JP2002121268A - Alternating copolyester and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new crystalline alternating copolyester which has both the advantages of PET and PEI. SOLUTION: The alternating copolyester is characterized in that at least 90 mol.% of the polymer repeating units comprise units represented by formula (1) (R is a 2 to 12C divalent aliphatic chain) and that an intrinsic viscosity measured in a phenol/1,1,2,2-tetrachloroethane mixture solvent (weight ratio: 6/4) at 35 deg.C is >=0.1. The alternating copolyester is obtained by reacting terephthalic chloride with bis(ω-2 to 12C hydroxyalkyl)isophthalate and/or by reacting isophthalic chloride with bis(ω-2 to 12C hydroxyalkyl)terephthalate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel alternating copolymerized polyester in which alkylene terephthalate structural units and alkylene isophthalate structural units are alternately arranged adjacent to each other in a polymer chain, and a method for producing the same.

[0002]

2. Description of the Related Art Thermoplastic polyesters containing an aromatic dicarboxylic acid as a whole or a part of a carboxylic acid component are:
Melt polymerization is possible, and it is possible to produce a polymer of any physical properties relatively easily according to the purpose by selecting its composition. A wide variety of brands are manufactured and used.

For example, polyesters represented by PET (polyethylene terephthalate) and PEI (polyethylene isophthalate) are excellent in mechanical, physical and chemical properties, and are therefore used in clothing and industrial fibers and films. Is widely used for various molded articles. In particular, terephthalate polyesters represented by PET have been preferably used in applications that utilize heat resistance and mechanical properties, and isophthalate polyesters represented by PEI have gas barrier properties and low pilling properties.

[0004] However, PET has gas barrier properties,
Improvements in pilling properties are required, and PEI has problems of low crystallinity and low impact resistance. As a technique for improving the disadvantages of each of these single polyesters, a method of partially copolymerizing different kinds of polyesters has been conventionally known. For example, PEI is used to improve the gas barrier properties of PET.
A method such as partially copolymerizing has been studied. But,
Since the copolymer obtained by this method has a primary structure in which terephthalate units and isophthalate units are randomly arranged, the intrinsic crystallinity of each polyester is significantly reduced, and as a result, the physical properties of the molded product are reduced. Is inadequate.

[0005]

SUMMARY OF THE INVENTION The main object of the present invention is to overcome the above-mentioned drawbacks by making the conventional copolymerized polyester chain into a regular primary structure, and to achieve excellent crystallinity and mechanical properties. An object of the present invention is to provide a novel alternating copolymerized polyester. Another object of the present invention is to provide a method for producing such a novel alternating copolymerized polyester.

[0006]

According to the present invention, at least 90 mol% of the polymer repeating units have the following formula (1).

[0007]

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A unit represented by the following formula, preferably

[0009]

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And a limiting viscosity of 0.1 as measured at 35 ° C. using a phenol / 1,1,2,2-tetrachloroethane mixed solvent (weight ratio: 6/4).
As described above, the present invention provides a novel alternating copolymer polyester, which is preferably 0.2 to 2.0.

Further, according to the present invention, ¹³ C-NMR measurement of the alternating copolymerized polyester after polymerization [23 ° C., deuterated chloroform / deuterated trifluoroacetic acid = 3/1 (v
/ V)], the isophthalic acid of the alternating copolymerized polyester comprising the repeating unit represented by the above formula (1)
Derived from the aromatic carbon C (T) directly connected to the carbonyl carbon in the terephthalic acid (T) unit (-IEETEI-) in which both ends are sandwiched between oxyethylene (IE) units Signal P {C (T)} _{-IE- T- EI-} is 133.53
133.49 ppm and 133.57 ppm, which are observed in the chemical shift from 133.54 ppm to 133.54 ppm and appear close to both sides of P {C (T)}- _IETEI- when randomized relative to the integrated intensity of this signal. signal ratio of integrated intensity sum of two signals (both attributed to P {C (T)} _-TETEI- of terephthalic acid aromatic carbon C (T)) (P { C (T)} -TETEI _- /
P {C (T)}- _IETEI- ) is 0.1 or less.

According to the present invention, as a method for producing the above-mentioned novel alternating copolymerized polyester, a hydroxyalkyl group represented by terephthalic acid chloride and bis (2-hydroxyethyl) isophthalate has 2 carbon atoms. And / or bis (ω-hydroxyalkyl) isophthalate, and / or bis (2-hydroxyethyl) terephthalate represented by bis (2-hydroxyethyl) terephthalate having 2 to 12 carbon atoms. A method for producing the above-mentioned alternating copolymerized polyester by reacting with (ω-hydroxyalkyl) terephthalate is provided. Further, according to the present invention, there are provided a method for producing a polyester by carrying out the above reaction in a polar organic solvent and a method for further increasing the degree of polymerization by solid-phase polymerization.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the novel polyester of the present invention, at least 90 mol%, preferably at least 95 mol%, more preferably at least 98 mol% of the polymer repeating unit has the following formula (1)

[0014]

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A unit represented by the following formula, preferably

[0016]

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Is a linear alternating copolymer polyester comprising units represented by the formula:

The alternating copolymerized polyester has two or more ethylene terephthalate units in a range not substantially impairing its properties, for example, less than 10 mol%, preferably less than 5 mol%, more preferably less than 2 mol%. Alternatively, the ethylene isophthalate units may be adjacent to each other.

The molecular weight of the alternating copolymerized polyester according to the present invention is determined by the intrinsic viscosity [η] measured at 35 ° C. using a phenol / 1,1,2,2-tetrachloroethane mixed solvent (weight ratio: 6/4). The value is 0.1 or more, preferably [η] = 0.2 to 2.0. In addition, intrinsic viscosity [η]
If the value is less than 0.1, the properties as a polymer are not sufficient, and the polymer is not suitable for use in ordinary uses such as molding.

In the present invention, the Tg (glass transition temperature) of the alternating copolymer polyester comprising the repeating unit represented by the above formula (1) is 0 ° C. or more, and more preferably 30 to 30 ° C.
75 ° C. Tm (melting point) is between 100 ° C and 260 ° C. Those having a Tm of 100 ° C. or less are not preferred because the crystallinity of the polyester may be low.

In the present invention, the above formula (1) ｛
Alternating weight consisting of a repeating unit represented by the above formula (2)｝
The synthetic polyester has good crystallinity,
as well as ¹³It is possible to identify by C-NMR measurement
You. The above formula (1) based on an X-ray wide-angle photograph, preferably the above formula
(2) copolymerized polyester having a repeating unit represented by
The crystal pattern of a polymer is a homopolymer of its constituents.
PET (polyethylene terephthalate), PEI (poly
Xylene is completely different from
Also from the line wide angle photograph, the alternating copolyester of the present invention is new
Clear polyester material
become. Also,¹³Represented by the above formula by C-NMR measurement
It is also possible to identify polyesters.

The above alternating copolymerized polyester is obtained by reacting terephthalic acid chloride with bis (2-hydroxyalkyl) isophthalate having a hydroxyalkyl group having 2 to 12 carbon atoms and / or isophthalic acid chloride and hydroxyalkyl group. With bis (2-hydroxyalkyl) terephthalate having a hydroxyalkyl group having 2 to 12 carbon atoms.

In a preferred embodiment of the present invention, there is provided a method of reacting terephthalic acid dichloride of the following formula (3) with bis (2-hydroxyethyl) isophthalate of the following formula (4):

[0024]

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Alternatively, it is produced by a method of reacting isophthalic acid chloride of the following formula (5) with bis (2-hydroxyethyl) terephthalate of the following formula (6), or a combination thereof.

[0026]

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In the method of the present invention, the combination of a diacid chloride and a diol may be a combination of a diacid chloride of the above formula (3) and a diol of the above formula (4) or a diacid of the above formula (5). Although a combination of chloride and the diol of the above formula (6) is used, a plurality of combinations of these components may be used simultaneously.

It is preferable that the charged amount of these monomers is such that the diacid chloride and the diol are substantially equimolar. At this time, the diacid chloride component and the diol component are all components of the diacid chloride and the diol. It is used in an amount of 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol to 100%. Here, if the content of the above components is less than 90 mol%, the crystallinity of the polyester may be significantly reduced, which is not preferable.

In the production of the alternating copolymerized polyester, a proportion of less than 10 mol%, preferably less than 5 mol%, more preferably less than 2 mol% is added to the repeating unit represented by the above formula in the polymer chain. To introduce ethylene terephthalate repeating units or ethylene isophthalate repeating units.
(Hydroxyethyl) terephthalate and / or bis (2
-Hydroxyethyl) isophthalate may be used in excess.

The above reaction is carried out by solution polymerization in a polar organic solvent. Organic solvents used for the solution polymerization reaction include N-methyl-2-pyrrolidone, N, N
-High boiling organic solvents such as dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, and sulfolane are used.

When the above-mentioned solution polymerization is carried out industrially, it is preferable to adopt a method in which each monomer component is dissolved in the same solvent in advance and the solutions are mixed by an appropriate method. The reaction temperature is from the freezing point of the solvent to
It is appropriately selected within the range of the boiling point.
Is preferred. It is also possible to adopt a method in which the temperature is set relatively low at the beginning of the reaction and the temperature is gradually increased as the reaction proceeds. The reaction time is suitably about 0.5 to 5 hours.
In a normal case, the reaction product (polymer) precipitates as a solid in the solution. Therefore, the target product can be obtained by filtering and washing with water.

When it is intended to produce a polyester having an intrinsic viscosity [η] of 0.1 or more, preferably 0.2 to 2.0 by the solution polymerization described above, the solution polymerization alone results in a [η].
Since it is often difficult to increase the molecular weight to 1.0 or more, it is possible to obtain a polyester having an increased molecular weight by further solid-phase polymerization.

For example, the above alternating copolymerized polyester (prepolymer) polymerized to an intrinsic viscosity [η] of about 0.1 by this solution polymerization reaction is crystallized, and then subjected to normal pressure under an inert gas stream. Alternatively, the polymer has a glass transition temperature (Tg) or higher and a melting point (Tg) in a high vacuum state of 1 mmHg or lower.
m) is heated to a temperature lower by 5 to 40 ° C., and the degree of polymerization of the polymer is increased by solid-phase polymerization, and ultimately the intrinsic viscosity [η] is 0.2 or more, preferably [η] 0.5 to 0.5. 2.
0 high molecular weight alternating copolymerized polyester.

The alternating copolymer polyester having a repeating unit represented by the above formula according to the present invention, as described above,
It can be identified by an X-ray wide-angle photograph and ¹³ C-NMR measurement. From the crystal pattern of the alternating copolymerized polyester represented by the above formula by X-ray wide-angle photography, it is completely different from the crystal patterns of its constituent homopolymers, PET and PEI. It is clear that Also, ¹³ C-N
It is possible to confirm the polyester represented by the above formula (1) by MR measurement.

Further, the alternating copolymer polyester according to the present invention
Primary structure is 23 ° C, deuterated chloroform / deuterated water
Trifluoroacetic acid in 3/1 (v / v)¹³C-
-It can be clarified by NMR measurement. example
See Macromolecules, [33], 459
6 (2000), random copolymerization of PET and PEI
of a body¹³The findings by C-NMR measurement are shown.
PET and P in measurement at 25 ° C in trifluoroacetic acid
On the aromatic ring of terephthalic acid in a random copolymer of EI
1,4 carbon (ie, α directly linked to carbonyl carbon)
Carbon)), focusing on its signal TC (T).
You. Thus, in the case of a completely random form,
When sandwiched from both sides by the taret unit (-IE-)
Signal P {C (T)}_{-IE- T -EI-}Against both
Next to the randomized signal P {C (T)}_{-TE- T
-EI-}Appears as two signals, and the signal P ｛C
(T)｝_{- IE- T -EI-}Product of these two signals with respect to
The theoretical intensity ratio of the sum of the partial intensities is approximately 1: 1.
Actually, the signal P {C (T)}_{-TE- T -EI-}Very close
A PET unit having a trimer or more such as -T-E-T-E-T-
P {C (T)}
_{-TE- T -EI-}/ P {C (T)}_{-TE- T -EI-}Is more than 1.0
Becomes However, the exchange produced by the method of the invention
For interpolyesters, signals based on alternating units
P {C (T)}_{-IE- T -EI-}Is mainly observed and this main
The other two derived from random copolymerization on the signal
P {C (T)}_{-T -E- T -EI-}Area ratio P of sum of signals
{C (T)}_{-TE- T -EI-}/ P {C (T)}_{- TE- T
-EI-}Is 0.1 or less, preferably 0.05 or less, more preferably
Or 0.03 or less.

[0036]

The novel alternating copolymer polyester of the present invention has the advantages of PET and PEI, is crystalline and has a T
It is a material that can reach m 130 ° C. or more and Tg 60 ° C. or more, and can be made into fibers, films, molded products and the like having excellent mechanical properties by melt molding, and is particularly suitable for bottles. In these molded products, problems such as low crystallinity and low impact characteristics, which are observed in PEI molded products, do not occur. In addition, the polyester is obtained by adding various additives such as a stabilizer, a colorant, an ultraviolet absorber, a release agent, a reinforcing material such as glass fiber, and a filler such as inorganic particles and organic particles. It can also be used as

[0037]

EXAMPLES The present invention will be described below with reference to examples and comparative examples, but these are intended to specifically explain the present invention, and the present invention is not limited thereto. In the examples, “parts” means “parts by weight” unless otherwise specified. The various evaluation items listed in the examples were obtained as follows.

(1) Measurement of intrinsic viscosity [η] The intrinsic viscosity [η] was measured in a phenol / 1,1,2,2-tetrachloroethane mixed solution (weight ratio 6/4) at 35 ° C.

(2) Measurement of melting point, crystallization temperature, glass transition temperature, etc. The glass transition temperature (Tg), melting point (Tm) and enthalpy of fusion (ΔHm) were measured using a Seiko DSC220 differential scanning calorimeter using a nitrogen gas. The temperature was increased at a rate of 10 ° C./min in an air current to perform the measurement.

(3) ¹³ C-NMR measurement The measurement by ¹³ C-NMR was carried out according to JEOL JNR-EX27.
Using 0, the measurement was performed at 23 ° C. in a mixed solvent of deuterated chloroform / deuterated trifluoroacetic acid = 3/1 (v / v).

(4) X-ray Diffraction Measurement Cu K-α1 using Rigaku Denki DX (RAD-B)
The sample was irradiated with X-rays of / 50 kV / 200 mA, and the X-ray wide-angle photograph was measured.

Example 1 25.40 parts of bis (2-hydroxyethyl) terephthalate was dissolved in a mixture of 16.6 parts of dry pyridine and 50 ml of dehydrated N-methyl-2-pyrrolidone at room temperature under a nitrogen stream. Then, a solution prepared by dissolving 20.31 parts of isophthalic acid chloride in 30 ml of dry N-methyl-2-pyrrolidone was added dropwise at 5 ° C on an ice bath, and the mixture was stirred at 5 ° C for 0.5 hours. Subsequently, the mixture was heated and stirred at room temperature for 1 hour, at 40 ° C. for 2 hours, and further at 60 ° C. for 2 hours, and then cooled to room temperature.
, And the precipitated white solid was separated by filtration. This is water 100
After washing 5 times with 0 ml and 2 times with 500 ml of acetone, the copolymer was dried in vacuo at 120 ° C.
5.5 parts (95% yield) were obtained.

The polymerization results and thermal properties [glass transition temperature (Tg), melting point (Tm), enthalpy of fusion (ΔH)] of this polymer are shown in Table 1 below. As shown in Table 1, this polymer had an intrinsic viscosity [η] = 0.60, Tg
= 70 ° C, Tm = 139 ° C, enthalpy of fusion ΔH = 3
It was 5.2 j / g.

The polymer obtained in the above experiment was converted to deuterated chloroform / deuterated trifluoroacetic acid = 3/1.
(V / v) ¹³ C-NMR measurement was performed at 23 ° C. in a mixed solvent, and the results were as shown in Table 2 below.

From the spectrum chart shown in FIG. 1, it can be seen from the isophthalic acid-oxyethylene ((IE) unit) of the alternating polyester that the terephthalic acid (T) unit (-IETE-E- _133.531 ppm of the signal P {C (T)}- _IETEI- derived from the aromatic carbon C (T) directly connected to the carbonyl carbon in I-)
Was observed. Also, when the polymer sequence are randomized, appear in close proximity to the P {C (T)} _-IETEI- on both sides 133.49ppm and 133.57ppm
(All of which belong to the aromatic carbon C (T) of terephthalic acid of P {C (T)}- _TETEI- ) were not confirmed at all.

Comparative Example 1 Next, as a comparative example, a random copolymer of PET and PEI was prepared. That is, 10
Dimethyl terephthalate 1 in a 0 ml three-necked flask
8.45 parts, 18.45 parts of dimethyl isophthalate, 29.80 parts of ethylene glycol (0.24 mol) and 0.25 ml of a 1% by weight solution of tetrabutoxytitanium in toluene (about 0.03 mol% based on the polymer) And heated to 190 ° C. under a nitrogen atmosphere, and stirring was started. As the transesterification proceeds, methanol as a by-product starts to distill, and in about 1 hour, almost the theoretical amount of methanol evaporates, and bis (2-
(Hydroxyethyl) terephthalate / isophthalate was formed.

Thereafter, the mixture was finally heated to 220 ° C. over 30 minutes to remove excess ethylene glycol, and the system was depressurized with a water aspirator, and a V1 reaction was carried out at 240 ° C. for 30 minutes. Finally, the pressure was reduced to 0.1 mmHg by a vacuum pump to start the V2 reaction, and polycondensation was further performed at 250 ° C. for 1 hour. Since the polycondensation proceeded sufficiently and almost the theoretical amount of ethylene glycol was distilled off, the reaction was completed and the PET / PEI was sampled and pelletized while the contents were warm.
A random copolymer was obtained.

The polymerization results and thermal properties of this polymer are shown in Table 1 above together with the polymer of Example 1. This polymer had an intrinsic viscosity [η] = 0.70 and Tg = 68 ° C., but was amorphous, and no melting point was observed.

This random copolymer was subjected to ¹³ C-NMR measurement in a mixed solvent of deuterated chloroform / deuterated trifluoroacetic acid = 3/1 (v / v) at 23 ° C.
Assigned as in Table 3.

From the spectrum chart shown in FIG. 2, terephthalic acid (T) in which both ends are interposed between isophthalic acid-oxyethylene (IE) units of the alternating copolymerized polyester.
A signal P derived from an aromatic carbon C (T) directly connected to a carbonyl carbon in the unit (-IEETEI-)
{C (T)}- _{IE- T- EI-} was observed at _133.531 ppm. Also, when randomized, P {C (T)}
_{133.49 ppm} appearing close to _both sides of -IETEI-
And 133.57 ppm signal (both P ｛C
(T)｝ _-TETEI- Terephthalic acid aromatic carbon C
(Attributed to (T)) are also clearly identified, P {C (T)}- _TETEI- / P {C (T)}
_-IETEI- integrated intensity ratio = 1.58.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

Example 2 The alternating copolymer polyester obtained in Example 1 and polyethylene terephthalate (PET) and polyethylene isophthalate (P
Each of the chips of EI) was annealed at 130 ° C. under a vacuum for 1 hour, and the wide-angle X-ray photographs were measured. Table 4 summarizes the results. As is clear from Table 4,
The polyester obtained in Example 1 was completely different from its constituents, PET and PEI, and showed a crystal pattern developed from PEI, which is a homopolymer.

[0055]

[Table 4]

[Brief description of the drawings]

FIG. 1 is a ¹³ C-NMR spectrum chart of an alternating copolymer polyester according to the present invention described in Example 1.

FIG. 2 is a ¹³ C-NMR spectrum chart of a random copolymer of PET and PEI described in Comparative Example 1.

Continuation of the front page F term (reference) 4J029 AA03 AB01 AB04 AC05 AD01 AD06 AD07 AD10 AE01 AE02 AE03 BA03 CB05A CB06A JC123 JC243 JC353 KB02 KC02 KD01 KE09 KE12

Claims (7)

[Claims] 1. The method of claim 1, wherein at least 90 of the polymer repeat units are present.
The mol% is represented by the following formula (1): [R in the above formula (1) is a divalent aliphatic chain having 2 to 12 carbon atoms. And a limiting viscosity of 0.1 as measured at 35 ° C. using a phenol / 1,1,2,2-tetrachloroethane mixed solvent (weight ratio: 6/4).
An alternating copolymerized polyester characterized by the above. 2. At least 90 of the polymer repeat units
The mol% is represented by the following formula (2): And a phenol / 1,1,1,
2,2-tetrachloroethane mixed solvent (weight ratio 6/4)
2. The alternating copolymer polyester according to claim 1, wherein the intrinsic viscosity measured at 35 ° C. by using styrene is 0.1 or more. 3. ¹³ C-NMR of alternating copolymerized polyester
In the measurement (23 ° C., in deuterated chloroform / deuterated trifluoroacetic acid = 3/1 (v / v)), the isophthalic acid-oxyethylene (IE) of the alternating polyester represented by the above formula (2) was obtained. ) Unit, the signal P 挟 C (T) derived from the aromatic carbon C (T) directly connected to the carbonyl carbon in the terephthalic acid (T) unit (-IEETEI-) )｝ _-IETEI- is 133.53p
pm from 133.54 ppm chemical shift,
In addition, with respect to the integrated intensity of this signal, 133.49 ppm and 133.57 ppm signals appearing adjacent to _both sides of P {C (T)}- _IETEI- when randomized (both P {C (T)}) _-TETEI- , which is attributed to the aromatic carbon C (T) of terephthalic acid) (P {C (T)} _-TETEI- /
_3. The alternating copolymerized polyester according to claim 2, wherein P {C (T)}- _IETEI- ) is 0.1 or less. 4. A reaction between terephthalic acid chloride and bis (ω-hydroxyalkyl) isophthalate having 2 to 12 carbon atoms of a hydroxyalkyl group, and / or isophthalic acid chloride and a hydroxyalkyl group having 2 carbon atoms.
A method for producing a polyester, characterized by obtaining the alternating copolymerized polyester according to claim 1 by reacting the polyester with bis (ω-hydroxyalkyl) terephthalate. 5. The alternation according to claim 2, wherein the reaction between terephthalic acid chloride and bis (2-hydroxyethyl) isophthalate and / or the reaction between isophthalic acid chloride and bis (2-hydroxyethyl) terephthalate. A method for producing a polyester, comprising obtaining a copolymerized polyester. 6. The method according to claim 3, wherein the reaction is performed in a polar organic solvent. 7. The process for producing a polyester according to claim 5, wherein after the reaction in a polar organic solvent, solid-phase polymerization is carried out to increase the degree of polymerization of the polymer.