMC의 제조방법을 제공하는 것이다.Another object of the present invention is to provide a method for preparing CMC with a high degree of substitution without a decrease in viscosity through a change in reaction conditions (reaction time, reactant input amount, etc.) in two or more reaction cycles.
상기 목적을 달성하기 위하여, 본 발명은 펄프 형태의 셀룰로오스에 에탄올과 수산화나트륨 (NaOH)을 첨가하여 알칼리 셀룰로오스를 제조하는 단계(단계 1) ; 상기 알칼리 셀룰로오스에 클로로아세트산 (MCA)를 첨가하여 반응물을 제조하는 단계(단계 2) ; 상기 반응물에 에탄올로 세척하며 pH조절제를 가하여 중화시키는 단계(단계 3) ; 상기 세척 및 중화된 반응물을 여과 및 건조시키는 단계(단계 4) ; 상기 건조된 반응물을 분쇄하여 CMC를 수득하는 단계(단계 5); 를 포함하는 CMC의 제조방법에 있어서, 상기 단계 1과 2를 반복하여 1.0 이상의 치환도를 가지는 CMC의 제조방법을 제공한다.In order to achieve the above object, the present invention comprises the steps of preparing alkali cellulose by adding ethanol and sodium hydroxide (NaOH) to pulp-type cellulose (step 1); preparing a reactant by adding chloroacetic acid (MCA) to the alkali cellulose (step 2); Washing the reactant with ethanol and neutralizing it by adding a pH adjusting agent (step 3); filtering and drying the washed and neutralized reactants (step 4); Grinding the dried reactant to obtain CMC (step 5); In the method for producing CMC comprising a, repeating steps 1 and 2 provides a method for producing CMC having a degree of substitution of 1.0 or more.
또한, 본 발명은 상기 단계 1과 단계 2를 반복하여 CMC를 제조하는 방법에 있어서, 상기 단계 1의 수산화나트륨 (NaOH)과 상기 단계 2의 클로로아세트산 (MCA)의 투입량 및 반응시간을 조절하여 1.0 이상의 치환도를 가지면서도 사용처의 요구에 대응할 수 있도록 다양한 점도를 가지는 CMC의 제조방법을 제공한다.In addition, in the method of producing CMC by repeating steps 1 and 2, the present invention adjusts the input amount and reaction time of sodium hydroxide (NaOH) in step 1 and chloroacetic acid (MCA) in step 2 to obtain 1.0 It provides a method for manufacturing CMC having various viscosities so as to respond to the needs of the place of use while having the above degree of substitution.
본 발명에 의한 CMC의 제조방법은 제조하기 쉽지 않은 고치환도 CMC를 비교적 간단하게 제조할 수 있으며, 특히 높은 치환도를 가지면서도 점도를 유지하는 CMC를 제조할 수 있다. 더 나아가 고치환도의 고점도 CMC를 제조할 경우에 유리한 효과가 있다.The method for producing CMC according to the present invention can relatively easily prepare CMC with a high degree of substitution, which is not easy to prepare, and in particular, can produce CMC that maintains viscosity while having a high degree of substitution. Furthermore, there is an advantageous effect in the case of producing a high viscosity CMC with a high degree of substitution.
도 1은 CMC의 제조과정을 순서대로 나타낸 도면이다.
도 2는 비교예 1 및 실시예 1-1 내지 3-3의 점도와 치환도를 각각 나타낸 그래프이다.
도 3은 비교예 2 및 실시예 4-1 내지 6-3의 점도와 치환도를 각각 나타낸 그래프이다.
도 4는 실시예 7 내지 10의 점도와 치환도를 각각 나타낸 그래프이다.1 is a view showing the manufacturing process of CMC in order.
2 is a graph showing the viscosity and degree of substitution of Comparative Example 1 and Examples 1-1 to 3-3, respectively.
3 is a graph showing the viscosity and degree of substitution of Comparative Example 2 and Examples 4-1 to 6-3, respectively.
Figure 4 is a graph showing the viscosity and substitution degree of Examples 7 to 10, respectively.
이하, 본 발명을 더욱 구체적이고 상세하게 설명한다. 본 발명에서 제공되는 구체적인 수치 또는 구체적인 실시예는 본 발명의 바람직한 실시 양태로서, 본 발명의 기술사상을 보다 상세하게 설명하기 위한 것일 뿐이며, 본 발명이 이에 한정되는 것이 아님은 명백하다. Hereinafter, the present invention will be described more specifically and in detail. Specific numerical values or specific examples provided in the present invention are only intended to explain the technical idea of the present invention in more detail as a preferred embodiment of the present invention, and it is clear that the present invention is not limited thereto.
또한, 본 발명의 명세서에 있어서, 이 기술분야에서 공지된 것으로서 통상의 기술을 가진 자에 의해 용이하게 창작될 수 있는 부분에 대해서는 상세한 설명을 생략하기로 한다. In addition, in the specification of the present invention, detailed descriptions of parts that are known in the art and can be easily created by those skilled in the art will be omitted.
또한, 본 발명은 하기 실시예에 의하여 더욱 구체적으로 설명한다. 그러나, 하기 실시예는 본 발명의 이해를 돕기 위한 것일 뿐, 어떤 의미로든 본 발명의 범위가 이러한 실시예에 의하여 한정되는 것은 아니다.In addition, the present invention is further specifically described by the following examples. However, the following examples are only for helping understanding of the present invention, and the scope of the present invention is not limited by these examples in any sense.
<비교예 1>: 일반적인 CMC 제조<Comparative Example 1>: Preparation of general CMC
에탄올이 담긴 니더에 분쇄한 린터펄프 100g을 투입하여 교반하였다. 교반 후에 알칼리화 단계로 NaOH 400g을 넣고 120분 동안 반응을 진행하였다. 그리고 카르복시메틸화 단계로 MCA 400g을 투입하고 25 ℃ 에서 60 ℃로 승온하여 30분 동안 반응을 진행하였다. 100 g of pulverized linterpulp was added to a kneader containing ethanol and stirred. After stirring, 400 g of NaOH was added as an alkalization step, and the reaction proceeded for 120 minutes. Then, 400 g of MCA was added to the carboxymethylation step, and the reaction was performed for 30 minutes by raising the temperature from 25 °C to 60 °C.
반응이 종료된 샘플에 에탄올로 세척하며 pH조절제를 가하여 중화시킨 후, 여과하여 건조기에 건조시켰다. 건조된 반응물을 분쇄하여 최종 수득물인 CMC를 제조하였다.After the reaction was completed, the sample was washed with ethanol, neutralized by adding a pH adjusting agent, filtered, and dried in a dryer. The dried reactant was pulverized to prepare CMC as a final product.
도 1은 CMC의 제조과정을 순서대로 나타낸 도면이다.1 is a view showing the manufacturing process of CMC in order.
<실시예 1-1>: 펄프 1배 반응물 투입 및 1회 반복<Example 1-1>: Pulp 1-times reactant input and repeat 1 time
에탄올이 담긴 니더에 분쇄한 린터펄프 100g을 투입하여 교반하였다. 교반 후에 알칼리화 단계로 NaOH 100g을 넣고 60분 동안 반응을 진행하였다. 그리고 카르복시메틸화 단계로 MCA 100g을 투입하고 25 ℃ 에서 60 ℃로 승온하여 15분 동안 반응을 진행하였다. 100 g of pulverized linterpulp was added to a kneader containing ethanol and stirred. After stirring, 100 g of NaOH was added as an alkalization step and the reaction proceeded for 60 minutes. Then, 100 g of MCA was added to the carboxymethylation step and the temperature was increased from 25 ° C to 60 ° C. The temperature was raised and the reaction proceeded for 15 minutes.
온도를 상온으로 냉각시켜 다시 상기 알칼리화 단계와 카르복시메틸화 단계를 1회 다시 반복하여 실시하였다. The temperature was cooled to room temperature, and the alkalization step and the carboxymethylation step were repeated once again.
반응이 종료된 샘플은 상기 비교예 1과 동일한 방법으로 세척, 중화, 건조 및 분쇄 과정을 실시하였다.The reaction-completed sample was washed, neutralized, dried, and pulverized in the same manner as in Comparative Example 1.
<실시예 1-2>: 펄프 1배 반응물 투입 및 2회반복<Example 1-2>: Pulp 1 times reactant input and repeat twice
상기 실시예 1-1과 동일한 방법으로 알칼리화 단계와 카르복시메틸화 단계를진행하여 실시하였고, The alkalinization step and the carboxymethylation step were carried out in the same manner as in Example 1-1,
온도를 상온으로 냉각시켜 다시 상기 알칼리화 단계와 카르복시메틸화 단계를 2회 다시 반복하여 실시하였다. 전체적으로 상기 알칼리화 단계와 카르복시메틸화 단계를 총 3회 실시하였던 것이다.The temperature was cooled to room temperature, and the alkalization step and the carboxymethylation step were repeated twice again. In total, the alkalinization step and the carboxymethylation step were carried out a total of three times.
반응이 종료된 샘플은 상기 비교예 1과 동일한 방법으로 세척, 중화, 건조 및 분쇄 과정을 실시하였다.The reaction-completed sample was washed, neutralized, dried, and pulverized in the same manner as in Comparative Example 1.
<실시예 2-1>: 펄프 1.5배 반응물 투입 및 1회 반복<Example 2-1>: Adding 1.5 times the reactant to the pulp and repeating it once
에탄올이 담긴 니더에 분쇄한 린터펄프 100g을 투입하여 교반하였다. 교반 후에 알칼리화 단계로 NaOH 150g을 넣고 60분 동안 반응을 진행하였다. 그리고 카르복시메틸화 단계로 MCA 150g을 투입하고 25 ℃ 에서 60 ℃로 승온하여 15분 동안 반응을 진행하였다. 100 g of pulverized linterpulp was added to a kneader containing ethanol and stirred. After stirring, 150 g of NaOH was added as an alkalization step and the reaction was carried out for 60 minutes. Then, 150 g of MCA was added to the carboxymethylation step, and the reaction was conducted for 15 minutes by raising the temperature from 25 °C to 60 °C.
온도를 상온으로 냉각시켜 다시 상기 알칼리화 단계와 카르복시메틸화 단계를 1회 다시 반복하여 실시하였다. The temperature was cooled to room temperature, and the alkalization step and the carboxymethylation step were repeated once again.
반응이 종료된 샘플은 상기 비교예 1과 동일한 방법으로 세척, 중화, 건조 및 분쇄 과정을 실시하였다.The reaction-completed sample was washed, neutralized, dried, and pulverized in the same manner as in Comparative Example 1.
<실시예 2-2>: 펄프 1.5배 반응물 투입 및 2회 반복<Example 2-2>: Pulp 1.5 times reactant input and repeated 2 times
상기 실시예 2-1과 동일한 방법으로 알칼리화 단계와 카르복시메틸화 단계를진행하여 실시하였고, The alkalinization step and the carboxymethylation step were carried out in the same manner as in Example 2-1,
온도를 상온으로 냉각시켜 다시 상기 알칼리화 단계와 카르복시메틸화 단계를 2회 다시 반복하여 실시하였다. 전체적으로 상기 알칼리화 단계와 카르복시메틸화 단계를 총 3회 실시하였던 것이다.The temperature was cooled to room temperature, and the alkalization step and the carboxymethylation step were repeated twice again. In total, the alkalinization step and the carboxymethylation step were carried out a total of three times.
반응이 종료된 샘플은 상기 비교예 1과 동일한 방법으로 세척, 중화, 건조 및 분쇄 과정을 실시하였다.The reaction-completed sample was washed, neutralized, dried, and pulverized in the same manner as in Comparative Example 1.
<실시예 3-1>: 펄프 2배 반응물 투입 및 1회 반복<Example 3-1>: Pulp twice reactant input and repeat once
에탄올이 담긴 니더에 분쇄한 린터펄프 100g을 투입하여 교반하였다. 교반 후에 알칼리화 단계로 NaOH 200g을 넣고 60분 동안 반응을 진행하였다. 그리고 카르복시메틸화 단계로 MCA 200g을 투입하고 25 ℃ 에서 60 ℃로 승온하여 15분 동안 반응을 진행하였다. 100 g of pulverized linterpulp was added to a kneader containing ethanol and stirred. After stirring, 200 g of NaOH was added as an alkalization step, and the reaction proceeded for 60 minutes. Then, 200 g of MCA was added to the carboxymethylation step, and the reaction was performed for 15 minutes by raising the temperature from 25 °C to 60 °C.
온도를 상온으로 냉각시켜 다시 상기 알칼리화 단계와 카르복시메틸화 단계를 1회 다시 반복하여 실시하였다. The temperature was cooled to room temperature, and the alkalization step and the carboxymethylation step were repeated once again.
반응이 종료된 샘플은 상기 비교예 1과 동일한 방법으로 세척, 중화, 건조 및 분쇄 과정을 실시하였다.The reaction-completed sample was washed, neutralized, dried, and pulverized in the same manner as in Comparative Example 1.
<실시예 3-2>: 펄프 2배 반응물 투입 및 2회 반복<Example 3-2>: Pulp twice reactant input and repeat twice
상기 실시예 3-1과 동일한 방법으로 알칼리화 단계와 카르복시메틸화 단계를진행하여 실시하였고, The alkalinization step and the carboxymethylation step were carried out in the same manner as in Example 3-1,
온도를 상온으로 냉각시켜 다시 상기 알칼리화 단계와 카르복시메틸화 단계를 2회 다시 반복하여 실시하였다. 전체적으로 상기 알칼리화 단계와 카르복시메틸화 단계를 총 3회 실시하였던 것이다.The temperature was cooled to room temperature, and the alkalization step and the carboxymethylation step were repeated twice again. In total, the alkalinization step and the carboxymethylation step were carried out a total of three times.
반응이 종료된 샘플은 상기 비교예 1과 동일한 방법으로 세척, 중화, 건조 및 분쇄 과정을 실시하였다.The reaction-completed sample was washed, neutralized, dried, and pulverized in the same manner as in Comparative Example 1.
상기 비교예 1 및 실시예 1-1 내지 3-2의 제조 조건을 아래와 같이 표 1에 나타내었다.The manufacturing conditions of Comparative Example 1 and Examples 1-1 to 3-2 are shown in Table 1 as follows.
상기 비교예 및 상기 실시예에 의하여 제조된 최종 CMC의 성능을 확인하기 위하여, 최종 CMC의 점도 및 치환도를 각각 측정하였다. In order to confirm the performance of the final CMC prepared according to the comparative example and the above example, the viscosity and degree of substitution of the final CMC were measured, respectively.
상기 점도는 브룩필드 점도계 (Brookfield Viscometer)를 이용하여 측정하였다. 구체적으로, 증류수 495 g에 상기 비교예 및 실시예에서 제조한 각각의 CMC 분말 5 g을 용해시켜 1%의 용액을 제조한 다음, CMC 용액의 온도를 25℃로 유지한 상태에서 각각의 CMC 용액의 점도를 측정하였다. The viscosity was measured using a Brookfield Viscometer. Specifically, 5 g of each CMC powder prepared in Comparative Examples and Examples was dissolved in 495 g of distilled water to prepare a 1% solution, and then each CMC solution while maintaining the temperature of the CMC solution at 25 ° C. The viscosity of was measured.
한편, 상기 치환도는 역적정으로 실험값을 얻어 하기 수학식 1을 통해 계산하였다. On the other hand, the degree of substitution was calculated through Equation 1 below by obtaining an experimental value by back titration.
< 수학식 1 >: 치환도 계산식<Equation 1>: Substitution degree calculation formula
상기 수학식 1에 있어서, In Equation 1,
V NaOH = 0.1 N NaOH 소비량 (ml)V NaOH = 0.1 N NaOH consumption (ml)
V H2SO4 = 0.1 N H2SO4 소비량 (ml)V H2SO4 = 0.1 NH 2 SO 4 consumption (ml)
M = 샘플량 (g) 이다. M = amount of sample (g).
상기 치환도는 CMC 수용액에 있어서, 마이크로 겔의 발생량을 감소시켜 주는 직접적인 요인이 되고 있고, 상기 마이크로 겔은 이차 전지의 극판의 표면에서 공극을 발생시키거나 핀홀을 발생시키는 원인이 되고 있다. The degree of substitution is a direct factor in reducing the amount of microgel generated in the CMC aqueous solution, and the microgel causes voids or pinholes on the surface of the electrode plate of the secondary battery.
상기 치환도는 이와 같이 이차 전지의 음극재 코팅 시 핀홀 결함의 발생량을 감소시켜 셀의 접착력을 높일 수 있도록 해줄 뿐만 아니라 이차 전지의 수명을 증가시키는 요인으로 작용할 수 있다. 따라서, CMC 제조방법에 있어서 고치환도는 매우 중요한 기술개발의 핵심적인 포인트라고 할 수 있다. The degree of substitution reduces the amount of pinhole defects during coating of the negative electrode material of the secondary battery, thereby increasing cell adhesion, and may act as a factor in increasing the lifespan of the secondary battery. Therefore, in the CMC manufacturing method, high substitution degree can be said to be a very important key point of technology development.
본 발명은 이와 같은 점들을 염두에 두고, 상기 비교예 및 상기 각 실시예를 통하여, 최종 CMC 제품의 점도 및 치환도를 측정하였고, 그 결과를 아래의 표 2로 나타냈다. With these points in mind, the present invention measured the viscosity and degree of substitution of the final CMC product through the comparative examples and each of the examples, and the results are shown in Table 2 below.
도 2는 비교예 1 및 실시예 1-1 내지 3-2의 점도와 치환도를 각각 나타낸 그래프이다.2 is a graph showing the viscosity and degree of substitution of Comparative Example 1 and Examples 1-1 to 3-2, respectively.
표 2에 나타난 바와 같이, 알칼리화 단계와 카르복시메틸화 단계를 2~3회 반복 시 1.0 이상의 DS 값을 나타냈다. 이렇듯 알칼리화 단계와 카르복시메틸화 단계를 반복하여 고치환도의 CMC를 얻을 수 있다. 그러나 반응횟수 및 시간이 길어질수록 치환도는 증가하지만 그에 따라 점도가 감소하는 현상을 보였다. As shown in Table 2, when the alkalization step and the carboxymethylation step were repeated 2 to 3 times, a DS value of 1.0 or more was exhibited. As such, the alkalization step and the carboxymethylation step may be repeated to obtain CMC with a high degree of substitution. However, as the number of reactions and time increased, the degree of substitution increased, but the viscosity decreased accordingly.
상기 언급한 문제를 해결하기 위해 본 발명에서의 반응 사이클 2회 이상에서 반응 조건 (반응시간, 반응물 투입량 등)의 변화를 통해 점도 감소 현상 없이 고치환도 CMC를 제조하는 방법을 제공한다. In order to solve the above-mentioned problems, a method for preparing CMC with high substitution degree without a decrease in viscosity through a change in reaction conditions (reaction time, reactant input amount, etc.) in two or more reaction cycles in the present invention is provided.
<비교예 2><Comparative Example 2>
에탄올이 담긴 니더에 분쇄한 린터펄프 100g을 투입하여 교반하였다. 교반 후에 알칼리화 단계로 NaOH 150g을 넣고 60분 동안 반응을 진행하였다. 그리고 카르복시메틸화 단계로 MCA 150g을 투입하고 25 ℃ 에서 60 ℃로 승온하여 15분 반응을 진행하였다. 100 g of pulverized linterpulp was added to a kneader containing ethanol and stirred. After stirring, 150 g of NaOH was added as an alkalization step and the reaction was carried out for 60 minutes. Then, 150 g of MCA was added to the carboxymethylation step, and the reaction was performed for 15 minutes by raising the temperature from 25 °C to 60 °C.
온도를 상온으로 냉각시켜 다시 상기 알칼리화 단계와 카르복시메틸화 단계를 2회 반복하였다. The temperature was cooled to room temperature, and the alkalization step and the carboxymethylation step were repeated twice.
반응이 종료된 샘플에 에탄올로 세척하며 0.1 M 염산(HCl)을 가하여 중화시켜서 pH 6.5 내지 7.5로 조정시킨 후, 여과하여 건조기에 건조시켰다. 건조된 반응물을 분쇄하여 최종 수득물인 CMC를 제조하였다.After the reaction was completed, the sample was washed with ethanol, neutralized by adding 0.1 M hydrochloric acid (HCl) to adjust the pH to 6.5 to 7.5, filtered, and dried in a dryer. The dried reactant was pulverized to prepare CMC as a final product.
<실시예 4-1>: 알칼리화 단계 시간 감소 1<Example 4-1>: Alkalization step time reduction 1
상기 비교예 2와 동일한 방법으로 CMC분말을 제조하되, 알칼리화 반응 시 1회에는 60분 동안, 2회에는 60분 동안, 그리고 3회에는 30분 동안 반응시켰다. CMC powder was prepared in the same manner as in Comparative Example 2, but the alkalization reaction was reacted for 60 minutes at the first time, 60 minutes at the second time, and 30 minutes at the third time.
알칼리화 반응 시간을 제외한 다른 조건은 비교예 2와 동일하게 진행하였다.Other conditions except for the alkalinization reaction time were carried out in the same manner as in Comparative Example 2.
<실시예 4-2>: 알칼리화 단계 시간 감소 2<Example 4-2>: Alkalization step time reduction 2
상기 비교예 2와 동일한 방법으로 CMC분말을 제조하되, 알칼리화 반응 시 1회에는 60분 동안, 2회에는 30분 동안, 3회에는 30분 동안 반응시켰다. CMC powder was prepared in the same manner as in Comparative Example 2, but the alkalization reaction was reacted for 60 minutes at the first time, 30 minutes at the second time, and 30 minutes at the third time.
알칼리화 반응 시간을 제외한 다른 조건은 비교예 2와 동일하게 진행하였다.Other conditions except for the alkalinization reaction time were carried out in the same manner as in Comparative Example 2.
<실시예 4-3>: 알칼리화 단계 시간 감소 3<Example 4-3>: Alkalization step time reduction 3
상기 비교예 2와 동일한 방법으로 CMC분말을 제조하되, 알칼리화 반응 시 1회에는 30분 동안, 2회에는 30분 동안, 3회에는 30분 동안 반응시켰다. CMC powder was prepared in the same manner as in Comparative Example 2, but the alkalization reaction was reacted for 30 minutes at the first time, 30 minutes at the second time, and 30 minutes at the third time.
알칼리화 반응 시간을 제외한 다른 조건은 비교예 2와 동일하게 진행하였다.Other conditions except for the alkalinization reaction time were carried out in the same manner as in Comparative Example 2.
<실시예 5-1>: 카르복시메틸화 단계 시간 감소 1<Example 5-1>: Carboxymethylation step time reduction 1
상기 비교예 2와 동일한 방법으로 CMC분말을 제조하되, 카르복시메틸화 반응 시 1회에는 15분 동안, 2회에는 15분 동안, 그리고 3회에는 7.5분 동안 반응시켰다. CMC powder was prepared in the same manner as in Comparative Example 2, but the carboxymethylation was reacted for 15 minutes at the first time, 15 minutes at the second time, and 7.5 minutes at the third time.
상기 카르복시메틸화 반응 시간을 제외한 다른 조건은 비교예 2와 동일하게 진행하였다.Other conditions except for the carboxymethylation reaction time were carried out in the same manner as in Comparative Example 2.
<실시예 5-2>: 카르복시메틸화 단계 시간 감소 2<Example 5-2>: Carboxymethylation step time reduction 2
상기 비교예 2와 동일한 방법으로 CMC분말을 제조하되, 카르복시메틸화 반응 시 1회에는 15분 동안, 2회에는 7.5분 동안, 그리고 3회에는 7.5분 동안 반응시켰다. CMC powder was prepared in the same manner as in Comparative Example 2, but the carboxymethylation was reacted for 15 minutes at the first time, 7.5 minutes at the second time, and 7.5 minutes at the third time.
상기 카르복시메틸화 반응 시간을 제외한 다른 조건은 비교예 2와 동일하게 진행하였다. Other conditions except for the carboxymethylation reaction time were carried out in the same manner as in Comparative Example 2.
<실시예 5-3>: 카르복시메틸화 단계 시간 감소 3<Example 5-3>: Carboxymethylation step time reduction 3
상기 비교예 2와 동일한 방법으로 CMC분말을 제조하되, 카르복시메틸화 반응 시 1회에는 7.5분 동안, 2회에는 7.5분 동안, 그리고 3회에는 7.5분 동안 반응시켰다. CMC powder was prepared in the same manner as in Comparative Example 2, but the carboxymethylation was reacted for 7.5 minutes at the first time, 7.5 minutes at the second time, and 7.5 minutes at the third time.
상기 카르복시메틸화 반응 시간을 제외한 다른 조건은 비교예 2와 동일하게 진행하였다. Other conditions except for the carboxymethylation reaction time were carried out in the same manner as in Comparative Example 2.
<실시예 6-1>: 반응물 투입량 감소 1<Example 6-1>: Reduction of reactant input 1
상기 비교예 2와 동일한 방법으로 CMC분말을 제조하되, 반응물 투입량을 NaOH, MCA 동량으로 1회에는 150g, 2회에는 150g, 3회에는 100g 투입하였다. CMC powder was prepared in the same manner as in Comparative Example 2, but the reactant input was 150 g at the first time, 150 g at the second time, and 100 g at the third time with the same amount of NaOH and MCA.
반응물 투입량을 제외한 다른 조건은 비교예 2와 동일하게 진행하였다.Other conditions except for the input amount of the reactants were performed in the same manner as in Comparative Example 2.
<실시예 6-2>: 반응물 투입량 감소 2<Example 6-2>: Reduction of reactant input 2
상기 비교예 2와 동일한 방법으로 CMC분말을 제조하되, 반응물 투입량을 NaOH, MCA 동량으로 1회에는 150g, 2회에는 100g, 3회에는 100g 투입하였다. CMC powder was prepared in the same manner as in Comparative Example 2, but the reactant input was 150 g at the first time, 100 g at the second time, and 100 g at the third time with the same amount of NaOH and MCA.
반응물 투입량을 제외한 다른 조건은 비교예 2와 동일하게 진행하였다.Other conditions except for the input amount of the reactants were performed in the same manner as in Comparative Example 2.
<실시예 6-3>: 반응물 투입량 감소 3<Example 6-3>: Reduction of reactant input 3
상기 비교예 2와 동일한 방법으로 CMC분말을 제조하되, 반응물 투입량을 NaOH, MCA 동량으로 1회에는 100g, 2회에는 100g, 3회에는 100g 투입하였다. CMC powder was prepared in the same manner as in Comparative Example 2, but the reactant input was 100 g at the first time, 100 g at the second time, and 100 g at the third time with the same amount of NaOH and MCA.
반응물 투입량을 제외한 다른 조건은 비교예 2와 동일하게 진행하였다.Other conditions except for the input amount of the reactants were performed in the same manner as in Comparative Example 2.
상기 비교예 2 및 실시예 4-1 내지 6-3의 제조 조건을 표 3에 나타내었다.Table 3 shows the manufacturing conditions of Comparative Example 2 and Examples 4-1 to 6-3.
상기 비교예 2와 실시예 4-1 내지 실시예 4-3; 실시예 5-1 내지 실시예 5-3; 그리고 실시예 6-1 내지 실시예 6-3에 의하여 얻은 최종 CMC의 성능을 확인하기 위하여, 각각 점도와 치환도를 위와 동일한 방식으로 측정하였다. Comparative Example 2 and Examples 4-1 to 4-3; Example 5-1 to Example 5-3; In addition, in order to confirm the performance of the final CMCs obtained in Examples 6-1 to 6-3, the viscosity and degree of substitution were measured in the same manner as above.
그 결과를 아래와 같이 표 4로 나타냈다. The results are shown in Table 4 as follows.
도 3은 비교예 2 및 실시예 4-1 내지 6-3의 점도와 치환도를 각각 나타낸 그래프이다.3 is a graph showing the viscosity and degree of substitution of Comparative Example 2 and Examples 4-1 to 6-3, respectively.
표 4에 나타난 바와 같이, 최종 CMC 제품의 치환도는 비교예 2와 비슷한 수준이지만, 그 점도는 매우 증가하였음을 알 수 있다. As shown in Table 4, it can be seen that the degree of substitution of the final CMC product is similar to that of Comparative Example 2, but the viscosity is greatly increased.
이는 상기 표 2에 의한 데이터와 상호 비교하였을 경우, 점도의 상승 효과를 더욱 확실하게 알 수 있다. When this is compared with the data according to Table 2, the synergistic effect of viscosity can be seen more clearly.
결과적으로, 상기 표 4에 의한 측정 데이터를 해석할 경우, 상기 알칼리화 단계와 상기 카르복시메틸화 단계의 반응 사이클을 2회 이상 실시하고, 그 반응 시간과 반응물의 투입량을 변화시킬 경우 최종 CMC의 점도를 감소시키지 않으면서도 고치환도의 제품을 얻을 수 있다는 점을 확인할 수 있었다. As a result, when interpreting the measurement data according to Table 4, the reaction cycle of the alkalization step and the carboxymethylation step was performed two or more times, and the viscosity of the final CMC was reduced when the reaction time and the input amount of the reactants were changed. It was confirmed that a product with a high degree of substitution could be obtained without having to do so.
더 나아가, 본 발명은 기존 합성방법으로는 쉽게 합성하기 어려운 고치환도의 고점도 CMC를 제조하였다. 이는 아래와 같이 하기 실시예 7 내지 10은 상기 실시예 4-1 내지 6-3의 제조조건을 최적화하였다.Furthermore, the present invention prepared a high-viscosity CMC with a high degree of substitution, which is difficult to synthesize easily by conventional synthesis methods. As follows, Examples 7 to 10 optimized the manufacturing conditions of Examples 4-1 to 6-3.
<실시예 7><Example 7>
에탄올이 담긴 니더에 분쇄한 린터펄프 100g을 투입하여 교반하였다. 교반 후에 알칼리화 단계로 NaOH를 넣고 반응을 진행하였다. 그리고 카르복시메틸화 단계로 MCA을 투입 및 승온하여 반응을 진행하였다. 온도를 상온으로 냉각시켜 다시 상기 알칼리화 단계와 카르복시메틸화 단계를 2회 반복하였다. 100 g of pulverized linterpulp was added to a kneader containing ethanol and stirred. After stirring, NaOH was added as an alkalization step and the reaction proceeded. In the carboxymethylation step, MCA was added and the temperature was raised to proceed with the reaction. The temperature was cooled to room temperature, and the alkalization step and the carboxymethylation step were repeated twice.
반응물 투입량을 NaOH, MCA 동량으로 1회 150g, 2회 100g, 3회 100g 투입하였으며, 알칼리화 반응 시 1회 60분, 2회 30분, 3회 30분, 카르복시메틸화 반응 시 1회 15분, 2회 7.5분, 3회 7.5분 반응시켰다.150g of NaOH and MCA were added at the same amount for the first time, 100g for the second time, and 100g for the third time. During the alkalization reaction, the first time was 60 minutes, the second time was 30 minutes, the third time was 30 minutes, and the carboxymethylation reaction was once 15 minutes, 2 times. It was reacted for 7.5 minutes each time and 7.5 minutes three times.
반응이 종료된 샘플에 에탄올로 세척하며 0.1 M 염산(HCl)을 가하여 중화시켜서 pH 6.5 내지 7.5로 조정하여 중화시킨 후, 여과하여 건조기에 건조시켰다. 건조된 반응물을 분쇄하여 최종 수득물인 CMC를 제조하였다.After the reaction was completed, the sample was washed with ethanol, neutralized by adding 0.1 M hydrochloric acid (HCl) to adjust the pH to 6.5 to 7.5, and then filtered and dried in a dryer. The dried reactant was pulverized to prepare CMC as a final product.
<실시예 8><Example 8>
상기 실시예 7과 동일한 방법으로 CMC분말을 제조하되, 반응물 투입량을 NaOH, MCA 동량으로 1회 100g, 2회 100g, 3회 100g 투입하였으며, 알칼리화 반응 시 1회 60분, 2회 30분, 3회 30분, 카르복시메틸화 반응 시 1회 15분, 2회 7.5분, 3회 7.5분 반응시켰다.CMC powder was prepared in the same manner as in Example 7, but the reactant input was 100 g at the first time, 100 g at the second time, and 100 g at the third time with the same amount of NaOH and MCA. 30 minutes for each time, and 15 minutes for 1 time, 7.5 minutes for 2 times, and 7.5 minutes for 3 times in the case of carboxymethylation reaction.
<실시예 9><Example 9>
상기 실시예 7과 동일한 방법으로 CMC분말을 제조하되, 반응물 투입량을 NaOH, MCA 동량으로 1회 150g, 2회 100g, 3회 100g 투입하였으며, 알칼리화 반응 시 1회 30분, 2회 30분, 3회 30분, 카르복시메틸화 반응 시 1회 15분, 2회 7.5분, 3회 7.5분 반응시켰다.CMC powder was prepared in the same manner as in Example 7, but the reactant input was 150 g at the first time, 100 g at the second time, and 100 g at the third time with the same amount of NaOH and MCA. 30 minutes for each time, and 15 minutes for 1 time, 7.5 minutes for 2 times, and 7.5 minutes for 3 times in the case of carboxymethylation reaction.
<실시예 10><Example 10>
상기 실시예 7과 동일한 방법으로 CMC분말을 제조하되, 반응물 투입량을 NaOH, MCA 동량으로 1회 100g, 2회 100g, 3회 100g 투입하였으며, 알칼리화 반응 시 1회 30분, 2회 30분, 3회 30분, 카르복시메틸화 반응 시 1회 15분, 2회 7.5분, 3회 7.5분 반응시켰다.CMC powder was prepared in the same manner as in Example 7, but the reactant input amount was 100g at the first time, 100g at the second time, and 100g at the third time with the same amount of NaOH and MCA. 30 minutes for each time, and 15 minutes for 1 time, 7.5 minutes for 2 times, and 7.5 minutes for 3 times in the case of carboxymethylation reaction.
상기 실시예 7 내지 실시예 10의 반응물 투입과 알칼리화 반응시간 및 카르복시메틸화 반응시간을 포함한 제조 조건을 아래와 같이 표 5에 나타내었다.Preparation conditions, including the input of the reactants and the alkalinization reaction time and the carboxymethylation reaction time of Examples 7 to 10, are shown in Table 5 as follows.
상기 실시예 7 내지 실시예 10에 의하여 얻은 최종 CMC의 성능을 확인하기 위하여, 각각 점도와 치환도를 위와 동일한 방식으로 측정하였다. In order to confirm the performance of the final CMC obtained in Examples 7 to 10, the viscosity and degree of substitution were measured in the same manner as above.
그 결과를 아래와 같이 표 6으로 나타냈다. The results are shown in Table 6 as follows.
도 4는 실시예 7 내지 10의 점도와 치환도를 각각 나타낸 그래프이다.Figure 4 is a graph showing the viscosity and substitution degree of Examples 7 to 10, respectively.
표 6에 나타난 바와 같이, 최종 CMC 제품의 치환도는 더욱 향상되어졌고, 고치환도를 유지한 상태에서 CMC 수용액의 점도의 경우에도 매우 향상되었음을 알 수 있다. As shown in Table 6, it can be seen that the degree of substitution of the final CMC product was further improved, and the viscosity of the CMC aqueous solution was also greatly improved while maintaining a high degree of substitution.
이는 비교예 1의 경우 점도가 1,540 cPs이고, 치환도가 0.78 이었던 것에 비하여, 상기 실시예 7의 경우 그 점도가 2,400 cPs이고, 치환도가 1.12 이었고, 상기 실시예 10의 경우 그 점도가 3,340 cPs이고, 치환도가 1.14 이었던 것에 의하여 객관적으로 확인되고 있었던 것이다. Compared to Comparative Example 1, which had a viscosity of 1,540 cPs and a degree of substitution of 0.78, Example 7 had a viscosity of 2,400 cPs and a degree of substitution of 1.12, and Example 10 had a viscosity of 3,340 cPs. , and the degree of substitution was objectively confirmed by the fact that it was 1.14.
결과적으로, 상기 표 6에 의할 경우에도, 상기 알칼리화 단계와 상기 카르복시메틸화 단계의 반응 사이클을 2회 이상 실시하고, 그 반응 시간과 반응물의 투입량을 변화시킬 경우 최종 CMC의 점도를 향상시키면서도 고치환도의 제품을 얻을 수 있다는 점을 확인할 수 있었다. As a result, even in the case of Table 6, when the reaction cycle of the alkalization step and the carboxymethylation step is performed twice or more, and the reaction time and the input amount of the reactants are changed, the viscosity of the final CMC is improved and the degree of substitution is high. It was confirmed that the product of
따라서, 본 발명에 따른 CMC 제조방법은 알칼리화 단계와 카르복시메틸화 단계를 반복함에 따라서 고치환도의 CMC를 얻을 수 있을 뿐만 아니라, 반응 조건을 변화시킴에 따라서 점도 감소 없이 고치환도의 CMC를 제조할 수 있다. 이에 더하여 반응 조건을 최적화함에 따라서 고치환도의 고점도 CMC를 제조할 수 있다. Therefore, the method for preparing CMC according to the present invention not only obtains CMC with a high degree of substitution by repeating the alkalization step and the carboxymethylation step, but also prepares CMC with a high degree of substitution without a decrease in viscosity by changing the reaction conditions. . In addition, by optimizing the reaction conditions, high viscosity CMC with high substitution degree can be prepared.
이상에서 본 발명에 의한 고치환도 CMC의 제조 방법을 구체적으로 제시하였으나, 이는 본 발명의 실시예를 설명하는 과정에서 구체화된 것일 뿐, 본 발명의 모든 특징이 위에서 언급한 항목에만 적용되는 것이라고 한정하여 해석되어서는 아니될 것이다. In the above, the method for producing CMC with high substitution degree according to the present invention has been specifically presented, but this is only embodied in the process of describing the embodiments of the present invention, and all features of the present invention are limited to being applied only to the items mentioned above. It should not be interpreted as such.
또한, 이 기술분야에서 통상의 지식을 가진 자라면 누구나 본 발명의 명세서의 기재내용에 의하여 다양한 변형 및 모방을 행할 수 있을 것이나, 이 역시 본 발명의 범위를 벗어난 것이 아님은 명백하다고 할 것이다. In addition, anyone skilled in the art will be able to make various modifications and imitations based on the description of the present specification, but it will be clear that this also does not deviate from the scope of the present invention.
Claims (2)
상기 알칼리화 단계와 상기 카르복시메틸화 단계를 1회 또는 2회 반복하여 진행함으로써,
최종 CMC의 수용액의 치환도를 1.0 이상으로 얻을 수 있도록 하는 것을 특징으로 한, 카르복시메틸 셀룰로오스의 제조방법.
An alkalization step (step 1) of preparing alkali cellulose by adding ethanol and sodium hydroxide (NaOH) to pulp-type cellulose; a carboxymethylation step (step 2) of preparing a reactant by adding chloroacetic acid (MCA) to the alkali cellulose; Neutralizing the reactant by washing with ethanol and adding a pH adjusting agent (step 3); filtering and drying the washed and neutralized reactants (step 4); Grinding the dried reactant to obtain CMC (step 5); In the manufacturing method of carboxymethyl cellulose comprising a,
By repeating the alkalinization step and the carboxymethylation step once or twice,
Characterized in that the degree of substitution of the final CMC aqueous solution can be obtained at 1.0 or more, a method for producing carboxymethyl cellulose.
상기 알칼리화 단계에서 수산화나트륨의 투입량과 반응시간을 조절하고, 상기 카르복시메틸화 단계에서 클로로아세트산 (MCA)의 투입량과 반응시간을 조절하고,
상기 알칼리화 단계 및 상기 카르복시메틸화 단계를 1회 또는 2회 반복하여 진행함으로써,
최종 CMC의 수용액의 점도를 감소시키지 않으면서 치환도가 1.0 이상을 얻을 수 있도록 하는 것을 특징으로 한, 카르복시메틸 셀룰로오스의 제조방법.
According to claim 1,
Adjusting the amount and reaction time of sodium hydroxide in the alkalization step, and adjusting the amount and reaction time of chloroacetic acid (MCA) in the carboxymethylation step,
By repeating the alkalinization step and the carboxymethylation step once or twice,
A method for producing carboxymethyl cellulose, characterized by obtaining a degree of substitution of 1.0 or more without reducing the viscosity of the final aqueous solution of CMC.
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| KR100650097B1 (en) | 1999-08-13 | 2006-11-27 | 볼프발스로데에이지 | Process for the Production of Carboxymethylcellulose |
| KR20200106358A (en) | 2019-03-04 | 2020-09-14 | 롯데정밀화학 주식회사 | Method of manufacturing carboxymethyl cellulose particles, carboxymethyl cellulose particles and absorbent articles including the same |
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| KR100650097B1 (en) | 1999-08-13 | 2006-11-27 | 볼프발스로데에이지 | Process for the Production of Carboxymethylcellulose |
| KR20200106358A (en) | 2019-03-04 | 2020-09-14 | 롯데정밀화학 주식회사 | Method of manufacturing carboxymethyl cellulose particles, carboxymethyl cellulose particles and absorbent articles including the same |
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