KR20060132209A - Process for preparing para-polyamide polymer - Google Patents
Process for preparing para-polyamide polymer Download PDFInfo
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- KR20060132209A KR20060132209A KR1020050052424A KR20050052424A KR20060132209A KR 20060132209 A KR20060132209 A KR 20060132209A KR 1020050052424 A KR1020050052424 A KR 1020050052424A KR 20050052424 A KR20050052424 A KR 20050052424A KR 20060132209 A KR20060132209 A KR 20060132209A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 27
- 239000004952 Polyamide Substances 0.000 title claims abstract description 21
- 229920002647 polyamide Polymers 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 50
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 24
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 23
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 23
- 239000001110 calcium chloride Substances 0.000 claims abstract description 23
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000000835 fiber Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000007792 addition Methods 0.000 claims abstract 2
- 239000004760 aramid Substances 0.000 abstract description 2
- 229920003235 aromatic polyamide Polymers 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 150000004984 aromatic diamines Chemical class 0.000 description 4
- -1 aromatic dicarboxylic acid halide Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- IQNTUYCIRRCRDY-UHFFFAOYSA-N 2,5-dichlorobenzene-1,4-dicarbonyl chloride Chemical compound ClC(=O)C1=CC(Cl)=C(C(Cl)=O)C=C1Cl IQNTUYCIRRCRDY-UHFFFAOYSA-N 0.000 description 1
- MGLZGLAFFOMWPB-UHFFFAOYSA-N 2-chloro-1,4-phenylenediamine Chemical compound NC1=CC=C(N)C(Cl)=C1 MGLZGLAFFOMWPB-UHFFFAOYSA-N 0.000 description 1
- MSWAXXJAPIGEGZ-UHFFFAOYSA-N 2-chlorobenzene-1,4-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C(Cl)=C1 MSWAXXJAPIGEGZ-UHFFFAOYSA-N 0.000 description 1
- OBCSAIDCZQSFQH-UHFFFAOYSA-N 2-methyl-1,4-phenylenediamine Chemical compound CC1=CC(N)=CC=C1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 description 1
- NTNUPCREDHXJEL-UHFFFAOYSA-N 2-methylbenzene-1,4-dicarbonyl chloride Chemical compound CC1=CC(C(Cl)=O)=CC=C1C(Cl)=O NTNUPCREDHXJEL-UHFFFAOYSA-N 0.000 description 1
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- XYQUZYVBQYBQDB-UHFFFAOYSA-N naphthalene-1,5-dicarbonyl chloride Chemical compound C1=CC=C2C(C(=O)Cl)=CC=CC2=C1C(Cl)=O XYQUZYVBQYBQDB-UHFFFAOYSA-N 0.000 description 1
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
- D01F6/905—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides of aromatic polyamides
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Polyamides (AREA)
Abstract
본 발명은 방향족 폴리아미드 섬유의 원료로 사용되는 파라-폴리아미드 중합체의 제조방법에 관한 것이다. 본 발명에 따르면, N-메틸-2-피롤리돈(NMP) 용매에 대하여 염화칼슘을 혼합하여 중합용매를 제조하는 단계; 상기 중합용매에 파라페닐렌 디아민(PPD)을 용해시켜 용액을 제조한 후 냉각하는 단계; 및 상기 용액에 테레프탈로일 클로라이드(TPC)를 두 번으로 나누어 첨가하는 단계를 포함하고, 상기에서 두 번의 첨가는 중량비 3:7로 순차적으로 첨가하는 단계를 포함하는 제조방법으로 파라-폴리아미드 중합체를 제조할 수 있다. The present invention relates to a process for the preparation of para-polyamide polymers used as raw materials for aromatic polyamide fibers. According to the present invention, a step of preparing a polymerization solvent by mixing calcium chloride with respect to N-methyl-2-pyrrolidone (NMP) solvent; Dissolving paraphenylene diamine (PPD) in the polymerization solvent to prepare a solution and then cooling it; And adding terephthaloyl chloride (TPC) in two portions to the solution, wherein the two additions are sequentially added in a weight ratio of 3: 7. Can be prepared.
Description
본 발명은 방향족 폴리아미드 섬유의 원료로 사용되는 파라-폴리아미드 중합체의 제조방법에 관한 것이다. 보다 구체적으로는 N-메틸-2-피롤리돈(N-methyl-2-pyrrolidone: NMP)에 염화칼슘을 용해시키고, 여기에 방향족 디아민과 방향족 디카르복실산 할라이드를 용해하여 중합시키는 파라형 폴리아미드 중합체의 제조방법에 관한 것이다.The present invention relates to a process for the preparation of para-polyamide polymers used as raw materials for aromatic polyamide fibers. More specifically, para-type polyamide in which calcium chloride is dissolved in N-methyl-2-pyrrolidone (NMP) and the aromatic diamine and aromatic dicarboxylic acid halide are dissolved and polymerized. A method for producing a polymer.
지금까지 파라형 방향족 디아민 및 파라형 방향족 디카르복실산 할라이드의 축중합체인 파라형 폴리 아미드류(이하, “파라형 폴리아미드류”라 한다)는 고강도, 고탄성율 및 고내열성을 지니고, -160℃에서도 섬유의 특성을 지니는 내한성을 가지고 있을 뿐만 아니라, 절연성, 내약품성 등이 모두 우수한 첨단의 소재인 것이 공지되어 있다.Until now, para-type polyamides (hereinafter referred to as “para-type polyamides”), which are condensers of para-type aromatic diamines and para-type aromatic dicarboxylic acid halides, have high strength, high modulus, and high heat resistance, -160 It is known that it is a high-tech material which not only has cold resistance which has the characteristic of a fiber at degrees C, but also excellent both insulation and chemical-resistance.
대표적인 파라형 폴리아미드 화합물로서는 폴리(파라-페닐렌 테레프탈아미드)(poly(p-phenylene terephthalamide): PPTA)를 들 수 있다. 일반적으로, PPTA는 아미드계 용매 내에서 테레프탈산 클로라이드(terephthaloyl chloride: TPC)와 파 라페닐렌디아민(p-phenylene diamine:PPD)의 용액축합중합반응에 의하여 중합된다.Representative para-type polyamide compounds include poly (para-phenylene terephthalamide) (poly (p-phenylene terephthalamide): PPTA). In general, PPTA is polymerized by a solution condensation polymerization reaction of terephthaloyl chloride (TPC) and paraphenylenediamine (PPD) in an amide solvent.
[반응식][Scheme]
그런데, PPTA는 유기용매에 대한 용해도가 극히 낮기 때문에 고분자량의 중합체를 얻기 위해서는 용매의 선택이 매우 중요하다. However, PPTA has a very low solubility in organic solvents, so the selection of a solvent is very important to obtain a high molecular weight polymer.
본 발명은 아미드계 용매에 대하여 중합체의 용해도가 향상되고, 고유점도가 3 내지 4 정도인 파라형 폴리아미드 중합체의 제조방법을 제공하는 것을 그 목적으로 한다. It is an object of the present invention to provide a method for producing a para-type polyamide polymer having improved solubility of the polymer in an amide solvent and having an intrinsic viscosity of about 3 to 4.
본 발명의 적절한 실시형태에 따르면, N-메틸-2-피롤리돈(NMP) 용매에 대하여 염화칼슘을 첨가하여 중합용매를 만드는 단계; 상기 중합용매에 파라페닐렌 디아민(PPD)을 용해시켜서 용액을 제조한 후 냉각하는 단계; 및 상기 용액에 테레프 탈로일 클로라이드(TPC)를 두 번으로 나누어 첨가하는 단계를 포함하는 파라 폴리아미드 중합체의 제조방법을 제공할 수 있다.According to a suitable embodiment of the present invention, adding a calcium chloride to the N-methyl-2-pyrrolidone (NMP) solvent to form a polymerization solvent; Dissolving paraphenylene diamine (PPD) in the polymerization solvent to prepare a solution and then cooling it; And it can provide a method for producing a para polyamide polymer comprising the step of adding terephthaloyl chloride (TPC) in two portions to the solution.
본 발명의 또 다른 적절한 실시형태에 따르면, 상기 테레프탈로일 클로라이드(TPC)는 3:7의 중량비로 순차적으로 첨가될 수 있다. According to another suitable embodiment of the present invention, the terephthaloyl chloride (TPC) may be added sequentially in a weight ratio of 3: 7.
본 발명의 또 다른 적절한 실시형태에 따르면, 상기 염화칼슘은 상기 N-메틸-2-피롤리돈(NMP)에 대하여 중량대비 6중량%로 포함될 수 있다.According to another suitable embodiment of the present invention, the calcium chloride may be included in 6% by weight relative to the N-methyl-2-pyrrolidone (NMP).
이하, 본 발명을 보다 상세하게 설명하기로 한다.Hereinafter, the present invention will be described in more detail.
본 발명에 따르면, 폴리아미드 중합체의 용해도를 높이기 위하여 N-메틸-2-피롤리돈(NMP)에 염화칼슘을 첨가하여 중합용매를 만들고, 상기 중합용매에 방향족 디아민과 방향족 디카르복실산 할라이드를 1:1의 몰비로 투입하여 중합시켜서 고유점도 등의 물성이 향상된 파라 폴리아미드 중합체를 제조할 수 있다. According to the present invention, in order to increase the solubility of the polyamide polymer, calcium chloride is added to N-methyl-2-pyrrolidone (NMP) to make a polymerization solvent, and aromatic diamine and aromatic dicarboxylic acid halide is added to the polymerization solvent. A para polyamide polymer having improved physical properties such as intrinsic viscosity can be prepared by adding a polymer in a molar ratio of 1: 1.
본 발명은 폴리아미드 중합체의 용해도를 높이기 위하여, 중합용매인 NMP와 염화칼슘의 혼합용매를 NMP에 대하여 6중량%의 염화칼슘을 첨가하여 제조하는 것이 바람직하며, 염화칼슘이 6중량% 미만으로 첨가되면 TPC와 PPD가 반응을 하는데 염화칼슘이 충분한 염으로서의 작용을 하지 못하고, 염화칼슘이 6중량%를 초과하게 되면 중합용매에 염화칼슘의 석출이 일어나 중합반응을 억제하게 된다.In order to increase the solubility of the polyamide polymer, it is preferable to prepare a mixed solvent of NMP and calcium chloride, which is a polymerization solvent, by adding 6% by weight of calcium chloride to NMP, and when calcium chloride is added below 6% by weight, TPC and When PPD reacts, calcium chloride does not act as a sufficient salt, and when calcium chloride exceeds 6% by weight, precipitation of calcium chloride occurs in the polymerization solvent to inhibit the polymerization reaction.
본 발명에서 사용할 수 있는 방향족 디아민은 파라페닐렌 디아민, 4,4'-디아미노비페닐, 2-메틸-파라페닐렌디아민, 2-클로로-파라페닐렌디아민, 2,6-나프탈렌디아민, 1,5-나프탈렌디아민, 4,4'-디아미노벤즈아닐리드 등을 사용할 수 있다. Aromatic diamines that can be used in the present invention are paraphenylene diamine, 4,4'-diaminobiphenyl, 2-methyl-paraphenylenediamine, 2-chloro-paraphenylenediamine, 2,6-naphthalenediamine, 1 , 5-naphthalenediamine, 4,4'-diaminobenzanilide, and the like can be used.
본 발명에서 사용할 수 있는 방향족 디카르복실산 할라이드는 테레프탈로일 클로라이드(TPC), 4,4'-벤조일 클로라이드, 2-클로로테레프탈로일 클로라이드, 2,5-디클로로테레프탈로일 클로라이드, 2-메틸테레프탈로일 클로라이드, 2,6-나프탈렌카르복실산 클로라이드, 1,5-나프탈렌디카르복실산 클로라이드 등을 들 수 있다.Aromatic dicarboxylic acid halides that can be used in the present invention include terephthaloyl chloride (TPC), 4,4'-benzoyl chloride, 2-chloroterephthaloyl chloride, 2,5-dichloroterephthaloyl chloride, 2-methyl Terephthaloyl chloride, 2,6-naphthalenecarboxylic acid chloride, 1,5-naphthalenedicarboxylic acid chloride, etc. are mentioned.
본 발명은 상기한 NMP와 염화칼슘의 혼합용매에 파라-페닐렌디아민을 첨가한 후, 테레프탈로일 클로라이드(TPC)를 투입하여 중합시켜서 파라-폴리아미드 중합용액을 얻는다. In the present invention, para-phenylenediamine is added to the mixed solvent of NMP and calcium chloride, and then terephthaloyl chloride (TPC) is added to polymerize to obtain a para-polyamide polymerization solution.
본 발명에서 테레프탈로일 클로라이드는 3:7의 비율로 두 번에 나누어 첨가한다. 중합은 0 내지 40℃ 이하의 온도에서 실시하는 것이 바람직하다. 첫 번째 테레프탈로일 클로라이드를 30% 초과로 첨가하면, 분자 사슬이 긴 고분자에 의해 두 번째로 첨가하는 테레프탈로일 클로라이드가 파라페닐렌 디아민과 만날 확률이 떨어지게 된다.In the present invention, terephthaloyl chloride is added in two portions at a ratio of 3: 7. It is preferable to perform superposition | polymerization at the temperature of 0-40 degreeC or less. If the first terephthaloyl chloride is added in excess of 30%, the second terephthaloyl chloride added by the polymer having a long molecular chain is less likely to encounter the paraphenylene diamine.
상기한 중합과정에서 얻어진 중합체의 양은 중합용매에 대하여 5 내지 20중량% 정도가 되게 하는 것이 바람직하다. 중합체의 양을 5중량% 미만으로 할 경우에는 중합속도가 저하하게 되고 장시간 동안 반응을 시켜야 하며, 반대로 중합체의양이 20중량%를 초과하게 할 경우에는 중합이 급격하게 진행되게 되어 공정관리에 어려움이 따라 바람직하지 않다.The amount of the polymer obtained in the above polymerization process is preferably about 5 to 20% by weight based on the polymerization solvent. If the amount of the polymer is less than 5% by weight, the polymerization rate is lowered and the reaction must be carried out for a long time. On the contrary, when the amount of the polymer is more than 20% by weight, the polymerization proceeds rapidly, which makes it difficult to manage the process. This is not desirable accordingly.
다음에서, 본 발명은 제한되지 않는 실시예에 의거하여 더욱 구체적으로 설명된다. 실시예 및 비교예에서 판단기준으로 사용된 고유점도(Inherent Viscosity)는 하기와 같이 정의된다. In the following, the invention is explained in more detail on the basis of non-limiting examples. Inherent Viscosity used as a criterion in Examples and Comparative Examples is defined as follows.
즉, 각각의 용액은 96% 황산 100ml에 파라 폴리아미드 중합체 0.5g을 용해시키거나 96% 황산 용액 자체로 제조되며, 유동시간은 모세관 점도계로 30℃에서 측정하였다. 고유 점도는 하기식에 따라 유동시간비로 계산한다:That is, each solution was dissolved 0.5 g of para polyamide polymer in 100 ml of 96% sulfuric acid or prepared as a 96% sulfuric acid solution itself, and the flow time was measured at 30 ° C. with a capillary viscometer. Intrinsic viscosity is calculated as the flow time ratio according to the following formula:
고유점도 = ln(T/T0)/CIntrinsic Viscosity = ln (T / T 0 ) / C
[상기식에서 T는 파라 폴리아미드/황산 용액의 유동시간을 나타내고, T0는 황산 자체의 유동시간을 나타낸다. C는 파라 폴리아미드/황산 용액중의 파라 폴리아미드중합체의 농도이다.][Wherein T represents the flow time of the para polyamide / sulfuric acid solution, and T 0 represents the flow time of the sulfuric acid itself. C is the concentration of para polyamide polymer in para polyamide / sulfuric acid solution.]
실시 예 1Example 1
1-1 믹싱 비이커가 부착되고 크라이오스태트에 연결되어 바닥이 냉각되어 있는 웨어링 블렌더에 24g의 염화칼슘 가루와 400g의 NMP를 넣어서 혼합하였다. 염화칼슘은 NMP에 대하여 6중량%가 되게 첨가하였다. A 1-1 mixing beaker was attached and connected to a cryostat to cool the bottom of the wear ring blender where 24 g of calcium chloride powder and 400 g of NMP were mixed. Calcium chloride was added to 6% by weight relative to NMP.
혼합용매는 염화칼슘이 고체 상태로 존재하는 것도 있는 현탁액 상태이다. 상기 현탁액에 12.816g의 PPD를 교반하면서 첨가하였다. 만들어진 혼합물을 0℃까지 냉각시켰다. 이어서, 냉각과 강한 교반을 계속하면서 24g의 TPC를 3:7의 비율로 2번으로 나누어 빠르게 첨가하였다. The mixed solvent is a suspension state in which calcium chloride is present in a solid state. To the suspension was added 12.816 g of PPD with stirring. The resulting mixture was cooled to 0 ° C. Then, 24 g of TPC was added rapidly in two portions at a ratio of 3: 7 while cooling and vigorous stirring were continued.
교반을 30분간 계속하면서, 온도를 약 30℃까지 올리면, 크럼이 형성되었다. 이는 중합체 용매에 대하여 PPTA가 7증량% 함유되어 있는 것이다. 크럼이 형성된 용액에 물을 첨가하고, 상기 크럼이 형성된 용액이 현탁액 상태로 되도록 강하게 교반하였다. 여과, 세정 및 건조 후에 고유점도가 3.7인 PPTA를 얻었다.While stirring was continued for 30 minutes, when temperature was raised to about 30 degreeC, a crumb formed. This is 7% by weight of PPTA with respect to the polymer solvent. Water was added to the crumb-forming solution and vigorously stirred to bring the crumb-solution into suspension. PPTA having an intrinsic viscosity of 3.7 was obtained after filtration, washing and drying.
실시 예 2Example 2
NMP에 대하여 염화칼슘을 6중량%가 되게 첨가하고, PPD를 10.986g, TPC를 20.46g 첨가한 것 이외에는 실시 예1과 동일하게 실시하였다. 그 결과, 중합체 용매에 대하여 PPTA가 6중량% 함유되고, 고유점도가 3.9인 PPTA를 얻었다. The same procedure as in Example 1 was carried out except that calcium chloride was added to 6% by weight with respect to NMP, and 10.986 g of PPD and 20.46 g of TPC were added. As a result, PPTA containing 6 weight% of PPTA with respect to a polymer solvent was obtained, and the intrinsic viscosity was 3.9.
실시 예 3Example 3
NMP에 대하여 염화칼슘을 6%가 되게 첨가하고, PPD를 14.648g, TPC를 27.28g 첨가한 것 이외에는 실시 예1과 동일하게 실시하였다. 그 결과, 중합체 용매에 대하여 PPTA가 8중량% 함유되고, 고유점도가 3.5인 PPTA를 얻었다. Calcium chloride was added to 6% with respect to NMP, 14.648g of PPD and 27.28g of TPC were added and it carried out similarly to Example 1. As a result, PPTA containing 8 weight% of PPTA with respect to a polymer solvent was obtained, and 3.5 intrinsic viscosity was obtained.
실시 예 4Example 4
NMP에 대하여 염화칼슘을 6중량%가 되게 첨가하고, PPD를 16.479g, TPC를 30.69g 첨가한 것 이외에는 실시 예1과 동일하게 실시하였다. 그 결과, 중합체 용매에 대하여 PPTA가 9중량% 함유되고, 고유점도가 3.3인 PPTA를 얻었다. Calcium chloride was added to 6% by weight with respect to NMP, and it carried out similarly to Example 1 except having added 16.479g PPD and 30.69g TPC. As a result, PPTA containing 9 weight% of PPTA with respect to a polymer solvent was obtained, and 3.3 intrinsic viscosity was obtained.
비교 예 1Comparative Example 1
NMP에 대하여 염화칼슘을 6중량%가 되게 첨가하고, PPD를 16.479g, TPC를 30.69g를 한번에 첨가한 것 외에는 실시 예1과 동일하게 실시하였다. 그 결과, 중합체 용매에 대하여 PPTA가 9중량% 함유되고, 고유점도가 2.1인 PPTA를 얻었다. Calcium chloride was added to 6% by weight relative to NMP, and 16.479 g of PPD and 30.69 g of TPC were added in the same manner as in Example 1. As a result, PPTA containing 9 weight% of PPTA with respect to a polymer solvent was obtained, and the intrinsic viscosity was 2.1.
비교 예 2Comparative Example 2
NMP에 대하여 염화칼슘을 2중량%가 되게 첨가하고, PPD를 16.479g, TPC를 30.69g를 한번에 첨가한 것 이외에는 실시 예1과 동일하게 실시하였다. 그 결과, 중합체 용매에 대하여 PPTA가 9중량% 함유되고, 고유점도가 1.2인 PPTA를 얻었다. Calcium chloride was added at 2% by weight relative to NMP, and 16.479 g of PPD and 30.69 g of TPC were added in the same manner as in Example 1. As a result, PPTA containing 9 weight% of PPTA with respect to a polymer solvent was obtained, and the intrinsic viscosity was 1.2.
비교 예 3Comparative Example 3
NMP에 대하여 염화칼슘을 2중량%가 되게 첨가하고, PPD를 16.479g, TPC 30.69g를 3:7의 비율로 2번으로 나누어 빠르게 첨가한 이외에는 실시 예1과 동일하게 실시하였다. 그 결과, 중합체 용매에 대하여 PPTA가 9중량% 함유되고, 고유점도가 2.1인 PPTA를 얻었다. Calcium chloride was added to 2% by weight with respect to NMP, and 16.479 g of PPD and 30.69 g of TPC were added in two portions at a ratio of 3: 7. As a result, PPTA containing 9 weight% of PPTA with respect to a polymer solvent was obtained, and the intrinsic viscosity was 2.1.
본 발명에 따른 파라형 폴리아미드 중합체는 고유점도가 3 내지 4로, 본 발명에 따른 중합체를 이용하여 제조하는 폴리아미드 섬유는 우수한 기계적 물성을 가지게 된다. Para-type polyamide polymer according to the present invention has an intrinsic viscosity of 3 to 4, polyamide fibers produced using the polymer according to the present invention will have excellent mechanical properties.
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| CN115787124B (en) * | 2022-12-27 | 2024-02-20 | 宁夏泰和芳纶纤维有限责任公司 | Preparation process of superfine denier para-aramid fiber |
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