JPS5953529A - Manufacture of polyester - Google Patents

Abstract

PURPOSE:To obtain a polyester of elevated polymerization degree, by incorporating a linear saturated polyester scrap with each specific bisoxazoline and bisoxazolone (or dinone) and/or bisbenzoxadinone to carry out a reaction under molten state. CONSTITUTION:The objective polyester can be obtained by incorporating a linear saturated polyester scrap with (A) 2,2'-bis(2-oxazoline) of formula I (R1-R8 are each H or organic group, D is divalent organic group; n is 0 or 1), and (B) 2, 2'-bis[5(4H)-oxazolone) and/or (C) 2,8-dimethyl-4H,6H-benzo[1,2-d:5,4-d']bis-[1,3]- oxazine-4,6-dione, to carry out a reaction under molten state the amount of the above ingredients will total 0.01-10wt% based on the scrap.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyester. More specifically, the present invention relates to a method for producing polyester, which comprises reacting a substantially linear saturated polyester with a compound having a specific structure in the melt.

Saturated linear polyesters, particularly polyethylene terephthalate, polybutylene terephthalate, etc., have excellent physical properties and are widely used as fibers, films, plastic ethylene, etc.

When this polyester is molded into textiles, films, plastics, etc., in addition to the products, polyester waste is generated, such as waste discharged at the start and end of production, film web waste, plastic container waste, etc.

It is an advantageous method in terms of productivity and cost to re-melt mold this scrap polyester alone or to mix it with new polyester and re-melt mold it to make a product. However, scrap polymers have a low degree of polymerization due to thermal decomposition during melt molding, etc., so products using scrap polymers have lower polymerization degrees than products using new polyester. It has the disadvantage of poor physical properties.

The present inventor has focused on this point, and has developed a method to improve the degree of polymerization of waste polymers even in a very short period of time and even under normal pressure or increased pressure. - As a result of intensive research on methods for producing polyester, it was discovered that the purpose could be achieved by modifying polyester using a certain specific compound, and the present invention was achieved.

That is, the present invention provides a substantially linear saturated y1': scrap polyester (A) consisting of a polyester and said d (0.01% by weight to 10% by weight relative to the polyester (A)) of the following general formula ( At least one compound CB) represented by I) and/or the polyester (0.01% to 10% by weight relative to Al) of the following general formula (IT), (II
At least one selected from the compounds (C) represented by I)
This invention relates to a method for producing polyester in which the seed is ink that does not undergo a reaction while the polyester is melted.

1110 In the present invention, the acid component constituting the substantially linear saturated polyester (A) is terephthalic acid.

Isophthalic acid, naphthanedicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid.

Aromatic dicarboxylic acids such as diphenyl ether dicarboxylic acid, methyl terephcuric acid, methyl isophthalic acid, etc.;
Aliphatic dicarboxylic acids such as succinic acid, azibi/V, cepatic acid, decanonecarboxylic acid, dodecanedicarboxylic acid, etc.; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; ε-oxycaproic acid, oxybenzoic acid, hydroxyethoxy Examples include oxycarboxylic acids such as benzoic acid, etc. Among these, aromatic dicarboxylic acids, particularly terephthalic acid, are preferred. In addition, in the above saturated polyester,
Examples of the glycol component when the acid component is a dicarboxylic acid include ethylene glycol; 1-atrimethylene glycol, tetramethylene glycol, hexamethylene glycol, Tecamerene glycol, and cyclohexane dimethylol. Glycol and tetramethylene glycol are preferred. It is also possible to use polyoxyalkylene glycol as the glycol component, such as polyoxyethylene glycol and polyoxypropylene glycol.

Examples include polyoxytetramethylene glycol and copolymers thereof. When polyoxyalkylene glycol is used, the preferred average molecular weight is SOO to 5o
oo, more preferably 600-4000. Particularly preferred is soo~3000, and furthermore, its use value is about 5~85 double proof in polyester, preferably 10~B.

ff1f reception, more preferably about 15 to 7s:ii%.

Further, the saturated polyester includes a trifunctional or higher functional compound such as trimethylolpropane or pentaerythritol within a substantially linear range (for example, 1 mole or less based on the total acid components).

Trimelinate acid, pyromellitic acid, etc. may also be co-infused with monofunctional compounds such as benzoylbenzoic acid, dinnylcarboxylic acid, etc.

The degree of polymerization of the above-mentioned saturated polyester is preferably such that the intrinsic viscosity measured at 35°C of orne chlorophenol is 0.3 or more, and particularly preferably KO, 4 or more.
.

In the present invention, a compound represented by the general formula (D) (B
) and/or general formula (n) or (
A high degree of polymerization polyester is obtained by adding one or more selected from the compounds (C) represented by m) and reacting them.Compounds (B) and (C) will be explained below.

First, compound (B), ie, the compound represented by general formula (I), will be explained.

4R8 In the general formula (1), R and ~R8 are each a hydrogen atom or -
Preferred examples of the -valent organic group include an alkyl group having 1 to 1 carbon atoms, and an alkyl group having 6 to 12 carbon atoms.
Examples include a 7-aryl group, a cycloalkyl group having 5 to 12 carbon atoms, and a 7-ralkyl group having 8 to 20 carbon atoms. Among these, it is most preferable that all of R1 to R8 are hydrogen atoms. In addition, D in the formula is a divalent organic group, for example, a fullkylene group having 1 to 10 carbon atoms, 7 having 6 to 12 carbon atoms,
Rielene group, carbon #! A cycloalkylene group having i5 to 12 carbon atoms, an aralkylene group having 8 to 20 carbon atoms, and the like can be used.

More specifically, examples of alkylene groups include methylene, ethylene, butylene, ptylene, pentyl, hexamethylene, octamethylene, nonamethylene, decamethylene, dimethylmethylene, etc., and arylene groups include phenylene and naphthylene.

Diphenylene, '(]hiRzo (here, R' is 10-2-
Co-, -8-, -8o2-, -CH,-, -C1
2CH, -1-C(CH3)2-, etc.), and the cycloalkylene group is cyclohexylene. Further, n in the formula is 0 or 1.

Most preferably, n is O, and when n is 1, it is preferably a 7-rylene group.

The compound represented by the general formula (I) is a compound called bisoxacili/, and the following compounds are exemplified.

2.21-His(2-Kizabrin), 2.2'-Bis(4-methyl-2-oxazoline), 2.2'-Bis(
4,4-dimethyl-2-oxazoline).

2.2'-bis(4-ethyl-2-oxazoline).

2.2'-bis(4,4-diethyl-2-oxazoline), 2.2'-his(4-purpyl-2-oxapurine), 2.2'-bis(4-butyl-2-oxazoline)
, 2,2'-bis(4-hexyl-2-oxazoline)
, 2.2'-bis(4-phe-2-oxazoline), 2.2'-bis(4-cyclohexyl-2-oxazoline), 2.2'-bis(4-benzyl-2-oxazoline), 2.2'-p-phenylenebis(2-oxazoline).

2.2'-m-phenylenebis(2-oxazoline).

2.2'-o-phenylenebis(2-oxazoline).

2.2'-p-phenylenebis(4-methyl-2-oxaprine), 2.2'-p-phenylenebis(4,4-
-dimethyl-2-oxazoline), 2,2'-m-phenylenebis(4-methyl-2-oxazoline)+2+2
'm-phenylenebis(414-dimethyl-2-oxazoline), 2,2'-ethylenebis(2-oxazoline), 2,2'-tetramethylenebis(2-oxazoline), 2,2'-hexamethylenebis (2-oxazoline), 2,2'-octamethylenebis(2-oxazoline).

2.2'-decamethylenebis(2-oxazoline).

2.2'-ethylenebis(4-methyl-2-oxazoline), 2.2'-tetramethylenebis(4,4-dimethyl-2-oxazoline), 2.2'-9,9'
- Diphenoxyethane bis(2-oxazoline).

2.2'-Cyclohetacilonbis(2-oxacillin)
, 2,2'-diphenylenebis(2-oxazoline), etc.

One type or 21 or more of these compounds are used, and the amount of such compounds used is 0.01% by weight to 10% by weight based on the polyester (A). If the amount is less than 0.01% by weight, the desired effect of the present invention will not be noticeable, and if the amount is less than 10% by weight,
If the amount exceeds that amount, no further effect can be expected. The amount used is more preferably 0.02% to 5% by weight, particularly preferably 0.03% to 3% by weight.

Next, compound (C) will be explained.

First, regarding the compound represented by general formula (n), D in the formula
' is a divalent cold group having the same meaning as above.

In addition, X is a divalent organic group, and such groups include, for example, a ethylene group, a substituted methylene group, an ethylene group, a [substituted ethylene group, an O-phenylene group, an O-phenylene group having an ffi substituent, etc. . Examples of the substituted methylene group and substituted ethylene group include an alkyl group having 1 to 10 carbon atoms, a 7-aryl group having 6 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, and an aralkyl group having 8 to 20 carbon atoms. Examples include a methyl group and an ethylene group having one or more types of substituents. Two of these substituents may be bonded to each other to form a 6-membered ring or a 5-membered ring. In addition, when X is an O-)22dine group or an O-phenylene group having a substituent,
The ring formed in the formula is a 6-membered ring, and has, for example, a carbon number of 1 to
10 alkyl group, a 7-aryl group having 6 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a 7-ralkyl group having 8 to 20 carbon atoms, and m is a number from 1 to 4). It will be done. The same applies when X is a naphthylene group or a naphthylene group substituted with 1. Specific examples of the alkyl group, aryl group, aralkyl group, and cycloalkyl group as the above-mentioned substituents include those exemplified for the organic group in D. X and -C device i Methylene, substituted ethylene, and 0-phenylene are preferred, and 0-phenylene is particularly preferred. l is 0 or 1, most preferably 0, and when l is 1, D' is preferably an arylene group.

The compound represented by the general formula (n) is called a bisoxacylone when the ring structure is a 5-membered ring, and is called a bisoxazinone when it has a 6-membered ring. These are easily prepared by dehydrating the appropriate NN'-diasilbis (α- or β-7 minocarboxylic acid) with a compound such as acetic anhydride. Examples of such compounds include the following compounds.

1) Bisoxacilone compound; 2.2'-bis(5(4H)-oxacilone).

2.2'-methylenebis(5(41)-oxacylone)
, 2,2'-ethylenebis(s(4H)-oxacylone), 2,2'-tetramethylenebis(s(41)-oxacine), 2,2'-hexamethylenebis(5(4)
1'l)-oxacylone) 2.2'-decamethylenebis(s(4H)-oxacilone), 2.2'-p-7 2-dinilenebis(5(4II)-oxacilone), 2.2
'-m-phenylenebis(5(4H)-oxacylone)
.

2.2'-su7talenebis(5(4H)-oxacylone), 2.2'-diphenylenebis(5(4H)-oxacylon), 2.2'-(1,4-(cyclohexylene)-bis (6(4H)-oxacylone), 2.2'
-bis(4-methyl-5(4H)-oxacylone), 2
．． 2'-methylenebis(4-methyl-5(4H)-oxazolone), 2,2'-ethylenebis(4-methyl-5
(4H)-oxacilone), 2.2'-tetramethylenebis(4-methyl-5(4H)-oxacilone), 2.
2'-hexamethylenebis(4-methyl-5(4H)-
oxacillone).

2.2'-decamethylenebis(4-methyl-5(4H)
-oxacylone), 2.2'-p-7enylenebis(4-methyl-5(411)-oxacylone), 2
．． 2'-m-phenylenebis(4-methyl-5(4H)
- oxacillone).

2.2'-naphthalenebis(4-methyl-5(4)I
) -oxacilone), 2,2'-diphenylenebis(
4-methyl-5(4H)-oxacilone), 2.
2'-(1,4-cyclohexylene)-bis(4-methyl-5(4H)-oxazopunn, 2.〆-bis(4
, 4-dimethyl-5(4H)-oxacylone), 2.2
'-Methylenebis(4,4-dimethyl-5(4H)-oxacylone), 2,2/-ethylenebis(4,
4-dimethyl-5(4H)-oxacilone), 2. Gutetramethylenebis(4,4-dimethyl-5(4H)-
oxacilone), 2,2'-hexamethylenebis(4,
4-dimethyl-5(4H)-oxacylone), 2.2'
-octamethylenebis(4,4=dimethyl-5(4H)
-oxacilone), 2,2'-decamethylene bik (4,
4-dimethyl-5(411)-oxacylone), 2.2
'-p-phenylenebis(4,4-dimethyl-5(4H
)-ox1zopn), 2,2'-m-phenylenebis(
4,4-dimethyl-5(4H)-oxacilone), 2.
2'-naphthalenebis(4,4-dimethyl-5(4H)
-oxacilone), 2,2'-diphenylenebis(4,
4-dimethyl-s (4H)-oxacilone),
2.2'-(1,4-cyclohexylene)-bis(4
, 4-dimethyl-5(4H)-oxazo μ7), 2.2
'-bis(4-isopropyl-s(4n)-oxacilone).

2,! -methylenebis(4-isopropyl-5(4H)
-oxacillone), 2. Z'-ethylenebis(4-isopropyl-5(4H)-oxacilone), 2,2'-tetramethylenebis(4-isopropyl-5(4H)-oxacilone).

2. Goohexamethylenebis(4-isopropyl-5(
4H)-oxacylone), 2.2'-p-phenylenebis(4-yne7'l=biru-5(4H)-oxacilone L2+2'm-7enylenebis(4-isopropyl-5(4H)-oxacilone), 2.2'-Naphthalenebis(4-isopropyl-5(4H)-oxacylone)
12.2'-bis(4-inbutyl-5(4H)-oxacilone), 2.2'-methylenebis(4-inbutyl-5(4H)-oxacilone), 2. Z'-ethylenebis(4-benzothyl-5(4H)-oxacylone), 2
．． 2'-tetramethylenebis(4-inbutyl-5(4
H)-oxacilone), 2.2'-hexamethylenebis(4-inbutyl-5(4H)-oxacilone), 2.
2'-p-phenylenebis(4-isobutyl-5(4H
)-oxacylone), 2,2'-m-phenylenebis(
4-isobutyl-5(4H)-oxacilone), 2.2
2) Bisoxazinone compounds: 2.2'-bis(3,1-benzoxazin-4-one), 2.2'-methylenebis(3 , 1-benzoxazin-4-one), 2,2'-ethylenebis(3,1-penzoxazin-4-one).

2.2'-tetramethylenebis(3,1-penzoxazin-4-one), 2.2'-hexamethylenebis(3
, 1-benzoxazin-4-one).

2.2′-decamethylenebis(3,J-benzoxazin-4-one), 2+” p-phenylenebis(3,
1-benzoxazin-4-one).

2.2'-m-phenylenebis(3,l-benzoxazin-4-one), 2.2'-naphthalenebis(3,1
-benzoxazin-4-one).

2.2'-(4,4'-diphenylene)bis(3,1
-benzoxazin-4-one), 2.2' -(
1,4-cyclohexylene)bis(3,1-penzoxazin-4-one), 2,2'-bis(4,4-dihydro-1,3,6H-oxazin-6-one).

2.2'-methylenebis(4,5-dihydro-113°6H-oxazin-6-one), 2.2'-ethylenebis(4,5-dihydro-1,3,6H-oxazin-6-one)
6-one), 2,2'-tetramethylenebis(4,5-
dihydro-1,3,6H-oxazin-6-one),
2.2'-p-phenylenebis(4,5-dihydro+i-1,3,6H-oxazin-6-one),
2.2'-yn-phenylenebis(4゜5-dihydro-
1,3,6H-oxazin-6-one), 2,2'-bis(4-methyl-5-hydro-1,3,6H-oxazin-6-one).

2.2'-ethylenebis(4-methyl-5-human I:I
-1,3,6H-oxazin-6-one).

2.2'-p-phenylenebis(4-methyl-5-hydro-1,3,6H-oxazin-6-one).

2.2'-m-phenylenebis(4-methyl-5-hydro-1,3,6H-oxazin-6-one).

2.2'-p-phenylenebis(4-hydro-52+2
'm-phenylenebis(4-hydro-5-methyl-
1,3,6H-oxazin-6-one), etc.

Next, the compound represented by general formula (m) will be explained.

+1 11 0 The compound represented by the general formula (10) is a compound called bisbenzoxazinone, and humans
A fused ring compound consisting of 2 to 3 benzene rings or an aromatic group represented by the general formula (■-R' J (nr is the same as above)) is preferable.

Also R,,R,. IJ5 is, for example, an alkyl group having 1 to 1 o carbon atoms, or a dichlorofurkyl group having 3 to 12 carbon atoms.

A 7-aryl group having 6 to 8 carbon atoms is preferable, and more specific examples of the furkyl group include methyl, ethyl, propyl, inpropyl, propentyl, hexyl, and octyl, and examples of the dichlorofurkyl group include: Examples include cyclopentyl and cyclohexyl, and examples of the 7-aryl group include phenyl and naphthyl groups.

The bisbenzoxazinone compound represented by the general formula (m) is composed of a diaminodicarboxylic acid represented by the following formula (■) [wherein, human is a tetravalent aromatic group] and an aromatic aliphatic group. N can be easily produced by heating the acid derivative in an organic solvent or in polyphosphoric acid. Particularly preferably, it is produced by reaction with an aromatic or aliphatic acid anhydride or an acid halide.The production of the bisbenzoxazinone compound is not limited to these methods.

Examples of such compounds include the following compounds.

2,8-dimethyl-414,6H-benzo[1,2-d
: 5,4-d')bis-(1,3)-'J-xazine-4,6-dione, 2,7-dimethyl-4H,9I
(-benzo(1,2-d : 4,5-d')bis-(
1,3)-oxazine-4,9-dione, 2,8-diphenyl-4H,6H-benzo (1,2-d: 5,4
-d') bis-(1,3)-oxazine-4,6-dione.

2.7-diphenyl-4H,9H-benzo[l,2-d
:4,5-d')bis-(1,3)-oxazine-4,
6-dione s, 6t-bis(2-methyl-4H, 3
, 1-benzoxane-4-one).

6.6'-bis(2-techφru4)1, 3.1-benzoxazin-4-one), 6.6'-bis(2-phenyl-4)1, 3.1-benzoxazin- 4-one), 6,6'-methylenebis(2-methyl-4H, 3
, 1-benzoxazin-4-one).

6.6'-methylenebis(2-phenyl-4H, 3゜1
-benzoxazin-4-one), 6.6'-ethylenebis(2-methyl-41(,3,1-benzoxazin-4-one), 6.6'-ethylenebis(2-phenyl-4H, 3,1-benzoxazin-4-one), 6.
6'-butylene bis(2-methyl-4H,3,1-benzoxazin-4-one) + L6'-butylene bis(2
-phenyl-4H, 3,1-benzoxazin-4-one).

6.6'-oxybis(2-phenyl-4H,3,1-
benzoxazin-4-one), 6,6'-sulfonylbis(2-methyl-4H, 3,1-benzoxazine-
4-τn), G, 6'-sulfonylbis(2-phenyl-411, 3,1-benzoxazin-4-one), 6
．． 6'-carbonylbis(2-methyl-4H, 3,1-
benzoxazin-4-one), 6,6'-carbonylbis(2-phenyl-4H, 3,1-benzoxazin-4-one).

71-demethylenebis(2-methyl-4H, 3,tbenzoxazin-4-one), 7,7'-methylenebis(
2-phenyl-4M, 3.1-benzoxazine-4-
), 7,7'-bis(2-methyl-4H, 3,1-
penzoxazin-4-one).

7.7/-ethylenebis(2-methyl-4H,3,summer-
penzoxazin-4-one), 7,7'-oxybis(2-methyl-4H, 3,1-benzoxazin-4-
), 7,7'-sulfonylbis(2-methyl-4H
, 3,1-benzoxazin-4-one), 71decarbonylbis(2-methyl-4H, 3,1-benzoxazin-4-one), and the like.

As the compound (C), at least one compound represented by the general formula (II) or (m) is used, and the amount of such compound used is 0.011% based on the polyester (A).
It's from welfare to toi quantity. If the amount is less than 0.011i%, the degree of polymerization will not increase sufficiently, and if it exceeds 10 i%, no further effect can be expected, or the degree of polymerization will be difficult to increase, which is undesirable. .

A more preferable amount is 0.02% to 5% by weight, particularly preferably 0.05% by weight. It is the quantity φ from lt to s.

In the present invention [311, under melting of polyester (A),
Polyester/L-(A) and a predetermined amount of compound '1kJfB)
and Compound (C) are mixed and reacted. The preferred range of this reaction temperature is 320"C above the melting point of polyester.
or less, more preferably 2 or more than the melting point of polyester.
The temperature is below 90°C. The reaction pressure may be increased pressure, but is preferably normal pressure or reduced pressure.

Preferable reaction time is 30 seconds to 60 minutes, more preferably 1 minute to 30 minutes, particularly preferably 1 minute to 1 minute.
It's 5 minutes.

This reaction is carried out in a conventional polyester polymerization reactor (A)
, (B) and/or (C) may be mixed and reacted with stirring, for example, in an extruder. Also scrap polymers (A) and (B)
and/or fc) is reacted, for example, when melting irregularly shaped scrap polymer to form a pellet, when remelting and molding the irregularly shaped layer polymer as it is, when melting and molding the pelletized scrap polymer, etc. ) and/or (C), and it is of course possible to mix new polyester at these times.

In addition, when carrying out a mixed reaction of (A), (B), and (C), by reacting the compound (B) with the polyester (A) in advance,
A method of reacting compound (C); reacting polyester (A) with compound (C) in advance, and then reacting compound (C) with compound (C);
A method of reacting compound (B) can also be used as appropriate.
) and/or compound (C) in a large amount (so-called master polymer) is prepared in advance, and a predetermined amount of this is added to polyester (A) for reaction. A so-called masterbatch method can also be preferably employed.

In the present invention, the above polyester and compound (B) and/or
Or, when reacting with compound (C), various additives such as ultraviolet absorbers, heat stabilizers, l&fuel agents, brighteners, lubricants, nucleating agents, pigments, fillers, etc. are added to the polyester or during the reaction. Good too.

The present invention will be described in detail below with reference to Examples. In addition, “
"Parts" means "parts by weight."

Examples 1 to 4 Comparative Example 1 100 parts of waste polyester (A) with an intrinsic viscosity of 0.62 generated when melt-molding polyethylene Tele 7 crate with a viscosity of 0.65 and the compound shown in Table 1 (B)
A predetermined amount of and/or (C) was added and mixed, and melt-extruded using an extruder at about 280°C for an average residence time of about 3 minutes. Table 1 shows the intrinsic viscosity of the obtained polymer.

As a comparative example, an example will be shown in which compounds (B) and (C) are not added.

As is clear from Part 1, addition of the compound (B) and/or (C) improves the degree of polymerization of the scrap polyester (A), making it suitable for practical use.

Examples 5-7 Comparative Example 2! 5 parts of scrap polyester (A) with an intrinsic viscosity of 0.62 generated when polyethylene terephthalate with a limiting viscosity of 0.65 was melt-molded and 50 parts of polyethylene terephthalate with an intrinsic viscosity of 0.65 were mixed with the compounds shown in Table 2 ( A predetermined amount of B) and/or (C) was added and mixed, and melt-extruded using an extruder at about 280° C. with an average residence time of about 3 degrees. Table 2 shows the intrinsic viscosity of the obtained polymer. As a comparative example, an example will be shown in which no compound is added. As is clear from Table 2, the addition of compounds CB) and/or (C) improves the degree of polymerization of the scrap polyester (A), making it suitable for practical use.

Claims (1)

[Scope of Claims] A scrap polyester (A) consisting of a substantially linear saturated polyester and a polyester (A) represented by the following general formula (1) in an amount of 0.01% by weight to 10% by weight based on the polyester (A). At least l f! of compound CB+ II and/or the polynisder (0.01% to 10% by weight relative to Al) compound represented by the following general formula (n), (nll) (
A method for producing polyester, which comprises reacting at least one member selected from C) while the polyester is melted. R,R. 1 4R8 11II 0