KR100369849B1 - Process for crystallizing polyethylene naphthalate - Google Patents
Process for crystallizing polyethylene naphthalate Download PDFInfo
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- KR100369849B1 KR100369849B1 KR1019950066611A KR19950066611A KR100369849B1 KR 100369849 B1 KR100369849 B1 KR 100369849B1 KR 1019950066611 A KR1019950066611 A KR 1019950066611A KR 19950066611 A KR19950066611 A KR 19950066611A KR 100369849 B1 KR100369849 B1 KR 100369849B1
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/88—Post-polymerisation treatment
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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
- C08G10/00—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only
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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
- C08G2250/00—Compositions for preparing crystalline polymers
Abstract
Description
본 발명은 폴리에틸렌나프탈레이트의 결정화 방법에 관한 것으로서, 더욱 상세하게는 용융중합으로 생성된 비결정성 폴리에틸렌나프탈레이트를 결정화할 때 테레프탈산을 투입함으로써 결정화시 발생될 수 있는 융착을 방지하는 방법에 관한 것이다.The present invention relates to a method for crystallizing polyethylene naphthalate, and more particularly, to a method for preventing fusion that may occur during crystallization by introducing terephthalic acid when crystallizing amorphous polyethylene naphthalate produced by melt polymerization.
일반적으로 고분자량의 폴리에스테르는 같은 조성을 갖는 저분자량의 폴리에스테르를 고상(固相)중합시켜 제조하고 있고, 저분자량의 폴리에스테르는 용융중합에 의해 제조하고 있다. 고분자량의 폴리에스테르 제조시 통상적으로 고상(固相)중합 단계를 거치게 되는데, 이는 용융중합에 의한 열분해에 의해 더 이상의 부반응물의 생성을 피하고 비결정성 수 지내에 존재하는 휘발성이 강한 아세트알데하이드 등의 저비점 물질을 제거하는 동시에 초고점도성 용융중합체의 분자량을 증가시키기 위함이다.In general, high molecular weight polyesters are produced by solid phase polymerization of low molecular weight polyesters having the same composition, and low molecular weight polyesters are produced by melt polymerization. In the preparation of high molecular weight polyester, a solid phase polymerization step is usually performed, which avoids the formation of further side reactions by pyrolysis by melt polymerization, and has high volatility such as acetaldehyde present in the amorphous resin. This is to remove the low boiling point material and at the same time increase the molecular weight of the ultrahigh viscosity melt polymer.
용융중합에 의해 생성된 저분자량의 폴리에스테르 즉, 폴리에틸렌테레프탈레이트(이하 "PET'로 표기함) 및 폴리에틸렌나프탈레이트(이하 "PEN'으로 표기함)를 포함하는 대부분의 열가소성 폴리에스테르는 비결정성 물질이며, 이러한 비결정성상태에 있는 저분자량의 폴리에스테르는 고상중합에 앞서서 결정성 상태로 전환시켜 고상중합시 저분자량의 폴리에스테르가 융착되지 않고 펠렛 또는 칩의 상태를 유지하도록 한다. 고상중합을 거치지 않는 경우에도 역시 필수적으로 건조공정을 거침으로써 성형시 가수분해를 방지하도록 하는 바, 건조공정중의 융착을 막기 위해서도 비결정성 폴리에스테르 펠렌 또는 칩은 반드시 결정화되어야만 한다.Most thermoplastic polyesters, including low molecular weight polyesters produced by melt polymerization, namely polyethylene terephthalate (hereinafter referred to as "PET") and polyethylene naphthalate (hereinafter referred to as "PEN"), are amorphous materials. The low molecular weight polyester in the amorphous state is converted to a crystalline state prior to the solid phase polymerization so that the low molecular weight polyester is not fused and maintained in the pellet or chip state during the solid phase polymerization. In the case of not undergoing the solid-state polymerization, it is also essential to prevent hydrolysis during molding by going through a drying process. In order to prevent fusion during the drying process, the amorphous polyester phenylene or chips must be crystallized.
일반적으로 비결정성 폴리에스테르를 결정성 물질로 결정화하기 위해서는 가열방법을 채택하는데, 비결정성 폴리에스테르는 유리전이온도(Tg) 이상의 온도에서 결정이 생기기 바로전까지 점착성을 띠게 된다. 비결정성 폴리에스테르중 PET의 경우, 유리전이온도는 79℃ 정도이고 결정화 온도영역은 대략 125℃ 정도로서 유리전이온도와 결정화 온도의 차이가 비교적 작고 결정화속도가 빠르다. 그러나 PEN의 경우, 유리전이온도가 118℃ 정도이고 결정화온도 영역은 대략 204℃정도로서 PET에 비교하여 유리전이온도와 결정화 온도의 차이가 크고 물질 자체의 결정화속도가 느려 결정화시에 융착이 발생하기 쉽다. 따라서 비결정성 PEN의 고상중합을 위해서는 비결정성 PEN이 융착현상없이 결정화되어야만 한다.In general, in order to crystallize the amorphous polyester into a crystalline material, a heating method is adopted. The amorphous polyester becomes tacky until crystals are formed at a temperature above the glass transition temperature (Tg). In the case of PET in amorphous polyester, the glass transition temperature is about 79 ° C and the crystallization temperature range is about 125 ° C. The difference between the glass transition temperature and the crystallization temperature is relatively small and the crystallization rate is fast. However, in the case of PEN, the glass transition temperature is about 118 ° C and the crystallization temperature range is about 204 ° C. The difference between the glass transition temperature and the crystallization temperature is higher than that of PET, and the crystallization rate of the material itself tends to be fusion-prone. . Therefore, in order to solidify the amorphous PEN, the amorphous PEN must be crystallized without fusion.
종래에도 비결정성 PEN를 결정화하기 위하여 촉매량을 감소시켜 탈장화를 방지하려는 방법을 시도한 바 있으나, 이러한 경우 탈장화는 방지할 수 있지만 융착현상이 발생하는 문제가 있다.Conventionally, in order to crystallize amorphous PEN, attempts have been made to reduce the amount of catalyst to prevent deamination, but in this case, deamination can be prevented, but there is a problem in that fusion occurs.
이에 본 발명에서는 비결정성 PEN이 융착현상없이 고상중합시킬 수 있는 방법에 대하여 연구노력한 결과, PEN 펠렛 또는 칩에 PET고상중합시 원료물질로 사용되고 있는 테레프탈산(terephthalic acid)을 혼합하여 결정화함으로써 본 발명을완성하였다.Therefore, in the present invention, as a result of research on a method for the solid phase polymerization of amorphous PEN without fusion phenomenon, the present invention by mixing the crystals of terephthalic acid (terephthalic acid), which is used as a raw material for PET solid phase polymerization to PEN pellet or chip Completed.
따라서 본 발명은 PEN의 융착현상 없이 비결정성 PEN을 결정화하는 방법을 제공하는데 그 목적이 있다.Accordingly, an object of the present invention is to provide a method for crystallizing amorphous PEN without fusion of PEN.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 비결정성 PEN을 결정화시키는 방법에 있어서, 상기 비결정성 PEN 100 중량부에 대하여 테레프탈산 0.5 ∼ 10 중량부를 혼합하여 결정화시키는 것을 그 특징으로 한다.The present invention is characterized in that the crystallization of amorphous PEN by mixing 0.5 to 10 parts by weight of terephthalic acid with respect to 100 parts by weight of the amorphous PEN.
이와같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명은 비결정성 PEN 펠렛 또는 칩에 테레프탈산을 첨가하여 결정화함으로써 통상적인 결정화방법에서 관측되는 융착현상을 방지하는 방법에 관한 것이다.The present invention relates to a method for preventing fusion phenomenon observed in a conventional crystallization method by crystallizing by adding terephthalic acid to an amorphous PEN pellet or chip.
본 발명에서 사용되는 테레프탈산은 PET고상중합시 사용되는 원료물질로서, 상온에서는 백색의 분말(powder)로 존재하고 300℃ 이상의 온도에서 승화한다. 테레프탈산이 PEN결정화에 사용될 수 있었던 것은 테레프탈산이 부피에 대비하여 표면적이 매우 커서 PEN펠렛 또는 칩 들이 서로 접촉할 수 있는 공간에 테레프탈산 미세분말이 배치됨으로써 소량의 테레프탈산의 첨가에 의해서도 PEN의 융착방지에 커다란 효과를 발휘하기 때문이다. 일반적으로 PEN의 결정화시 결정화 온도가 낮을수록 융착율은 감소하는 경향을 보이나, 온도가 너무 낮을 경우 결정화 속도가 느려 결정화공정예 많은 문제가 있었다. 그러나 본 발명의 제조방법에 의해 테레프탈산을 첨가하여 결정화하는 경우 결정화 속도가 가장 빠른 높은 온도에서도 융착현상 없이 결정화를 실시할 수 있다. PEN결정화시 사용되는 테레프탈산의 사용량은결정화온도 및 결정화 설비에 따라 달라질 수 있는바, 결정화 온도가 낮거나 또는 교반기(stirrer)가 장착된 결정화 설비내에서는 소량의 테레프탈산 첨가에 의해 충분히 PEN의 융착을 방지할 수 있고, 결정화 온도가 높거나 또는 교반기(stirrer)가 장착되어 있지 않은 결정화 설비내에서는 상대적으로 많은 양의 테레프탈산 첨가하여야 한다. 따라서, 대략적으로 PEN펠렛 또는 칩 100 중량부에 대하여 테레프탈산 0.5 ∼ 10 중량부를 혼합하는 것이 바람직하다. 또한 상기 결정화 반응은 180 ∼220 ℃에서 진행됨이 바람직한 바, 만약 결정화온도가 180 ℃ 미만이면 결정화속도가 느려 상업화 하기가 어렵고, 220 ℃를 초과하면 융착현상이 과도하게 발생한다.Terephthalic acid used in the present invention is a raw material used in PET solid phase polymerization, which is present as a white powder at room temperature and sublimates at a temperature of 300 ° C. or higher. Terephthalic acid was able to be used for PEN crystallization because terephthalic acid has a very large surface area for volume, so that terephthalic acid fine powder is placed in a space where PEN pellets or chips can come into contact with each other. This is because it is effective. In general, when PEN is crystallized, the lower the crystallization temperature, the fusion rate tends to decrease, but when the temperature is too low, the crystallization rate is slow, and thus there are many problems in the crystallization process. However, when the crystallization by the addition of terephthalic acid by the production method of the present invention can be crystallized without fusion phenomenon even at high temperature with the fastest crystallization rate. The amount of terephthalic acid used in PEN crystallization may vary depending on the crystallization temperature and the crystallization equipment. In the crystallization facility having a low crystallization temperature or agitator, the addition of a small amount of terephthalic acid prevents the fusion of PEN sufficiently. In a crystallization plant which is capable of high crystallization temperatures or which is not equipped with a stirrer, relatively large amounts of terephthalic acid have to be added. Therefore, it is preferable to mix 0.5-10 weight part of terephthalic acid with respect to 100 weight part of PEN pellets or a chip approximately. In addition, the crystallization reaction is preferably carried out at 180 ~ 220 ℃ bar, if the crystallization temperature is less than 180 ℃ crystallization rate is difficult to commercialize, if it exceeds 220 ℃ excessive fusion occurs.
상기와같은 본 발명의 제조방법에 의해 테레프탈산을 첨가하여 PEN을 결정화한 경우, PEN의 결정화 속도가 가장 빠른 온도인 대략 200℃의 고온에서도 융착현상 없이 PEN 을 결정화할 수 있고, 그리고 기존의 PET 결정화설비에서도 융착현상 없이 PEN을 결정화할 수 있다.When PEN is crystallized by adding terephthalic acid by the manufacturing method of the present invention as described above, PEN can be crystallized without fusion even at a high temperature of about 200 ° C., which is the fastest PEN crystallization rate, and conventional PET crystallization. Even in plants, PEN can be crystallized without fusion.
이와같은 본 발명을 다음의 실시예에 의거하여 더욱 상세히 설명하면 다음과 같은바, 본 발명이 실시예에 의해 한정되는 것은 아니다.If the present invention will be described in more detail based on the following examples, the present invention is not limited by the examples.
실시예 1 ~ 2 및 비교예 1 ~ 2Examples 1 and 2 and Comparative Examples 1 and 2
다음 표1에 나타낸 함량비애 의해 PEN펠렛에 테레프탈산을 고루 섞은 후, 15 rpm의 교반속도로 교반하면서 200℃ 오븐에서 30분간 결정화 시켰다.Next, terephthalic acid was mixed evenly in the PEN pellet by the content ratio shown in Table 1, and then crystallized in an oven at 200 ° C. for 30 minutes while stirring at a stirring speed of 15 rpm.
표 1.Table 1.
상기 표1의 결과에 의하면 본 발명에 따른 실시예 1 ∼ 2에서는 융착현상이 관측되지 않았으나, 비교예 1은 테레프탈산을 첨가하지 않고 결정화한 경우로서 PEN펠렛간의 융착이 발생하여 덩어리 형태로 굳어졌고, 비교예 2는 본 발명의 한정범위를 초과하는 경우로서 융착현상 방지에 효과가 없다.According to the results of Table 1, the fusion phenomenon was not observed in Examples 1 to 2 according to the present invention. In Comparative Example 1, when the crystallization was performed without addition of terephthalic acid, fusion between PEN pellets occurred and it solidified in a lump form. Comparative Example 2 is ineffective in preventing fusion phenomenon as it exceeds the limited range of the present invention.
따라서 본 발명의 PEN의 결정화 방법은 PEN 고상중합 전처리 및 건조전처리 과정에 특히 유용하다.Therefore, the crystallization method of PEN of the present invention is particularly useful in the PEN solid state polymerization pretreatment and the drying pretreatment process.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS62119265A (en) * | 1985-11-20 | 1987-05-30 | Diafoil Co Ltd | Polyester film for packaging |
JPH0477523A (en) * | 1990-07-16 | 1992-03-11 | Mitsui Petrochem Ind Ltd | Hollow-formed pack |
KR930012978A (en) * | 1991-12-30 | 1993-07-21 | 이승동 | Crystallization Method of Polyethylenenaphthalate |
KR930019721A (en) * | 1992-03-19 | 1993-10-18 | 이다가끼 히로시 | Oriented polyester film |
KR0181939B1 (en) * | 1989-09-18 | 1999-05-15 | 카알 에이취.크루코우 | Process for crystallization of polyethylene naphthalate |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS62119265A (en) * | 1985-11-20 | 1987-05-30 | Diafoil Co Ltd | Polyester film for packaging |
KR0181939B1 (en) * | 1989-09-18 | 1999-05-15 | 카알 에이취.크루코우 | Process for crystallization of polyethylene naphthalate |
JPH0477523A (en) * | 1990-07-16 | 1992-03-11 | Mitsui Petrochem Ind Ltd | Hollow-formed pack |
KR930012978A (en) * | 1991-12-30 | 1993-07-21 | 이승동 | Crystallization Method of Polyethylenenaphthalate |
KR930019721A (en) * | 1992-03-19 | 1993-10-18 | 이다가끼 히로시 | Oriented polyester film |
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