KR100347314B1 - Process for producing polyamide excellent in flexibility and transparency - Google Patents
Process for producing polyamide excellent in flexibility and transparency Download PDFInfo
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- KR100347314B1 KR100347314B1 KR1019960076044A KR19960076044A KR100347314B1 KR 100347314 B1 KR100347314 B1 KR 100347314B1 KR 1019960076044 A KR1019960076044 A KR 1019960076044A KR 19960076044 A KR19960076044 A KR 19960076044A KR 100347314 B1 KR100347314 B1 KR 100347314B1
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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- 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
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Abstract
Description
본 발명은 성형제품을 위한 나일론의 제조에 관한 것으로, 보다 상세하게는 두가지 이상의 물성을 혼합하여 비교적 융점이 낮으면서도 사출이 가능한 강도와 투명성을 갖는 것을 특징으로 하는 유연성이 우수면서도 투명성이 우수한 폴리아미드의 제조방법을 제공하는 것이다.The present invention relates to the production of nylon for molded products, more specifically, polyamide having excellent flexibility and excellent transparency, characterized in that it has a relatively low melting point and injection strength and transparency by mixing two or more physical properties It is to provide a manufacturing method.
각각의 개별된 물성을 혼합하며 얻어지는 장점으로 잘 알려진 것은 나일론6 과 나일론66 의 예인데 이들의 혼합물은 많은 영역에서 열가소성적인 특성을 더욱 잘 나타내는 물질이 된다. 하지만 이를 폴리아미드의 부분적 결정성은 투명성을 떨어뜨리고, 이들로 이루어진 투명한 공중합 폴리아미드는 융점이 매우 낮은 단점과 성형이 용이한 강도를 얻기가 어려운 단점이 있다. 또한, 기존의 반방향족 카르복실산을 사용한 투명한 나일론은 우수한 강도를 지니는 반면에 유연성 면에서 단점이 있다.Well-known examples of the benefits of mixing the individual properties are nylon 6 and nylon 66, which are mixtures of materials that exhibit better thermoplastic properties in many areas. However, the partial crystallinity of the polyamide is poor in transparency, the transparent copolymer polyamide consisting of these disadvantages are very low melting point and easy to obtain strength that is easy to form. In addition, the transparent nylon using the conventional semi-aromatic carboxylic acid has a disadvantage in terms of flexibility while having excellent strength.
따라서 투명성과 유연성이 함께 요구되는 성형에 어려움이 많았다.Therefore, there were many difficulties in molding which required transparency and flexibility.
일반적인 투명 폴리아미드의 제조방법으로는 디아민과 이소프탈산 ( U.S.2,696,482 ) 또는 테레프탈산(U.S.2,516,585) 과 같은 반방향족 디 카르복실산에 의한 방법이 알려져 있는데, 이들의 생성물은 용융점도가 매우 높기 때문에 열가소성 중합물로서 중합하기가 매우 어렵다.As a general method for preparing a transparent polyamide, a method using semi-aromatic dicarboxylic acids such as diamine and isophthalic acid (US 2,696,482) or terephthalic acid (US 2,516,585) is known. Since their products have a very high melt viscosity, thermoplastic polymers are known. It is very difficult to polymerize.
또다른 예로는 아디프산, 헥사메틸렌디아민, 카프로락탐과 같은 폴리아미드의 조성물을 합성하여 투명한 폴리아미드를 만드는 것인데 이 폴리아미드는 용제에 매우 불안정하고 구형을 만들면 탁해지는 단점이 있다.Another example is the synthesis of compositions of polyamides such as adipic acid, hexamethylenediamine, caprolactam to make transparent polyamides, which have the disadvantage of being very unstable in solvents and becoming turbid when spherical.
독일 특허 1,595,354 에 비스-(4-아미노-시클로헥실)프로판 과 아디프산 을 기초로하는 폴리아미드는 결정화 경향이 매우 약한 것으로 되어 있어 투명성이 좋으나 이 중합법은 전이점이 매우 높기 때문에 바람직하지 못하다. 낮은 융점을 지닌 폴리아미드로는 아디프산과 같은 선형 디카르복실산과 비스-(4-아미노-시클로헥실)프로판 으로 이루어지는 폴리아미드를 들 수 있는데(미국특허 2,585,163) 이것은 높은 결정성으로 인해 투명성이 좋지 않은 단점이 있다.Polyamides based on bis- (4-amino-cyclohexyl) propane and adipic acid in German Patent No. 1,595,354 have very weak crystallization tendencies and have good transparency, but this polymerization method is not preferred because of its high transition point. Low melting point polyamides include polyamides consisting of bis- (4-amino-cyclohexyl) propane and linear dicarboxylic acids such as adipic acid (US Pat. No. 2,585,163). There is a disadvantage.
독일 특허 1,933,395의 투명 폴리아미드는 비스-(4-아미노-시클로헥실)프로판 과 헥사메틸렌디아민과 테레프탈산 등의 화합물로 이루어져 있는데 특별한 점은 폴리아미드의 치수안정성을 상당히 개신해주는 비스-(4-아미노-시클로헥실)프로판의 비율이 50%를 넘지 않는다는 것이다. 따라서 더 높은 비율의 비스-(4-아미노-시클로헥실)프로판 으로 이루어진 용융점도가 높은 폴리아미드에 비해 사출성형이 용이한 잇점이 있다.The transparent polyamide of German Patent No. 1,933,395 consists of bis- (4-amino-cyclohexyl) propane, hexamethylenediamine and terephthalic acid, and the special feature is bis- (4-amino- which significantly improves the dimensional stability of polyamide. Cyclohexyl) propane does not exceed 50%. Therefore, there is an advantage of easy injection molding compared to a high melt viscosity polyamide composed of a higher proportion of bis- (4-amino-cyclohexyl) propane.
독일특허 2,215,906 (미국특허3,808,181) 에 제안되어 있는 비스-(4-아미노-시클로헥실)프로판과 3-에틸-1,10-데판 디카르복실산의 공중합물은, 용이한 방법으로 투명성이 얻어지기는 하였지만 길고 가지친 탄소고리를 지닌 디카르복실산은130℃ 이상에서 치수안정성을 떨어뜨리는 단점이 있다.The copolymer of bis- (4-amino-cyclohexyl) propane and 3-ethyl-1,10-depane dicarboxylic acid proposed in German Patent No. 2,215,906 (US Pat. No. 3,808,181) can be obtained by an easy method. However, dicarboxylic acid having a long and branched carbon ring has a disadvantage of lowering the dimensional stability above 130 ℃.
더우기 이 폴리아미드의 기본적인 원료인 3-에틸-1,10- 데칸 디 카르복실산의 구입이 용이하지 않은 문제점이 있다.Moreover, there is a problem that it is not easy to purchase 3-ethyl-1,10-decane dicarboxylic acid which is a basic raw material of the polyamide.
또한, 독일특허 2,642,244 에 제안된 투명폴리아미드는 비스-(4-아미노-시클로헥실)프로판, 이소프탈산 그리고 선형의 디아민 염으로 이루어져 있고 아미드 그룹에 대한 메틸렌그룹의 평균수는 최소한 9 정도이다. 이 폴리아미드는 열적인 치수 안정성이 충분하지 못한데 이것은 긴 고리로 된 성분들 때문이며 끓는 물에서는 투명성도 좋지않은 문제점도 있다.In addition, the transparent polyamide proposed in German Patent No. 2,642,244 consists of bis- (4-amino-cyclohexyl) propane, isophthalic acid and linear diamine salts with an average number of methylene groups of at least 9 for the amide group. The polyamides do not have sufficient thermal dimensional stability, which is due to the long ring components and also poor transparency in boiling water.
따라서 본 발명자들은 상기의 문제점을 해결하기위하여 투명성은 물론 성형에서의 강도와 유연성을 갖는 나일론을 개발 하고자 하였다.Therefore, the present inventors have attempted to develop a nylon having transparency and strength and flexibility in molding to solve the above problems.
즉, 20 내지 40 중량%의 카프로락탐과 60 내지 80중량%의 폴리에테르디아민과 방향족 카르복실산의 염을 조성으로 하는 유연성과 투명성이 우수한 폴리아미드의 제조방법을 제공하는 것이다.That is, the present invention provides a method for producing a polyamide having excellent flexibility and transparency comprising 20 to 40% by weight of caprolactam, 60 to 80% by weight of a polyetherdiamine, and a salt of an aromatic carboxylic acid.
일반적으로 나일론의 제조에 사용되는 지방족디아민은 직쇄상 지방족 디아민과 알킬측쇄를 가진 지방족 디아민, 예를들면 테트라메틸렌디아민, 펜타메틸렌디아민, 헥사메틸렌디아인, 옥타메틸렌디아민, 노나메틸렌디아민, 운데카메틸렌디아민, 도데카메틸렌디아민, 5-메틸-노난디아민, 2,4,4-트리메틸헥사메틸렌디아민, 2,2,4 - 트리메틸헥사메틸렌디아민 등이 있다.Aliphatic diamines generally used in the production of nylon are linear aliphatic diamines and aliphatic diamines with alkyl side chains, for example tetramethylenediamine, pentamethylenediamine, hexamethylenediaine, octamethylenediamine, nonamethylenediamine, undecamethylene Diamine, dodecamethylenediamine, 5-methyl-nonanediamine, 2,4,4-trimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, and the like.
본 발명에서는 폴리에테르디아민을 사용 하였고, 그 구조는 다음과 같다.In the present invention, polyetherdiamine was used, and its structure is as follows.
위 구조에서 X는 3 내지 4이다.In the above structure X is 3 to 4.
이 폴리에테르디아민은 테레프탈산 및 이소프탈산과 결합하여 축쇄를 형성하는 역할을 하고 방향족의 카르복실산은 강도를 유지할 수있는 역할을 한다.This polyetherdiamine combines with terephthalic acid and isophthalic acid to form a condensed chain, and the aromatic carboxylic acid plays a role in maintaining strength.
본 발명에서는 테레프탈산이나 이소프탈산같은 디카르복실산 특히 테레프탈산과 폴리에테르 디아민으로 이루어지는 염과 카프로락탐을 사용하여 제조되는 것으로 만약 이소프탈산과 테레프탈산의 혼합물을 디카르복실산으로 사용할 경우 이소프탈산의 양은 전체 카르복실산의 30 중량%가 넘지 않도록 하여야 한다.In the present invention, a dicarboxylic acid such as terephthalic acid or isophthalic acid, in particular, is prepared using a salt consisting of terephthalic acid and polyether diamine and caprolactam. If the mixture of isophthalic acid and terephthalic acid is used as the dicarboxylic acid, the amount of isophthalic acid is total. It should not exceed 30% by weight of carboxylic acid.
테레프탈산이나 이소프탈산과 폴리에테르디아민은 동몰로 투입되며 이들의 염 60 내지 80 중량%, 카프로락탐은 10 내지 40 중량% 정도의 비율로 넣는것이 좋은데, 더욱바람직하기로는 우수한 사출성형을 위해 서카프로락탐은 전체의 20 내지 40 중량% 정도로 유지하는 것이 좋다. 테레프탈산과에테르디아민 염의 비율이 높을 수록 유연성은 떨어지게된다.Terephthalic acid, isophthalic acid, and polyetherdiamine are added in an equimolar amount, and salts of 60 to 80% by weight and caprolactam are preferably added at a ratio of about 10 to 40% by weight, and more preferably circaprolactam for excellent injection molding. It is preferable to maintain about 20 to 40% by weight of silver. The higher the ratio of terephthalic acid and etherdiamine salts, the lower the flexibility.
본 발명에 따른 제조방법을 나타내면 다음과 같다.The manufacturing method according to the present invention is as follows.
1) 방향족의 카르복실산과 폴리에데르디아민으르 이루어진 염의 수용액 을 반응기에 투입한다. 이때 방향족의 카르복실산은 테레프탈산이나 테레프탈산과 이소프탈산과의 혼합물중에 선택한다.1) An aqueous solution of a salt consisting of aromatic carboxylic acid and polyetherdiamine is introduced into the reactor. At this time, the aromatic carboxylic acid is selected from terephthalic acid or a mixture of terephthalic acid and isophthalic acid.
2) 일정비율의 카프로락탐을 반응기에 넣는다.2) Add a proportion of caprolactam to the reactor.
3) 가압하에서 이 수용액을 가열하고 물을 밖으로 방출시키면서 일정압력을 유지한다.3) Maintain constant pressure while heating this aqueous solution under pressure and releasing water out.
4) 반응기의 압력을 대기압으로 낮춘다.4) Lower the pressure of the reactor to atmospheric pressure.
5) 일정점도를 유지 하면서 배출한다.5) Discharge while maintaining a constant viscosity.
이때, 상용의 폴리아미드에 사용되는 열 안정제나 산화방지제 혹은 자외선안정제등을 본 발명의 폴리아미드에 첨가시킬 수 있는데 첨가시기는 중합 전, 후 원하는 단계에서 첨가할 수 있다.At this time, heat stabilizers, antioxidants or ultraviolet stabilizers used in commercial polyamides can be added to the polyamides of the present invention. The addition time can be added at a desired stage before and after polymerization.
본 발명에 따른 폴리아미드는 우수한 투명성, 내약품성,열안정성을 가지며 용융상태에서 변형이 좋고 다양한 사출물과 압출물를 제조할 수 있는 효과를 갖는다.The polyamide according to the present invention has excellent transparency, chemical resistance, thermal stability, good deformation in the molten state, and has the effect of producing various injection moldings and extrudates.
이하 실시예 및 비교예를 들어 본 발명을 더욱 상세히 설명하고자 한다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
실시예 1Example 1
2490g의 테레프탈산과 4595g의 폴리에테르디아민 용액과 3000g의 카프로락탐을 반응기에 넣는다. 여기에 증류수 4000g을 투입하고 질소 분위기로 반응기 내부를 유지하고 260℃에서 2시간동안 반응시키면서 17기압으로 유지하고 280℃로 승온 하면서 반응기 내부의 압력을 상압으로 감소 시킨다. 이렇게 얻어진 공중합 폴리아미드는 열분석기로 측정한 결과 245℃의 융점을 갖는다.2490 g of terephthalic acid, 4595 g of polyetherdiamine solution and 3000 g of caprolactam are placed in the reactor. 4000 g of distilled water was added thereto, and the inside of the reactor was maintained in a nitrogen atmosphere, and the reaction was maintained at 17 atm while reacting at 260 ° C. for 2 hours. The copolymer polyamide thus obtained has a melting point of 245 ° C. as measured by a thermal analyzer.
실시예 2Example 2
1950g의 테레프탈산과 540g의 이소프탈산 그리고 4595g의 폴리에테르디아민용액과 3000g의 카프로락탐을 반응기에 넣는다. 여기에 증류수 4000g을 투입하고실시예1과 동일한 방법으로 중합한다. 이렇게 얻어진 공중합물 폴리아미드는 240℃의 융점을 갖는다.1950 g terephthalic acid, 540 g isophthalic acid, 4595 g polyetherdiamine solution and 3000 g caprolactam are placed in the reactor. 4000 g of distilled water was added thereto and polymerized in the same manner as in Example 1. The copolymer polyamide thus obtained has a melting point of 240 ° C.
비교예 1Comparative Example 1
3320g의 테레프탈산과 3340g의 헥사메틸렌디아민 용액과 3600g의 카프로락탐을 반응기에 넣는다.여기에 5000g의 증류수를 투입하고 실시예 1과동일한 방법으로 중합한다. 이렇게 얻어진 공중합폴리아미드는 255℃의 융점을 갖는다.3320 g of terephthalic acid, 3340 g of hexamethylenediamine solution, and 3600 g of caprolactam are added to the reactor. 5000 g of distilled water is added thereto and polymerized in the same manner as in Example 1. The copolymer polyamide thus obtained has a melting point of 255 ° C.
상기 실시예 및 비교예의 물성을 평가 하여 표.1에 나타내었다.The physical properties of the Examples and Comparative Examples were evaluated and shown in Table 1.
표 1Table 1
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| KR1019960076044A KR100347314B1 (en) | 1996-12-30 | 1996-12-30 | Process for producing polyamide excellent in flexibility and transparency |
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| Country | Link |
|---|---|
| KR (1) | KR100347314B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114605631B (en) * | 2020-12-08 | 2024-03-12 | 台湾化学纤维股份有限公司 | Method for producing transparent polyamide copolymer |
| CN116606433A (en) * | 2023-04-28 | 2023-08-18 | 湘潭大学 | Preparation method and application of heat-resistant transparent polyether amide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6243417A (en) * | 1985-08-20 | 1987-02-25 | Toray Ind Inc | Production of polyether amide resin |
| US5086162A (en) * | 1990-04-10 | 1992-02-04 | Texaco Chemical Company | Polyether amide from polyalkylene glycol diamine and diacid mixture |
| JPH04248836A (en) * | 1991-01-25 | 1992-09-04 | Mitsui Petrochem Ind Ltd | Polyamide resin composition and its production |
-
1996
- 1996-12-30 KR KR1019960076044A patent/KR100347314B1/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6243417A (en) * | 1985-08-20 | 1987-02-25 | Toray Ind Inc | Production of polyether amide resin |
| US5086162A (en) * | 1990-04-10 | 1992-02-04 | Texaco Chemical Company | Polyether amide from polyalkylene glycol diamine and diacid mixture |
| JPH04248836A (en) * | 1991-01-25 | 1992-09-04 | Mitsui Petrochem Ind Ltd | Polyamide resin composition and its production |
Also Published As
| Publication number | Publication date |
|---|---|
| KR19980056774A (en) | 1998-09-25 |
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