JPH06508860A - Copolyesters for high modulus fibers - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] An example of copolyesters for high modulus fibers! The present invention relates to high modulus polyester fibers. More specifically, the present invention , novel polyester compositions, and fibers with excellent tensile properties at room and elevated temperatures. The present invention relates to fibers produced using said composition having the following properties.

background Polyethylene phthalate ("PET"), nylons, e.g. Nylon 6 and nylon 66, as well as rayon, are used for tire yarn and tire cord. are the main synthetic polymers used to make Each polymer is It has its own advantages and disadvantages. PET, the most widely used of these, is Tensile strength and modulus, high glass transition temperature, and good stability have Nylon has excellent strength, stiffness and fatigue resistance, but its glass Because the transition temperature is low and creep is easy, “flat spots” are formed in the tire. This has the serious disadvantage of causing flat spotting. Rayo The material retains a high percentage of its tensile properties at high temperatures, e.g. 150°C. hold Much research has been done to improve the properties of these materials.

One approach is to use materials with higher tensile strength and higher tensile modulus than PET. Attempts are being made to synthesize polyester that retains these properties even at high temperatures. I've been exposed to it. Such materials generally benefit from the inherent advantages of polyesters, e.g. , retain chemical stability. Other polyesters manufactured and evaluated is a condensation polymer of ethylene glycol and 2,6-naphthalene dicarboxylic acid. - Bo! ethylene naphthalate) diPEN’) and 4,4°-biamine 1 ro, incense 1m<4.4”-bibenzoic acid) and ethylene glyco Examples include roul and noholimer. 4.4'-bibenzoic acid and/or 2.6~ Copolymers containing naphthalenedicarboxylic acid as a comonomer in PET are European Patent Application No. 202. Reported in June. 4,4-bi rest Copolymer of aromatic acid, 2,6-naphthalene dicarboxylic acid and ethylene glycol is such that the molar ratio of 4,4'-bibenzoic acid to 2,6-naphthalene dicarboxylic acid is approximately 1= 4 or less, it is particularly useful for producing tire yarn, as disclosed in Japanese Patent Application Laid-Open No. 1973- 135333. This reference indicates that 4.4'-bibenzoic acid is , it has a low softening temperature and a low Young's modulus )], the composition is described as having no value as a tire yarn.

This conclusion suggests that the monomer units derived from 4,4'-bibenzoic acid are two diacids. (i.e. 4.4°-bibenzoic acid) monomer units derived from 2,6-naphthalene dicarboxylic acid In a copolymer (with a ratio of monomer units of 1=3), the softening temperature is similar to that of PEN. This is supported by an example showing that the temperature decreased from 275°C to 238°C. Ru.

In view of the teachings of the above-mentioned patents, monomers derived from 4,4°-bibenzoic acid mer units versus moles of monomer units derived from 2,6-naphthalene dicarboxylic acid The ratio is greater than 1:3 with 2,6-naphthalene dicarboxylic acid and 4.4°- Copolymers of benzoic acid and ethylene glycol are stable at both room temperature and high temperature. It is surprising that the same yields fibers with excellent tensile properties.

Fish screaming example man! The present invention relates to 4,4°-bibenzoic acid, 2,6-naphthalene dicarboxylic acid and ethyl dicarboxylic acid. Contains monomer units derived from lene glycol, but not from terephthalic acid. First, a few monomer units of about 50% or more of the total diacid component are added to 4,4゛-bibenzoin. Copolyester compositions in which the ratio of acid to 2.6-naphthalene dicarboxylic acid is greater than 3. It is a thing. Preferably, the composition has a crystalline melting point of less than about 320°C and an equal volume of In solution of safluoroisopropanol and pentafluorophenol, weight, body On a product basis, at a concentration of O1% and a logarithmic viscosity number of at least about Q, 8 dl/g. Best composition for melt spinning high modulus fibers The compounds are derived from 4,4'-bibenzoic acid and 2,6-naphthalene dicarboxylic acid. containing monomer units in a ratio of about 40:60 to 60:40, the best results are Approximately equimolar amounts of the two diacids are obtained.

To make the polymer suitable for melt spinning, the logarithmic viscosity should be between 0.5 dl/g and approx. A copolyester with an intermediate molecular weight having a range of 1° Odl/g or less is produced by melt polymerization. The polymer is then heated in the solid state at a temperature of about 220 to about 270°C. The number viscosity is at least about 1. Heat for sufficient time to increase to Qdl/g. middle The molecular weight of the copolyester is (1) dialkyl 2,6-naphthalenedicarboxy About 40 to about 60 parts on a molar basis of sylate, dialkyl 4,4゛-bibenzoate and at least about 100 parts of ethylene glycol. The molten mixture is heated with a transesterification catalyst to a temperature of approximately 200°C to ensure sufficient by-product atomization. The alcohol is distilled off to produce a low molecular weight polyester, (2) this low molecular weight polyester is polyester in a molten state together with a polycondensation catalyst at a temperature of about 240°C to about 290°C. Upon heating, an intermediate viscosity having a logarithmic viscosity ranging from 0.8 dl/g to about 1.0 dl/g It can be produced in two steps by producing a molecular weight polyester. can. A preferred dialkyl ester of the two diacids is dimethyl ester. , at this time, the by-product alcohol is methanol.

The copolyesters of the invention spin at high drawdown ratios at relatively low melt temperatures. This allows for high modulus fibers to be melt spun in one step [i.e., boss 1 - No spinning drawing process (post-spinning draw 5tep) ]. Higher melting temperatures result in spun fibers with higher modulus Requires a higher drawdown ratio. The fiber produced by this method has at least The most preferred compositions have a modulus of about 150 gpd, and the most preferred compositions have a modulus of at least about 20 gpd. It has a modulus of 0gPd.

Nagitomo on the same car as the plate I2111 profiles the melting temperature of the copolyesters of the invention as a function of composition. One composition is the one containing 4.4 for the two diacid monomer units combined. Expressed as mol% of 4'-bibenzoic acid.

Figure 2 shows a composition containing equimolar amounts of two diacids at several different melting temperatures. Figure 2 is a plot of fiber modulus as a function of drawdown ratio for .

Figure 3 shows that 1.4.4'-bibenzoic acid and 2,6-naphthalene dicarboxylic acid are 50= For compositions with a molar ratio of 50 and a molar ratio of 60:40, the drawdown ratio versus fiber It is the logarithm of the modulus multiplied by 10 nods.

Figure 4 shows the results for a single fiber of PET and two diacids in a 50:50 molar ratio. Stress-strain at room temperature and 150°C for copolyesters of the invention with Show a curve.

A detailed account of fish roe The present invention relates to the number of monomer units derived from 4,4"-bibenzoic acid versus 2,6"-bibenzoic acid. The ratio of the number of monomer units derived from phthalene dicarboxylic acid is greater than about 1:3 2,6-naphthalene dicarboxylic acid, 4.4゛-bibenzoic acid and ethylene glycol Polyester compositions containing monomer units derived from recalls are disclosed.

These polymers can be made into injection or compression molded films, shaped articles, and Useful in producing high modulus fibers. The melting temperature of the polymer is less than about 320°C. Certain compositions are preferred for applications requiring melt processing.

The polymers of this invention are particularly useful for making high modulus fibers.

4. Monomer units derived from 4'-bibenzoic acid versus 2,6-naphthalenedical As long as the ratio of monomer units derived from bonic acid has a melting temperature of less than about 320°C. If the ratio is greater than 1.3, the fiber is easily produced by melt spinning. can be done. For fiber spinning, the ratio of monomer units derived from two diacids Better results are obtained when the ratio is in the range of about 40:60 to about 60:40. The best results are obtained when approximately equal amounts of the 62 diacids are present.

Compositions useful for melt spinning include fibers that can no longer be melt spun or , Fl or does not change the properties of the fiber to such an extent that it is no longer useful. However, other monomers can also be included. So, for example, below The 2,6-naphthalene dicarboxylic acid monomer unit represented by the following structural formula On the subject of -6-naphthoic acid (III) or a mixture thereof may also be included in the composition. can be done.

Similarly, 4.4°-bibenzoic acid monomer unit (IV) is disclosed herein. Although essential to the composition, 4.4"-biphenol (V), 4-hydroxy -4″-biphenylcarbon 1i9 (Vl) and mixtures thereof are also included. be able to.

It is also within the scope of the present invention to replace some hydrogens in the aromatic ring with non-reactive groups. include. Suitable substituents include halogen atoms, e.g. fluorine, chlorine, odor element or iodine: a lower alkyl group having up to about 4 carbon atoms, e.g. thyl, ethyl, n-butyl or t-butyl; and up to about 4 carbon atoms Examples include methoxy, hydroxy or butoxy. can be lost. Minor bonds other than ester bonds, such as amide bonds, are also within the scope of the present invention. Included within. Therefore, amines of alcohol and phenolic monomers Analogs can also be included at low levels, examples of these include ethylene diamide and 4-aminobenzoic acid. Prephthalic acid is also derived from terephthalic acid. Unless the derived monomer units account for more than about 50% of the diacid monomer units, the It can be contained as a monomer.

In addition, small amounts of higher glycols, such as 1,3-propanediol, 1,4- Substitute ethylene glycol with butanediol and propylene glycol You can also do that. Finally, for other difunctional or polyfunctional numerals, Although not specifically mentioned above, these may also be included.

In order to achieve the high molecular weights required for good fiber properties, It is necessary that the number of hydroxy groups is approximately equal to the number of carboxylic acid groups. did Therefore, pure 2,6-naphthalene dicarboxylic acid and pure 4,4°-bibenzoic acid For compositions in which is the acid monomer, the amount of ethylene glycol on a molar basis must be approximately equal to the sum of these two three hara. Other Mihara When substituted with monomers, the chemistry required to produce high molecular weight polyesters The amount of glycol required to achieve stoichiometry will vary.

The monomers used in the present compositions are readily prepared by methods well known in the art. It will be done. Diacid monomers can be used as fine diacid monomers as free acids or their dimethyl esters. It can be purchased from commercial sources of genomics. Ethylene glycol is It is commercially available from the manufacturer.

2.6-naphthalene dicarboxylic acid, 4.4°-bibenzoic acid and ethylene glyco The crystalline melting point of the copolyesters varies according to the relative temperature of the two miharas.

The melting points of several of these compositions are shown in Table 1 after Example 6; in Figure 1 as a function of the amount of 4.4°-bibenzoic acid, measured as mol % of , to plot. 4. The mole percent of 4°-bibenzoic acid is in the range of about 40% to about 60%. In some cases, the melting point of the copolyester ranges from about 60°C to about 305°C. .

This is the preferred range for melt spinning fibers.

At the upper end of the above range, pyrolysis of the polymer achieves high tensile properties of the fiber. The molecular weight decreases so quickly that it is difficult to do so. At the lower end of the above temperature range, the point Lyesters have low crystallinity and result in poor tensile properties of the fibers. fiber melting The best combination of thermal properties and crystallinity for spinning lies in the middle of this range. . The melting point and crystallinity measured by ΔH in the DSC data shown in Figure 1 are , when the mole percent of 4,4°-bibenzoic acid is within the range of about 20% to about 40%, It seems to pass through the minimum value.

The copolyesters disclosed herein are commonly used to produce polyesters. It can be manufactured by the method used. These methods include glycol Examples include interfacial condensation with trigenic acid chlorides. Polymers are glycol It can also be produced by melt condensation with similar acids or esters of acids. these Methods of are generally well known in the art.

In order to achieve the desired fiber properties, a high logarithmic viscosity number (“1.V,”) As suggested, it is necessary to achieve high molecular weight. Spun fibers have equal volume In a solution of parts of hexafluoroisopropanol and pentafluorophenol, Preferably, when measured at a concentration of 0.1% on a weight 17 volume basis and at 25°C, ■ It has a V value of at least about 0.8 dl/g. Generally, after spinning, 1. V In order to achieve , 1. V, having at least about 1.0 dl/g Polymers are melt-spun, and thermal decomposition and hydrolysis due to trace amounts of water occur during spinning. ■v of the fibers obtained should not be reduced to a value less than about 0.8 dl/g. is preferred.

Melt spinning of polymers having T, V less than about 1.0 dl/g cannot be carried out effectively. However, moisture needs to be removed more carefully, and at high temperatures The residence time of the polymer used in the process needs to be shortened.

High as above 1. V, the polymer has 1. V, range 0.5~ A mid-molecular weight polyester having about 1.0 dl/g is prepared and then solid phase weight By combining, the molecular weight is increased; 1. V, to be at least about 1.0 dl/g. It can be manufactured by

A preferred method of producing intermediate molecular weight polyesters for in-phase polymerization is melt polymerization. This is a two-step method of making a real stick. The first step of melt polymerization involves the formation of two Mihara dialkyls. of esters with ethylene glycol in the presence of a transesterification catalyst. It consists of a transesterification reaction at a temperature range of about 200°C to about 240°C. transesterified anti The reaction is carried out under anhydrous conditions and in an inert atmosphere (eg, nitrogen). dimethyl ether Stell is a preferred dialkyl ester. Diesters are transesterified In the presence of a medium, it is mixed with excess ethylene glycol in the desired ratio. transesterification Catalysts to catalyze the reaction are well known in the art and include Lewis acids and bases, zinc acetate, Calcium acetate, titanium tetrabutoxide, germanium tetraethoxide, and manganese acetate. Manganese acetate is preferred. transesterification reaction As the process proceeds, by-product alcohol is removed by distillation. Preferably When using methyl ester, the by-product is methanol. transesterification The reaction is usually complete in less than about 10 hours, preferably within 2 to 3 hours; 1. V.

Leading to very low molecular weight material with less than about 0.2 dl/g.

In the second step of melt polymerization, a single polycondensation catalyst is added and the temperature is adjusted to about 40℃ to about 290℃. It consists of a polycondensation reaction that raises the range. This reaction removes ethylene glycol Preferably, it is carried out under reduced pressure since the desired intermediate molecular weight needs to be achieved. It will be done. Catalysts for polycondensation reactions are well known in the art and include, for example, Lewis acids and Base, polyphosphoric acid, antimony trioxide, titanium tetraalkoxide, germanium Mutetraethoxide, organic phosphates, organic phosphites, and mixtures thereof A mixture of triphenyl phosphate and antimony trioxide is preferred. stomach. The polycondensation reaction consists of 1. V is in the range of about 0.5 dl/g to about 1.0 dl/g. It is usually completed in less than about 10 hours, preferably in 2 to 3 hours. There are two steps to complete the process.

Mid-molecular weight polyesters are ground into powder or Otherwise, it is pelletized. The powder is dried and then exposed to an inert atmosphere (e.g. nitrogen). Plain flow) r or under reduced pressure, 1. V, increases to at least about 1.0 dl/g It is heated to a temperature in the range of about 20° C. to about 270° C. for about 7 minutes. Achieves high molecular weight The typical time required to accomplish this ranges from about 16 hours to about 24 hours.

The time required to achieve high molecular weight depends on the temperature and the molecular weight of the powder. It can be made long or short. Generally, the higher the temperature, the faster the reaction do. However, the temperature may cause the polymer to coagulate, which can hinder the progress of polymerization. It is best to set the height so that they do not merge.

■ Polyester with a high ~' is suitable for melt spinning into high modulus industrial fibers. Particularly appropriate. Melt spinning methods are well known in the art and are commonly used in the production of PET fibers. and is widely used.

The polyester of the present invention is dried immediately before spinning, preferably in a dry atmosphere or is dried by heating under reduced pressure. The polyester is then passed through a heating zone. 6 where the molten polymer is heated above its melting temperature. are filtered by conventional methods, each with one or more spindles having - or more holes. It is extruded through a thread nozzle. As the polymer is extruded, the extrusion rate The fish are also pulled into the reel at a much faster speed. The ratio of withdrawal speed to extrusion speed is It is a ratio. As the fibers are extruded, they are quenched (cooled) in a gas or air stream The point at which fiber stretching occurs is localized.

The copolyesters of the present invention unexpectedly show that the copolyesters of the present invention can melt-spinning behavior characteristic of remers or thermotropic liquid crystal polymers. It was discovered that it shows. Conventional fibers are typically manufactured separately to achieve high tensile properties. It is necessary to stretch in several post-spinning steps. Thermotropic liquid crystal polymers can be spun into high modulus fibers, usually without the need for a subsequent drawing step. can be done. However, liquid crystal polymers usually cannot be stretched.

The copolyesters of the present invention have the ability to maintain relatively low melt temperatures and high draw down ratios. With this, excellent tensile strength can be achieved in a single spinning process without the need for a subsequent drawing process. tensile properties can be achieved. The melting temperature is just above the melting point of the copolyester. In some cases, excellent tensile properties can also be achieved at relatively low drawdown ratios.

As the melt temperature increases, higher drawdown ratios are required to achieve high tensile properties. Essential. These data are based on approximately equimolar amounts of 2,6-naphthalene dicarboxylic acid. Examples 9-27 for copolyesters containing and 4.4°-bibenzoic acid and are shown in detail in Table 2.

Similar results were obtained for copolyesters containing various amounts of the two Miharas. It was. For example, Figure 2 shows a sample containing equimolar amounts of the two ternary components at 300″C. for the composition (H-contained at 285°C) and at 315°C and 334°C. 4.4'-bibenzoic acid and 2.6-naphthalenedical in a molar ratio of 60.40 Regarding a composition containing a monomer derived from bonic acid (melting point: 304°C) Figure 2 shows a plot of the logarithm of the drawdown ratio as a measure of the fiber modulus. In the composition of both Accordingly, it is observed that the spinning modulus increases with the drawdown ratio. Also, For the 60:40 composition, as the melt temperature increases, the specific modulus It is also recognized that higher drawdown ratios are required to achieve this. In Figure 3 shows that a composition containing equimolar amounts of the two miharas has a higher modulus than a 60:40 composition. It is clear that it generates a curve.

The fiber modulus of spun fibers when keeping the melting temperature low and the drawdown ratio high The fact that it is higher is due to the stress during spinning. at lower temperatures However, the higher the melting temperature and the higher the drawdown ratio, the greater the stress during spinning and the finer the fibers. The long polymer chains themselves increase the ease with which they are stretched in the fiber direction.

Therefore, high stress increases the tensile modulus in spun fibers. becomes.

Copolyesters are melt-spun under conditions that produce high tensile properties in spun fibers. In general, the fiber can only be drawn by a few percent, stomach. However, the fibers are spun under low stress conditions so that the tensile properties are relatively low. In a subsequent process, the spun fibers are drawn at high temperatures to improve their tensile properties. It behaves at least as well as conventional fibers in that it can increase the fiber The tensile properties of are improved upon stretching, but these are achieved under high stress. (i.e., low melting temperature and high draw down ratio).

Delivers high tensile properties in a single spinning step without the need for subsequent drawing steps The fact that fibers can be spun under conditions suggests that it simplifies fiber production methods. It has great value because it can be transformed into In contrast, PET is a continuous process However, this method requires stretching the PET fibers after spinning, so this method is not suitable for this method. It is more complex than the method of invention.

The valuable properties of the fibers of this invention are their excellent tensile properties both at room temperature and at elevated temperatures. It is to have sex. For example, 4,4゛-bibenzoic acid and 2,6-naphthalene di Fibers made of 50.50 copolymers with carboxylic acids were found at room temperature (382 gpd vs. 115 gpd) and 150°C (154 gpd vs. 57 gpd) , commercially available PET tire yarn [Hoechst Ce1anese Cor The registered trademark Trevira Tybe 800 (T revira Type 800) Tensile modular of high denier industrial tire yarn It has a tensile modulus more than twice that of steel.

Another valuable property of the fibers of the present invention is that they The main reason for this is that the hot air shrinkage rate is small. For example, made of 50:50 copolymer The yarn has a hot air shrinkage rate of about 0.7-0.8%, whereas Hoechst C Registered trademark Trevira D 240 manufactured by e1anese Corporation (Trevira mouth 240) High denier industrial yarn has a hot air shrinkage rate of approximately 5.4% has.

Fibers and yarns made using the copolyesters taught herein are Like many other polyester fibers 1i (e.g. PET), subsequent processing is required after spinning. It can be processed in about 20 minutes. Therefore, fibers and yarns are It can be treated with - or more finishing steps. The yarn can also be made using conventional techniques. manufacturing tire cords by twisting or pasting them together. Can be done.

The copolyesters of the present invention can be used for other purposes besides industrial fibers and bases. have For example, copolyesters are monofilament high denier single filament It can be extruded as ment fiber. Copolyesters also have high tensile It can be injection molded into shaped articles with special characteristics or extruded into tapes. Wear. Films, including biaxially oriented films, type 11, are prepared by methods well known in the art. 6 Shaped articles that can be made from these copolyesters are also It can also be manufactured by compression molding. This is especially true for very high melting point compositions. It is useful for

In order that those skilled in the art may more fully understand the present invention, examples are set forth below, including: This does not limit the invention.

Bookmarked Nitrogen inlet and outlet, thermometer, condenser, and mechanical stirrer Add dimethyl 2,6-naph to a 1, IJ 71-hole three diameter resin flask equipped with 29 g<0.11888 mol) of thalene dicarboxylate, dimethyl 4,4°- Bibenzoate 32.1. g (0,11888 mol), ethylene glycol 36 ．． 77 g (0°5930 mol) and 0.070 g of manganese acetate tetrahydrate were added. It was. The mixture was heated to 220° C. for 2.5 hours while the methanol was distilled off. . Triphenyl phosphate 0.0675g and antimony trioxide 0.0225g A polycondensation catalyst consisting of 9 g was added to the mixture. The resulting mixture is stirred , and heated to 270"C. Then, vacuum was applied and the temperature was increased to 283"C. Hold temperature for 2.5 hours. The formed polymer was cooled to room temperature and divided into equal parts by volume. In a solution of hexafluoroin 10 panol and pentafluorophenol, weight / concentration of 0.1% by volume and L V determined at 25 °C, 0.85 dl/ A copolyester of intermediate molecular weight was obtained having g. The polymer has a melting point of 287°C, It had a heat of fusion of 44.6 j/g as measured by D, S, and C.

The above intermediate molecular weight polymer is crushed and passed through a No. 20 mesh sieve. Keshita. The powder was then subjected to solid state polymerization at 220°C for 24 hours under reduced pressure, resulting in the following Under the conditions of 1. V, increased molecular weight polyester with 1.38 dl/g I got Le.

The melting temperature was 288° and the heat of fusion was 62j/g.

Examples 2 to 6 Ethylene glycol, 4,4°-bibenzoic acid and 2,6-naphthalene dicarboxylic acid Other polymer compositions made from phosphoric acid were prepared according to the method of Example 1.

Example 1 4,4°-bibenzoic acid: 50=5 of 2,6-naphthalene dicarboxylic acid The thermal properties of these compositions, including the 0 composition, are summarized in Table 1. The melting point is two Measured as Mihara's mole 06 and plotted in Figure 1 as a function of the amount of 4,4'-bibenzoic acid. Lower 1-shita.

Mol l"' IJ, Temperature" Tg AHf illusion! fi BBA package V1” anus-A u-Ms.

1 50 147 285° None 622 0 0.58 265° 998 763 20 1.25 238° 123° 414 40 N, D, "2 63° 126″'445 60 1.40 304° None 6°6 100 363° None 89 (1) Combining 4,4'-bibenzoic acid and 2,6-naphthalene dicarboxylic acid Mol% of 4,4'-bibenzoic acid expressed as mol% of (2) by DSC endothermic peak (3) Pentafluorophenol/hexafluoroisopropanol solution contains Melt. I can't decide.

Cold voice-1 A sample of a polymer having the composition of Example 1 and having an L V of 1.32 was heated under reduced pressure for 13 min. It was dried overnight at 0°C. The polymer was melt-spun at a melt temperature of 297°C, with an extrusion rate of 0.1 Passed through a 0020” diameter capillary at 28 g/min to produce a single filament fiber. I let it happen. The fibers are quenched in air before being taken off at 175 pf/min, resulting in a fiber density of 6.66 pf. I got the answer. This corresponded to a spin ratio of 360. fart Tensile properties of single fibers were measured using STM test method D3822. this exam was performed at 3” gauge length and 60% strain rate. gPd toughness (T)/I elongation (E )/gpd modulus (11) is T/E/M= 11, 6gpd/3, 8%/382gPd. The fibers are hot - (hot 5 hoe), further stretching was not possible.

Example 8 A set similar to Example 7 was prepared using a melt temperature of 283° C. and an extrusion rate of 0.161 g/min. 1. Another sample of the polymer having V, 1.15 was described in Example 1. I pushed it out in the same way I put it on. Fibers at 5.8 dpf were drawn at 250 carbon per minute.

This corresponds to a spinning drawdown ratio of 409, which was measured according to the method described above in Example 7. has tensile properties T/E/1l=8.4gpd/4.1%/406gpd gave filament.

X Kenreki-22λヱ Composition of Example 1; 1. Spun another sample of the polymer with V, 1.46. Dry prior to threading. By changing the melt temperature during spinning, fiber samples were taken at various speeds. The polymer was extruded as in Example 7, except that it was collected at 100 ml. single fiber The tensile properties and fiber take-off ratios are shown in Table 2. According to the method described in Example 7, Tensile properties were measured.

clothes Melting temperature withdrawal Tensile properties withdrawal [Friend 191 (T,) (g+/win) DPF T(d)E$)/M(d lP-931F° 25 72 2.2/82/87 3310 3+B 50 34 2j/47/I11 7011 3+7° 100 20 3j/ 29/149 12012 317° 200 5.9 5.2/llj/22 3 402+3 317° 330 6.0 5.415.8/264 395 +4 308° 25 67 1.8/96/67 3615 308° 50 39 2.6/19/153 5916 3011° 100 14 4.0 /6.0/201 17517 308° 200g, 6 7.1/6.7/ 269 275+g 30g @ 330 4.11 9.515.2/33849 0+9 298" 25 47 2.0/15/+011 5220 299' ″50 27 4.4/+1/235 81121 299″’+00 1 3 5.3/4.5/267 18022 299° 200 5.9 11. 7/4.9/315 400213 299° 330 3.5 10.7/4 ．． 11/345 68024 290° 25 46 2.9/9.8/118 5225 290' 50 30 5.415.4/285 7926 2B 9” 100 13 9.215.6/322 19027 2g9° 200 7.0 +0.2/4.5/366 340 These data are based on toughness and The fiber tensile properties of durus increase with increasing drawdown ratio and decreasing spinning melt temperature. For example, when copolyester is spun at a melting temperature of 290°C , this melting temperature is only about 5°C higher than the melting point, and the spun fibers are modulus with a drawdown ratio of 79. (Example 25).

If this same polymer has a melting temperature of about 317°C, the spun fiber will have a The draw ratio is about 149 gpd (Example 11), but the draw ratio is 120. 400, the modulus of the spun fibers is within the range of approximately 223-264 gpd ( Examples 12 and 13), the best tensile properties were the lowest melting temperature and highest drawdown. It can also be seen from Table 2 that the ratio can be obtained. For this polymer, several different The fiber modulus vs. draw down ratio is plotted in Figure 2 at the melt temperature. general trend This trend is also evident in Fig. 2, and in order to achieve high tensile properties, a higher Drawdown ratios are required at higher melt temperatures.

Three samples were prepared with the lowest drawdown ratio and higher spinning temperature, Example 9. 14 and 19 are stretched at 200°C on a hot shoe (hOj 5hoe) , giving fibers with improved tensile properties. Other fiber samples are , cannot be stretched. The improved tensile properties of the drawn fibers are shown in Table 3.

Enjusen Chichirei Eiharifusai Nuu1J4 usufl, , Ding (d) / E ($) / II (d9 3, + 6. 0/I0.47228+4 2.1 5.0/11.1/+911+9 1.4 4.7/3.5/240X Jeonggawa-Sumi As described in Example 7, the tensile properties of the fibers were first measured at room temperature and then at 15 Three copolyesters at high temperature by measuring in a heated atmosphere at 0 °C The tensile properties of the composition were evaluated. Commercially available polyester tire yarn, t(oe chst Ce1anese Corporation. High density of registered trademark Trevira Type 800 (Trevira Type 800) A single filament sample of an industrial tire was tested under the same conditions for comparison. . The results are shown in Table 4.

Also used to spin single filament fiber samples of the polymers of the invention Fiber grade PET polymer samples were woven into single filament fibers using the same equipment as It was melt spun into fibers. Polyester at 8% concentration in 0-chlorophenol, 25°C When measured with 1. V, 0.92 dl/g. 1 of this same sample. V, is equal parts of hexafluoroinpropertool and pentafluorophenol 1.22 dl/g at 0.1% weight/volume concentration in solution and at 25°C. Measured. After spinning, the single filament PET fiber was passed through two hot shoes (ho t5hoes) to fully develop tensile properties. Next, add 2 fibers Heat the fibers in a rack placed at % strain in an oven under vacuum at 200°C for 30 minutes. hardened. The tensile properties of this "PET control" are also shown in Table 4. and at room temperature and 150°C for 50.50 copolyester. Figure 4 shows the stress strain curve.

deep red 40:6ONDA:BBA car 5.8gpd/2.5g/324gpd 2.4 gpd/1. H/135gpd50:5ONDA:BBA car +1.6gpd/ 3.8$/382gpd 5.8gpd/4.0$/154gpd60:4ON DA: BBA car 3. Ogpd/4.0/178gpd Trevira without measurement 8. 5gpd/+3.7$/115gpd 5.4gpd/15.5$157gpd type 800 PUT control 10, Ogpd/9.4$/170gpd 6. Ogpd/9. 6g/37gpd*NDA=2.6-naphthalene dicarboxylic acid BBA=4.4' -Bibenzoic acid Big Claw - Suyu Having the composition of Example 1, 1. A sample of the copolyester having V, 1.36 was vacuumed. It was dried overnight at 130°C. The polymer was melted in a 1” diameter extruder and The extrudate is metered into a spin pack using a pump where it is loaded with 70/120 crushed metal. (shattered metal).0.020″ diameter cap. Push the melt at 289 °C through a 20-hole annular spinneret with pillars. I put it out. Crossflow quench is applied to the resulting filament. uench) to localize the fiber drawing points (drag paint). This provides a stable spinning environment and allows the fiber to have a low denier variation along its length. A stable spinning process was generated that produced 1111 fibers with motion. godet system The yarn was redressed with a spinning finish before being passed around.

This thread is eventually taken over by a Leesona type wine goo. It was. The bomber throughput was 7.06 g/min. Pick up at 300+e/min The 210 denier yarn (drawdown ratio = 224) has a tensile property of T/E/1l = 9.5. It had gpd15.2% 7295gPd. Thread pulled at 400 songs/minute The drop ratio -298) is the tensile property T/E/l1l=10.6gpd/4.9%/32 It had 1gpd. The spinning melt temperature was carefully selected as low as possible, but Do not select a force so low that it prevents good performance of the yarn process.

2% hot stretching at 200°C changes the tensile properties of the yarn to T/E/l1=9.3 gpd15. Increase from 9% 7267gpd to 10.5gpd/4.1%/300gpd I also saw this at 1λ. Using AST-Test Method D885, 10” length and 6 Tested with strands (Trick 1) at 0% strain rate.

X-mode - Yumaro Dry pot 1 dieste with equimolar amounts of two Mihara and L V, 1.36 A slot die having a length of 0.250" and a width of 0.005" is melted. was extruded through at 0.3 g/min. The extrudate is cooled in air and the resulting tape is It was picked up at a slow pace. ^Using STM test 0882, the tensile properties of the tape sample were The properties were measured and shown in Table 5. For comparison, Hoechst Ce1anese Corporation's registered trademark Vectra liquid crystal polymer. A sample was similarly extruded into a tape, and the bow I tensile properties were 69 kpsi toughness. ; Elongation, 2.3%; Modulus, 3.5 kkps+.

Table 5 Melting temperature Drawing width Thickness Drawing ratio -1 ff1 (℃) 1 minute (inch) ( shi)) T (kpsi) / E (1) / M (kkpsi) 297° 5 0.0 70 +, 00! 7.9 43j/2.1/3.0290° 5 0.200 1.30 4.8 34.7/3.2/1.729 pi 4 0.080 +, 54 10.1 34.2/2j/2j287° 10 0.060 +, 10 111.9 61.2/3.6/2.9% Example-Yuyu Plasticor Model 64 (Plasticor Model 64) injection molding Logarithmic viscosity number 1.21 prepared according to the method of Example 1 at 310°C using a molded apparatus. Injection molding copolyester with dl/g, 1/8" x 3/8" x 2-1/ 2” tensile and bending test specimens. STM Test Methods D638 and D790 The following mechanical properties were measured using Tensile strength, 6.9Ksi; Modulus , 645Ksi; Elongation at break, 1°28%: Bending strength at break, 13 ．． 84Ksi; bending strength at 5% strain, 17.97Ksi; and bending Modulus, 560 Ksi. For comparison, several commercially available substances are The modulus was measured. ■, PET molding resin with V, 0.76 dl/g, 3 17Ksi; Registered trademark Celanex 2002 (CELA) IEX 2002) Polybutylene terephthalate, 370Ksi; and nylon 66 (Nyl on66), 172Ksi, these modulus values are It was significantly lower than the modulus value of 645bi for Le.

Otetsutsuba - Yuno Produced according to the method of Example 29 using a composition containing equimolar amounts of the two Miharas. The hot air shrinkage rate of the yarn was measured. No stress or strain applied Heat the length of thread to be measured in an oven at 350°F for 30 minutes, and then place the sample in the room. Measurements were made by cooling to room temperature and then determining the % change in length.

High denier workmanufactured by Hoechst Ce1anese Corporation Regarding a sample of industrial yarn, registered trademark Trevira D240 (Trevira 0240) Comparative measurements were also carried out using a similar method.

The yarn of the invention shows a hot air shrinkage of 0.7-0.8%, while Trevira D240 showed a hot air shrinkage rate of 5.4%.

The above-described embodiments of the invention are merely examples, and those skilled in the art will be able to understand (i', variations thereof) It should be understood that it is possible to Therefore, my present invention, Not to be limited to the embodiments described herein, but also to the claims appended hereto. It is intended to be limited and defined only by the claims appended hereto.

FIG.i The mol% of 4,4'-bibenzoic acid in the combined Mihara i Adhi = 1--^U dark blue 1 mountain pot thing (Article 184-8 of the Patent Law) The scope of the claims 1.2.6-naphthalene dicarboxylic acid, 4.4'-bibenzoic acid and ethylene glycol Contains seven units derived from Recall, but derived from TeI/phthalic acid First, deposit the monomer unit at about 50% or more of the total Mihara monomer unit, 2.6-naphtha. The number of monomer units derived from dicarboxylic acid versus 4,4゛-bibenzoic acid The ratio of the number of seven units induced is in the range of about 40:60 to about 60:40. Yes, equal parts of hexafluoroisopropanol and pentafluorophenol When measured at 0.1% concentration on a weight/volume basis and at 25°C in solution with A high molecular weight polyester composition having a viscosity number of at least about 1.0 dl/g.

2. The polyester composition of claim 1 having a crystalline melting point of about 320° C. or less. thing.

3. The polyester composition of claim 1, wherein the ratio is about 50:50. thing.

4. The fiber has an initial modulus of at least about 300 gpd at 25°C. , a fiber comprising the polyester composition of claim 3.

5. Having a tensile strength of at least about 8 g/denier at 25°C. II&W.

6. The fiber has an initial modulus of at least about 200 gpd at 25°C. A fiber comprising the polyester composition according to claim 1.

7. The fiber has an initial modulus of at least about 300 gpd at 25°C. A fiber comprising the polyester composition according to claim 1.

8. A film comprising the polyester composition according to claim 1.

9. A biaxially stretched film comprising the polyester composition according to claim 1.

10. A method for producing the polyester composition according to claim 1, comprising: Dissolution of equal parts of hexafluoroinpropanol and pentafluorophenol Low intrinsic viscosity, measured in liquid at 0.1% concentration on a weight/volume basis and at 25°C. Synthesize an intermediate molecular weight polyester having at least about 0.5 dl/g; To, The medium molecular weight polyester is heated in a solid state at a temperature of about 20°C to about 270°C. C for a period of time sufficient for its logarithmic viscosity to increase to at least about 1.0 dl/g. 0 heat.

A method including each step.

11. The synthesis step includes: 2.6-Naphthalene dicarboxylic acid or its alkyl or dialkyl ester from about 40 to about 60 parts on a molar basis, 4,4°-bibenzoate or its alkyl about 60 to about 40 parts of alcohol or dialkyl ester, and ethylene glycol. The molten mixture containing at least about 100 parts of Heating to a temperature of 00°C to about 240°C forms a low molecular weight polyester and Furthermore, The low molecular weight polyester is heated in the molten state at a temperature of about 24°C in the presence of a polycondensation catalyst. Heating from 0°C to about 290°C to produce the intermediate molecular weight polyester: 11. The method according to claim 10, comprising the steps of:

international search report international search report Continuation of front page (81) Designated countries EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IT, LU, MC, NL, SE), 0A (B F, BJ, CF, CG, CI, CM, GA, GN, ML, MR, SN, TD, T G), AT, AU, BB, BG, BR, CA, CH, DE, DK.

ES, FI, GB, HU, JP, KP, KR, LK, LU, MG, MW, NL, No, PL, RO, SD, SE, SU

Claims (23)

[Claims] 1.2,6-naphthalene dicarboxylic acid, 4,4'-bibenzoic acid and ethylene glycol Contains monomer units derived from recall, but monomer units derived from terephthalic acid. does not contain more than about 50% of the total diacid monomer units, and does not contain 2,6-naphthalene units The number of monomer units derived from dicarboxylic acid versus 4,4'-bibenzoic acid A polyester composition in which the ratio of the number of derived monomer units is greater than 1:3. 2. The polyester composition of claim 1, wherein the polyester composition has a crystalline melting point of less than about 320°C. . 3. Equal parts of hexafluoroisopropanol and pentafluorophenol logarithm when measured at 0.1% concentration on a weight/volume basis and at 25°C in a solution of The polyester of claim 1, having a viscosity number of at least about 0.8 dl/g. Composition. 4. 2. The fiber of claim 1, wherein the fiber has a modulus of at least about 150 gpd. A high modulus fiber containing a polyester composition. 5. A shaped article comprising the composition of claim 1. 6. The number of monomer units derived from said 2,6-naphthalene dicarboxylic acid versus 4 , 4'-bibenzoic acid, the ratio of the number of monomer units derived from about 40:60 to about A polyester composition according to claim 1 in the range of 60:40. 7. The number of monomer units derived from the 2,6-naphthalene dicarboxylic acid is approximately equal to the number of monomer units derived from said 4,4'-bibenzoic acid. Item 1. The polyester composition according to item 1. 8. Claim: The polyester fiber has a modulus of at least about 200 gpd. 7. A high modulus polyester fiber comprising the polyester composition according to 7. 9. The polyester of claim 1 having a logarithmic viscosity number of at least about 1.0 dl/g. 1. A method for synthesizing a composition comprising: (a) equal parts by volume of hexafluoroyl; In a solution of sopropanol and pentafluorophenol, on a weight/volume basis, 0. Intrinsic viscosity number from about 0.5 dl/g to about 1.0 dl, measured at 1% concentration and 25°C Synthesize an intermediate molecular weight polyester having /g; (b) The medium molecular weight polyester is heated in a solid state at a temperature range of about 220°C to about 2°C. At 70°C, the logarithmic viscosity of the polyester increases to at least about 1.0 dl/g. heat for a sufficient period of time to A method including each step. 10. The polyester composition of claim 6 having a logarithmic viscosity of 1.0 dl/g. A method for synthesizing things, (a) dialkyl 2,6-naphthalene dicarboxylate from about 40 to about 60 parts, about 60 to about 40 parts dialkyl 4,4'-bibenzoate on a molar basis , and at least about 100 parts on a molar basis of ethylene glycol. The compound is heated to a temperature range of about 200°C to about 240°C with a transesterification catalyst for 10 minutes. Heat until the by-product alcohol is distilled off and low molecular weight polyester is produced. death; (b) The low molecular weight polyester is heated in a molten state together with a polycondensation catalyst at a temperature Heating to about 240°C to about 290°C, the logarithmic viscosity number is about 0.5 dl/g to about 1.0 d (c) producing a polyester having an intermediate molecular weight of 1/g; The molecular weight polyester is heated in the solid state at a temperature in the range of about 220°C to about 270°C. heating for a sufficient period of time to increase the logarithmic viscosity of the material to a value greater than about 1.0 dl/g. ; A method including each step. 11. The dialkyl 2,6-naphthalenedicarboxylate is dimethyl 2, 6-naphthalene dicarboxylate, and the dialkyl 4,4'-bibenzo ate is dimethyl 4,4'-bibenzoate, and the by-product alcohol is , methanol for synthesizing the polyester composition according to claim 10. Method. 12. The polyester composition according to claim 2 is extruded in a molten state, and the extrusion A high modulus polyester that includes each process of extracting polyester as a continuous fiber. A method for producing an ester fiber, wherein the continuous fiber has a low modulus. A method in which the melt temperature and drawdown ratio are selected such that both have about 150 gpd. 13. A high modulus polyester fiber produced by the method of claim 12. 14. A tire cord comprising the high modulus fiber of claim 13. 15. Extruding the polyester composition according to claim 7 in a molten state, A high modulus polyester that includes each process of extracting polyester as a continuous fiber. A method for producing an ester fiber, wherein the continuous fiber has a low modulus. The method in which the melt temperature and draw down ratio are selected such that both have about 200 gpd. 16. A high modulus polyester fiber produced by the method of claim 15. 17. A tire cord comprising the high modulus fiber of claim 16. 18. A shaped article comprising the composition of claim 1. 19. An extruded tape comprising the composition of claim 1. 20. A biaxially oriented film comprising the composition according to claim 1. 21. A high strength monofilament comprising the composition of claim 1. 22. Essentially 2,6-naphthalene dicarboxylic acid, 4,4'-bibenzoic acid and A polyester composition consisting of monomer units derived from ethylene glycol and ethylene glycol. and the number of monomer units derived from 2,6-naphthalene dicarboxylic acid The ratio of the number of monomer units derived from 4,4'-bibenzoic acid is about 40:60 to A polyester composition in the range of about 60:40. 23. A high modulus polyester fiber comprising the composition of claim 22.