JPS6264826A - Production of aromatic polyester molding - Google Patents

Abstract

PURPOSE:To obtain quickly a molding of an aromatic polyester of a degree of polymerization increased to the desired one, by mixing an aromatic polyester with a biscycloiminoester compound at the melting temperature of the polyester in a melt molding machine and melt molding the mixture. CONSTITUTION:A linear, fiber-forming or film-forming aromatic polyester prepared from an acid component based on a hydroxyl group-terminated aromatic dicarboxylic acid and a glcyol component based on an alkylene glycol or based on an alkylene glycol and a polyalkylene glycol is mixed with a biscycloiminoester compound of formula I or II in a melt molding machine at a temperature higher than the melting temperature of the aromatic polyester to bond the aromatic polyester chains together through the terminal hydroxyl groups. In formula II, A is a group of formula III (wherein R2 is a monovalent hydrocarbon group) or formula IV, R is a tetravalent aromatic group which may contain a hetero atom and R<1> is a monovalent hydrocarbon group.

Description

[Detailed description of the invention] The present invention relates to a method for manufacturing aromatic polyester molded articles.

More specifically, it relates to a method for rapidly producing an aromatic polyester IIt type product v81i with a higher degree of polymerization by bonding the molecular chains of aromatic polyester together by reacting the terminal hydroxyl groups with a biscyclic iminoester compound. .

Conventionally, as a method for rapidly increasing the degree of polymerization of aromatic polyester, there has been a method in which a relatively low molecular weight aromatic polyester is reacted with a diaryl carbonate such as diphenyl carbonate under reduced pressure in a molten state (US Patent @ 3).
444141), a method of reacting a diaryl ester of an aromatic dicarboxylic acid such as diphenyl terephthalate (see U.S. Pat. No. 3,433,7706), a method of reacting a diaryl ester of oxalic acid or malonic acid (U.S. Pat. 34
33770), polyethylene oxa 1/-
A method of reacting polyalkylene oxalate such as
(see Specification No. 9) is known.

However, since all of the above polymerization accelerators react with aromatic polyesters to produce byproducts such as 11M gas or phenols, the reaction is carried out in the melt and under reduced pressure to quickly remove the byproducts. It was necessary to remove it from the reaction system. That is, when phenols, which are by-products, remain in the reaction system, they react with the ester groups of the aromatic polyester molecular chain, resulting in a decrease in the degree of polymerization of the aromatic polyester.

Furthermore, when polyalkylene oxalate such as polyethylene oxalate is used as a polymerization accelerator, the polymerization accelerator itself undergoes a transesterification reaction with the aromatic polyester and has the effect of lowering the polymerization degree of the aromatic polyester. It's ringing.

However, there are also known polymerization promoters which do not produce the above-mentioned by-products, but which are incorporated into the molecular chain. Jepoxy compounds are typical of such polymerization accelerators (see US %VLF No. 3,553,157). However, since the jepoxy compound generates two hydroxyl 1s when bonding the molecular chains of polyester, the polycondensation reaction proceeds further through the hydroxyl groups, resulting in the disadvantage of producing branched polynisdels. .

In addition, a powder coating consisting of a polymer base having an average of more than two hydroxyl groups in the molecular chain and having a low molecular weight and which sometimes gives rise to a melt with extremely low viscosity when heated is crosslinked with a biscyclic iminoester. A method for forming a network that becomes a coating film is also known (DT
-082,522,192).

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to produce an aromatic polyester molded product having a rapidly increased degree of unity by bonding the molecular chain structure of an aromatic polyester through its terminal hydroxyl group in a melt molding machine.

Another object of the present invention is to perform a bonding reaction between the molecular chains of an aromatic polyester in a bath melt molding machine, and to produce an aromatic polyester purple resin having a desired increased degree of unity; ``Our objective is to provide 16 methods for manufacturing molded products consisting of left-sided characters.

Further objects and advantages of the invention will become apparent from the description below.

According to the most basic concept of the present invention, one such object and advantage of the present invention is that the aromatic dicarbonate IjI! has a terminal hydroxyl group. is the main acid component and alkylene glycol or alkylene glycol and polyoxyalkylene glycol are the main glycol components. A substantially linear fiber-forming or film-forming aromatic polyester is prepared by the following formula [1], where: Y is a hydrogen ashing group which may contain a heteroatom.

X forms a wrinkled iminonis ring Has 1 or 2 barring atoms , unreactive divalent under the reaction conditions O-legged hydrogen group, l is 0 or 1, Or the following formula [■] Here, A is the following formula [11)-a Here, W is a monovalent hydrocarbon group.

Or the following formula (IT)-b I　　　　　　　　　　　　　　　-b＼N′ゝR1 Here, the definition of R2 is the same as above.

A biscyclic group represented by R is a tetravalent aromatic group which may contain a heteroatom, and R1 is a monovalent hydrocarbon group which is the same as or different from By mixing the iminoester compound with the aromatic polyester in a melt molding machine at a temperature higher than the melting temperature of the aromatic polyester, the molecular chains of the aromatic polyester are bonded to each other through terminal hydroxyl groups, which is the q# characteristic, and the extremely fat viscosity is further increased. This is achieved by a method for producing molded products made from aromatic polyester.

Hereinafter, the present invention will be explained in detail.

(A) Aromatic polyester raw material The aromatic polyester used in the present invention has a terminal hydroxyl group, has aromatic carbone WR as the main acid component, and has fullkylene glycol or alkylene glycol and polyoxyalkylene glycol as the main glycol components. It is made of substantially KM-like polyester. These aromatic polyesters and methods of making them are well known in the art.

Examples of aromatic dicarboxylic acids include prelental acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenoxyethane dicarboxylic acid, diphenyl ether dicarboxylic acid, methyl terephthalic acid, methyl inphthalic acid, etc. be able to.

In addition, examples of alkylene glycols include ethylene glycol, trimethine/glycol, hexamethylene glycol, decamethylene glycol, etc.
10 polymethylene glycol and cyclohexane dimethylol.

Further, as the polyoxyalkylene glycol, for example, polyoxyethylene glycol.

Examples include polyoxypropylene glycol, polyoxytrimethylene glycol, polyoxytetramethylene glycol, and copolymerized polyoxyalkylene glycols having 2111 or more of these oxyalkyne units as repeating units.

Aromatic polyester I having aromatic dicarboxylic acid as the main IIX component and alkylene glycol as the main glycol component; or a homopolymer or copolymer containing 2 g or more of glyfur as a main component, such as polyethylene terephthalate, polytrimethylene terephthanate, polytetramethylene terephthalate, polyethylene 2,6-naphthalene dicarpoxylate, polyethylene terephthalate-in Examples include phthalates.

In addition, aromatic polyesters containing aromatic dicarboxylic acid as the main acid component and alkylene glycol and polyoxyalkylene glycol as the main glycol components,
It is generally called a so-called polyester elastomer because it has elasticity, and contains one or more of the above aromatic dicarboxylic acids as the main acid component,
It is a copolymer whose main glycol components are one or more of the above-mentioned alkylene glycols and one or more of the above-mentioned polyoxyalkylene glycols. For example, there may be mentioned a polyester elastomer having terephthalic acid as an acid component and tetramethylene glycol and polyoxytetramethylene glycol as glycol components.

As polyoxyalkylene glycol, average molecular weight 5
00~5.000. Preferably &1600~4,000.
Particularly preferred is a polyester elastomer having a molecular weight of 800 to 3.0+10, and the polyoxyalkylene moiety derived from the polyoxyalkylene glycol used is 5 to 85% by weight of the polyester elastomer.

Preferably 10-80% by weight, preferably 15=7
The aromatic polyester used in the present invention is preferably a polyester elastomer which accounts for 5% by weight.

Aromatic dicarbonate # as above! is used as the acid component and the glycol component is not limited to the above-mentioned alkylene glycol or alkylene glycol and polyoxyalkylene glycol, but may be composed of these main components and a secondary component other than 71.

Such secondary components include, for example, succinic acid.

Adipic acid, sepatic acid, decanedicarboxylic acid.

Aliphatic dicarboxylic acid such as dodeca/dicarboxylic acid #R: Alicyclic dicarboxylic acid such as cyclohexane dicarboxylic acid;
Secondary acid components such as e-oxycapro/oxybenzoic acid, human-xyethoxybenzoic acid, and trifunctional or higher functional compounds such as trimethylolpropane, pentaerythritol, trimellitic acid, pyromellitic acid, or benzoylbenzoic acid, Mention may be made of monofunctional compounds such as diphenylcarboxylic acid.

Among these, the secondary acid component is 20 mol% or less, preferably 15 mol% or less of the total acid components.

Particularly preferably, it can be contained in an amount of 10 mol% or less, and the trifunctional or higher functional compound is contained in an amount such that the aromatic polyester is substantially linear, that is, usually in an amount of 1 mol% or less of the total acid component. can be included. Monofunctional compounds that block the terminal hydroxyl group have no particular meaning in use unless there is a special reason, but those that block the carboxyl terminal have little effect on the reaction of the present invention 41-f kotonana(, can be used.

Among these, the aromatic polyester in the present invention is one containing terephthalic acid as the main acid component and ethylene glycol or tetramethylene glycol as the main glycol component, or one containing terephthalic acid as the main acid component and containing tetramethylene glycol and polytetramethine. Those containing glycol as the main glyfur component are preferably used for q#.

These aromatic polyesters used in the present invention can be produced by a method known per se by a transesterification method or a direct polymerization method in the presence of a known catalyst. For example, polyester elastomers are produced by heating aromatic dicarboxylic acid or its ester-forming fermented derivative, tetramethylene glycol and polytetramethidi/glycol to 180 to 220°C in the presence of a titanium catalyst such as titanium tetrabutoxide, and gradually reducing the pressure. It can be manufactured by raising the

The aromatic polyester used in the present invention has terminal hydroxyl groups and has substantially linear fiber-forming or film-forming properties.

Having a terminal hydroxyl group should not be understood to mean that all the terminals of an aromatic polyester are hydroxyl groups (nor should it be interpreted to mean that the concentration of terminal hydroxyl groups is greater than the terminal carboxyl group).

As will be explained in detail later, since the reaction of the present invention involves bonding the molecular chains of aromatic polyesters together through terminal hydroxyl groups, the degree of polymerization of the aromatic polyester rapidly increases as the reaction progresses. This is because the aromatic polyester obtained at the time when the aromatic polyester has a sufficient concentration can still have a sufficient concentration of terminal hydroxyl groups.

The aromatic polyester having a terminal hydroxyl group 1 that can be used as the aromatic polyester in the present invention generally requires using a stoichiometrically larger amount of a glycol component than an acid component in the reaction system when producing the aromatic polyester. Accordingly, a polyester having more terminal hydroxyl groups than terminal carboxyl groups can be easily obtained.

A preferable terminal hydroxyl group concentration is 60 equivalents or more, particularly 70 equivalents or more of the total amount of terminal groups.

In addition, the term "fiber-forming property" or "film-forming property" means a property that has a certain degree of polymerization and can be formed into a fibrous or film form. The physical properties of the fiber or film obtained by molding here do not matter. Therefore, aromatic polyesters with fiber-forming or film-forming properties are
It can be expressed by the solution viscosity which depends on the degree of polymerization.

Oruncu I: Extreme fat viscosity controlled at 35°C in lG + phenol, preferably 0.3 or more, particularly preferably #↓
0.4 or more, aromatic dicarbon #V main WR #: 1.29/dlr) 9 degrees Reduced viscosity (gap/c) measured at 35°C for the solution dissolved in C)
) or preferably 0.5 or more, particularly preferably 0.6 or more, particularly 0.8 or more, aromatic dicarbo, /II is the main acid component and alkylene/glycol and polyoxyalkylene glycol are the main glycols The polyester elastomer as a component can be advantageously used in the present invention as an aromatic polyester raw material having a fiber-forming property and a film-forming property of 1. From the viewpoint of physical properties, uses, etc. of the resulting aromatic polyester, it is desirable that one point of the aromatic polyester raw material has a temperature of 200° C. or higher.

[B] His cyclic imino ester The bis cyclic imino ester used in the present invention is:
The following formula [1] or the following formula [IJ] Here, A is the following formula [■] -a or the following formula (n) -b.

It is expressed as

In the above formula CI), Y! It is a divalent hydrocarbon group which may contain 2 heteropants, X has one ring member return atom forming the iminoester ring, and N has two, under the reaction conditions. It is a non-reactive divalent hydrocarbon group, and l is 0 or l.

In the following formula [01, R1'i is a tetravalent aromatic group which may contain a heteroatom, and gl and W are the same or different 1@ hydrocarbon groups.

The 2@ hydrocarbon group (Y in formula (I)) which may contain an I:I atom is preferably an I*.

divalent hydrocarbon groups containing heteroatoms such as oxygen or sulfur atoms, preferably 15 to 3 oxygen or sulfur atoms, which are non-reactive substitutes with the aromatic polyester under the reaction conditions. It may have a group. Such 2f#
As the swelling water X group, for example, a fluorine group having 1 to 10 carbon atoms.

Arylene M having 6 to 12 carbon atoms, a cycloalkylene group having 5 to 12 vertical primes, a fulquin-arylene-alkylene group having 8 to 20 RIAs, and one or more of these tassel atoms.
Preferred examples include groups in which 3Il is substituted with a heteroatom. Further, examples of the non-reactive substituent include 1, for example, an alkyl group having 1 to 10 carbon atoms.

Schiff- of 7-lyl group and 1 leg element a5-12 having 6 to 12 carbon atoms
Preferred examples include 7-ralkyl groups having 8 to 20 furkyl 111 numbers.

Preferred specific examples of such divalent hydrocarbon groups include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene. Octamethylene snow nonamethylene.

Decamethylene, dimethylmethylene, m bulk a1-10
A4 Kylene group; phenylene, naphthylene, diphenylene, formula % -C-C-C-, -C(CH,), -.

A 7-liylene crystal of envy a6-12 such as the group n represented by;
Cyclopentylene cyclohexylene.

Examples include a cycloalgylene group having 5 to 12 vertical primes such as cyclododecamethylene; a fullkylene-7-rylene-alkylene group having 8 to 20 carbon atoms such as p-xylylene and m-xylylene; Among these, fullylene or arylene groups are particularly preferred.

Preferred specific examples of substituents include those having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, hexyl, and decyl.
Alkyl group; phenyl.

7 reels with vertical prime numbers 6 to 12 like naphthyl & Nijiklobenal, Schiff l-l1\xyl like charcoal g i5 to 12
Cycloalkyl; translation like phenethyl! c number 8-20
Examples include a 1-ralkyl group. Among these, an alkyl group or an aryl group is particularly preferred.

As a divalent reconstituted water group (formula [1) X) which has one or two ring carbon atoms forming an iminoester ring and is non-reactive under the reaction conditions.

For example, methine groups, ethylene groups, orthophenylene groups, and these groups substituted with substituents that are non-reactive under the reaction conditions can be mentioned as preferred. These substituents include the same substituents mentioned above for Y, and the two optionally substituted t-groups of the orthophenylene group are bonded to each other to form a ring. It's okay. Among these, methylene chloride,
[Reduced ethylene and orthophenylene are preferred, and orthophenylene is particularly preferred.

jl in formula CI] is O or 1, and when l is 00, formula (1) represents that the 2@ cyclic iminoester group is directly bonded.

Het I: A tetravalent aromatic group which may contain an I atom (
Preferred examples of R) in formula (n) include a monocyclic, m-fused ring, or polycyclic tetravalent aromatic group represented by the formula 1 (2 is the same as Bo above). Particularly preferred.

These may be substituted with the substituents described above for Y.

As the monovalent aspect ratio hydrogen group representing R1 and R2 in formula CII), preferable examples include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, and an aryl group having 6 to 18 carbon atoms. It can be given as follows. Among these, alkyl groups having a vertical prime number of 1 to 10 are preferred.

Preferred specific examples of these include the same as those mentioned above.

As mentioned above, A in formula CI is represented by formula [■] -a is represented by formula (II) -b, but formula (II) -a and formula [11] - are all (the same group) Therefore, R in formula (If)
On the other hand, Ji! It shows that they match.

Therefore, as one skilled in the art will readily understand, in the case of 1'C, a compound of formula (II) is a compound of formula (II)
) represents either a compound represented by the following formula (when A is a group of formula (II) -b): Although these two compounds are completely different compounds, either compound can be used in the present invention.

Preferred specific examples of the compound tube represented by the above formula [I] are as follows. These compounds are called bisoxacylone when X is a Mizuki group with one ring member atom, that is, the iminoester ring is 5 members, and when X is a hydrogen swollen hydrogen atom with two ring members. When the iminoester ring is 6 members, it is called a bisoxazinone.

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

2.2I-methylenebis(5(4H)-oxacylone)
s 2m2'-ethylenebis(5(4H)-oxacylone), 212'-tetramethylenebis(5(4H)
)-oxacilone'j, 212'-hexamethylene bis(5(41)-oxacine), 2,2'-decamethylene bis(5(4I()-oxacilone) +
2.2'p-phenylenebis(5(4H)-oxacylone)+2+2'-m-phenylenebis(5(4H)
-Oxacylon) 1212'-su7 sauce/bis(5(
4H)-oxacylone), 2.2'-diphenylenebis(5(4H)-oxacylone), 2.2'-
(1,4-(cyclohexylene)-bis(5(4H)-
oxacylone), 2,2'-bis(4-methyl-5
(4H)-oxacilone).

2.2'-ethylenebis(4-methyl-5(4H)-oxazone), 2.2'-ethylenebis(4-methyl-5(4H)-oxacilone) + L2'-tetramethylenebis(4-methyl -5(4H)-oxazolone), 212'-hexamethylenebis(4-methyl-
5(4H)-oxacilone).

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

2+2' m-phenylenebis(4-methyl-5(4
H)-oxacillone), 2.2'-su7 sauce/bis(
4-methyl-5(4H)-oxacilone).

2.2'-diphenylenebis(4-methyl-5(4B)
-oxacylone) * 2+2' (1+4-cyclohexylene)-bis(4-methyl-5(4H)-oxacylone), 2,2'-bis(4,4-dimethyl-5(
4H)-oxacylone), 2,2'-methylenebis(4,4-dimethyl-5(4H)-oxacylone),
2.2'-ethylenebis(4,4-dimethyl-5(4
H)-oxacylone) 12.2'-tetramethylenebis(4,4-dimethyl-5(4■)-oxacylone)
, 2.2'-hexamethylenebis(4,4-dimethyl-5(4H)-oxacilone).

2.2'-octamethylenebis(4,4-dimethyl-5
(4H)-oxacylone), 2,2'-decamethylenebis(4,4-dimethyl-5(4H)-oxacylone)+
L2'-p-7 22lenebis(4,4-dimethyl-5(
4H)-oxacilone), L2'-m-phenylenebis(4,4-dimethyl-5(4H)-oxazopy)+
L2'-naphthalenebis(4,4-dimethyl-5(4H
)-oxacylone), 2,2'-diphenylenebis(4I4-dimethyl-5(4H)-oxacylone), 2
．． 2'-(1,4-cyclohexylene)-bis(4,4
-dimethyl-5(4H)-oxacillone), 2.2'-
Bis(4-inpropyl-5(4H)-oxacine)
, 2,2'-ethylenebis(4-inpropyl-5
(4H)-oxacylone), 2,2'-ethylenebis(4-isopropyl-5(4H)-oxacylone'J
, 2.2'-tetramethylenebis(4-isopropyl-5(4B)-oxacylone) + 2+2'-hexamethylenebis(4-isopropyl-5(4H)-oxacylon), 2.2'-p-phenylene Bis(4-isopropyl-5(4H)-oxacylone), L2'-m-
Phenylenebis(4-isopropyl-5(411)-oxacylone) s 2s2'-naphthalene/bis(4-e30-pyl-5(4H)-oxacylone).

2,2'-bis(4-inbutyl-5(4H)-oxacilone), 2,2'-methylenebis(4-isomethyl-
5(4)i)-oxacylone), 2,2'-ethylenebis(4-inbutyl-5(4H)-oxacylone)
, 2.2'-tetramethylenebis(4-inbutyl-
5(4H)-oxacilone).

2.2'-hexamethylenebis(4-isobutyl-5(
4H)-oxazon) + 2,2' p-phenylenebis(4-isomethyl-5(4H)-oxacilone), L2'-m-phenylenebis(4-inbutyl-
5(4H)-oxacilone).

212'-Naphthalenebis(4-inbutyl-5(4H)
) - oxacillone) group.

2.2'-bis(3,1-benzoxazin-4-one) l 2+2'-methylenebis(3,1-penzoxazin-4-one) + 212'-ethylenebis(3
, 1-benzoxazin-4-one), 2+2'-tetramethylenebis(3,1-benzoxazin-4-one), 2,2'-hexamethylenebis(3--benzoxazin-4-one) + 2+2'-decamethylenebis(3,1-benzoxazin-4-one), 2.
2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-m-722lenebis(3
, 1-benzoxazin-4-one), 2.2'-
Naphthalenebis(311-benzoxazin-4-one), 2,2'-(4,4'-diphenylene)bis(3,
1-benzoxazin-4-one) l 2,2' -
(114-cyclohexylene)bis(3,1-benzoxazin-4-one) t 2+2'-bis(4,5-
dihydro-1,3,6H-oxazin-6-one) +
212'-methylenebis(4,5-dihydro-1,3
, 6H-oxazin-6-one) + 2+2'-ethylenebis(4,5-dihydrol'-11316H-oxazin-6-one), 2,2'-tetramethylenebis(4,5-dihydro-1, 3,6H-oxazine-6-
on).

2+2' p-phenylenebis(4,5-dihydroμ-
1,3+6H-oxazin-6-one), L2'-m-
Phenylenebis(4,5-dihydro-1,3,6H-oxazin-6-one) + 2+2'-bis(4-methyl-5-human p-1+3+6H-oxazin-6-
), 2,2'-ethylenebis(4-methyl-5
-hydro-1+3+6H-oxazin-6-one), 2
．． 2'-p-7enylenebis(4-methyl-5-human I
:l-1+:L6 H-oxazin-6-one)+2+
2'-m-phenylene (4-methyl-5-human I:I-
1,3,6H-oxazin-6-one).

2+2' p-phenylenebis(4-human p-5-methyl-1,3,6H-oxazin-6-one).

2+2' m-phenylenebis(4-hydro-5-methyl-1,3,6H-oxazin-6-one) and the like.

These bisoxacylones and bisoxazinones (compounds of formula (I) above) have the following formula where x, Y and l! can be easily produced by subjecting N,N'-diacylbis (α- or β-7minocarboxylic acid), which is the same as defined above, to an intramolecular dehydration reaction using a dehydrating agent such as acetic anhydride.

#1 Preferred specific examples of the compound represented by formula (n) are as follows. These compounds are called bisbenzoxazinones.

2.8-dimethyl-4HI6H-benzo[l,2-d
: 5,4-d')bis-Ltta)-oxazine-4I6-dinone+217-dimethyl-4H,9H-benzo(1,2-d: 415-d')bis-(1,3
)-xazine-4,9-dione, 2,8-diphenyl-4H,8H-benzo(1,2-d: 514-d'
]Bis-[t+3)-xazine-4,6-dio/I2
．． 7-diphenyl-4H,9H-benzo(1,2-d:
4,5-d')bis-L113)-oxaza/-4
, 6-dione, 6,6'-bis(2-methyl-4H, 3
, 1-benzoxazin-4-one).

6.6'-bis(2-ethyl-4H, 3,1-penzoxazine-4-o'7), 6.6'-bis(2-phenyl-4H, 3,1-benzoxazine-4 -on)
, 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-4H+ 3,1-benzoxazin-4-one) + 6+6'-ethylenebis(2-phenyl-4H) a, t- benzoxazin-4-one)
+ 6.6'-butylenebis(2-methyl-4H, 3
, 1-benzoxazin-4-one), 6.6'-7'
Tyrenebis(2-phenyl-4H, 3,1-benzoxazin-4-one).

6.6'-oxybis(2-methyl-4H, 3,1-benzoxazin-4-one), 6.6'-oxybis(2-phenyl-4Ht Ll-benzoxadi/-
4-one) + 6+6'-sulfonylbis(2-methyl-4H, 311-benzoxazin-4-one) +
6+6'-sulfonylbis(2-phenyl-4H-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) + 7+7'
-methylenebis(2-methyl-411,3,1-benzoxazin-4-one), 7.7'-methylenebis(2-phenyl-4H+ 3+1-benzoxazin-
4-one), 7,7'-bis(2-methyl-4H*3
+1-benzoxazin-4-one) +7.7'-ethylenebis(2-methyl-aH,3,i-benzoxazin-4-one), 7.7'-oxybis(2-methyl-4H+ 3+1- benzoxadi/-4-one)
+ 7+7'-sulfonylbis(2-methyl-4H,
3,1-benzoxazin-4-one), 7.7'
-carbonylbis(2-methyl-4)1, 3,1-benzoxazin-4-one) and the like.

These bisbenzoxazinones represented by the formula LII) are combined with an aromatic diaminodicarboxylic acid represented by the following formula, where R is the same as defined above, and the following formula %formula%, where BI is as defined above. It's the same.

V with a reactive sieve conductor of a monocarboxylic acid, preferably an acid anhydride or an acid halide.

AK can be produced by a condensation reaction in an inert organic solvent or polyphosphoric acid.

In the present invention, the bis-bulky iminoester of the above formula [11 and formula [river] is 1 [i or 2 m 1 in any combination]
The above can be used together.

(C) Reaction and reaction conditions of the present invention The method of the present invention is carried out by reacting the above-described aromatic polyester and biscyclic iminoester at an elevated temperature. Through this reaction, the following reaction formula (
As shown in II and (21), the aromatic polyester molecules 1IljIWl are bonded by their terminal hydroxyl groups, and the aromatic polyester with a higher degree of polymerization is rapidly formed. Reaction formula ill is the reaction between polyethylene te I/'7 tallate and 2,2'-bis(3,1-benzoxazin-4-one), and the reaction formula (2
) is polyethylene terephthalate and 2,8-dimethyl-
4H+6H-benzo (IJ d :5+4 d'
) with bis(3,1)oxazine-4,6-dione.

0〇In the above reaction formulas (1) and (21), n and m! represent the number of ethylene terephthalate repeating units, that is, the degree of polymerization.As is clear from the above reaction formula, 1. The reaction of the present invention It is a reaction in which chains are bonded together through terminal hydroxyl groups, and an aromatic polyester molecular chain with a polymerization degree of m + n is obtained from an aromatic polyester molecular chain with a polymerization degree of n and an aromatic polyester molecular chain with a polymerization degree of m. It can be seen that an aromatic polyester with a higher degree of dispersion can be rapidly produced.

As is also clear from the above reaction formula, according to the reaction of the present invention, an amide bond is generated in the aromatic polyester molecular chain obtained as a result of the reaction. The aromatic polyester molecular chain obtained according to reaction formula III has an amide bond in the main chain, and the aromatic polyester molecular chain obtained has a bender/thorn loop (p@n
An aromatic polyester having one amide group is provided as a dantgroup. However, in both reactions, the reactions proceed in exactly the same manner in that the molecular chains of the aromatic polyester form amide bonds and are bonded by terminal hydroxyl groups.

In the method of the invention, the above reaction proceeds at elevated temperatures. The reaction is carried out in the solid or bath melt state, ie, in intimate contact of the aromatic polyester and the bis-bulk iminoester at a localized temperature.

The reaction carried out in the I@l melting state is carried out by intimately mixing the aromatic polyester and the bis-bulk iminoester at a temperature above the temperature at which the aromatic polyester melts.

The reaction temperature is generally higher than the melting point of the aromatic polyester.
The temperature is 0°C or lower, preferably 1% higher than the melting point of the aromatic polyester and 350°C or lower, and preferably 15°C higher than the melting point of the aromatic polyester and 330°C or lower.

The reaction can be carried out under elevated pressure, normal pressure or reduced pressure. The reaction of the present invention proceeds very rapidly, and generally takes about 15 minutes to proceed sufficiently after the molten aromatic polyester and biscyclic iminoester are brought into close rc contact. That is, according to the research of the present inventor, the reaction of the present invention can be applied to about 30% in some cases.
It has been shown that the migration may occur in a short period of time, such as a few seconds, and that the desired aromatic polyester with increased degree of concentration can be obtained in such a short period of time.

The reaction time of the method of the present invention described above explains that the reaction of the present invention proceeds extremely rapidly.

In actual operations, there is no problem in mixing the molten aromatic polyester and the biscyclic iminoester for a longer time than the above reaction time, and it may even be preferable depending on the combination. In practice, therefore, it is generally about 30 seconds to 60 minutes, preferably about 1 minute to 30 minutes, particularly preferably about 2 minutes to 15 minutes.

The reaction is preferably carried out under an inert atmosphere, e.g. under a surrounding atmosphere.

The reaction of the present invention, which is carried out while the aromatic polyester is in a molten state, is performed while the aromatic polyester is in a molten state]! Any reactor can be used as long as it can form a reaction system that can maintain IK. For example, one reaction can be carried out in an aromatic polyester polycondensation reaction vessel,
It can also be carried out, for example, in a melting IIL type machine.

In the polycondensation reaction vessel, a reaction can be carried out by adding and mixing a predetermined amount of bis-lumped iminoester to the molten aromatic polyester that has undergone polycondensation to 1 degree and has fiber-forming properties. In addition, in the melt M and W machines, aromatic polyester and a predetermined amount of bis-cyclic iminoester are mixed in advance and charged into the melt-molding machine, or aromatic polyester and a predetermined amount of bis-cyclic imino ester are mixed in the bath melt M and mold machine. The reaction can be carried out by charging separately.

When the reaction is carried out in a polycondensation reaction vessel.

By the method of the present invention, an aromatic polyester with an increased degree of polymerization can be obtained, and therefore, when the obtained aromatic polyester with an increased degree of polymerization is made into a product such as a fiber, a film, etc., it is melted in the machine. is melted.

In some cases, when the reaction is carried out in #molten mll, jl
Il! Since the reaction of the present invention proceeds within the above range, a product consisting of an aromatic polyester with a higher degree of polymerization can be obtained from the aromatic polyester raw material only by the bath III forming operation.

Of course, the method of the present invention involves carrying out the reaction of the present invention in a polymerization reaction vessel and adding an additional f1 polymer to the desired 1 degree flattened aromatic polyester. It can also be carried out by carrying out the reaction of the present invention in one machine.

In addition, the reaction of the present invention was carried out once in a bath lilIIM and in a mold machine, and the obtained aromatic polyester with an increased degree of polymerization was not directly converted into a laminar product as described above, but was processed to have an increased degree of polymerization. Aromatic polyester lumber for use in Ilt-type articles can be obtained and, if necessary, can be melted again in a bath melt molding machine to form a finished product.11 The reaction of the present invention can also be carried out in the same phase state.

Reactions that occur in the same phase are aromatic polyesters and biscyclic iminoesters! producing a mixing tube in contact with the v-can;
This is then carried out by heating to a temperature below the melting point of the aromatic polyester.

The reaction is preferably carried out at a temperature of about 8 m below the melting point of the aromatic polyester.
The reaction is carried out at a temperature of 0° C. or higher and lower than the melting point, under normal pressure to reduced pressure, preferably in an inert atmosphere such as 6-Element.

The mixing tube in which the aromatic polyester and the bis-bulk iminoester are in close contact is used to mix the aromatic polyester and the bis-cyclic iminoester under conditions such that the entire amount used of the bis-bulk iminoester does not react. Alternatively, the aromatic polyester is brought into contact with the bis-bulk imino ester 1 at a temperature above the melting point, or the bis-cyclic imino ester is dissolved in an aromatic polyester such as toluene or xylene. It can be produced by contact impregnation with an organic S* bath solution such as carbonized wood.

The reaction of the present invention in the same phase state is advantageous when carried out after the aromatic polyester is made into a molded product such as a fiber or film.

For the bottom plate operation, normal conditions for aromatic polyesters can be used, and for example with increased degree of polymerization,
The product is made of an aromatic polyester with a higher degree of polymerization by carrying out the reaction of the present invention on a molded product without using the molding conditions for aromatic polyester with a high degree of polymerization such as a viscosity of 1.0 or more. This is because the finished product can be easily obtained.

As is clear from the above reaction formulas 11+ and (2), chemically speaking, the reaction of the present invention proceeds between 25 terminal hydroxyl groups of an aromatic polyester and 1 mole of bis lumpy iminoester. ).

However, what is illegal in the present invention is a method for producing an aromatic polyester having a high degree of polymerization using the above reaction, and it is necessary that all the terminal hydroxyl groups of the aromatic polyester used react with the bis-lump iminoester! There isn't.

Therefore, even if the amount of biscyclic iminoester is stoichiometric to the terminal hydroxyl group of aromatic polyester, or the biscyclic iminoester is less than the stoichiometric amount to the terminal hydroxyl group of aromatic polyester. Of course, when an ester is used, not all of the hydroxyl groups at the ends of the aromatic polyester are obliterated by the method of the present invention. On the other hand, when a biscyclic iminoester of chemical negative or higher is used for the terminal hydroxyl group of an aromatic polyester,
Even when all of the terminal hydroxyl groups are consumed, a portion of the biscyclic iminoester remains unreacted and is contained in the aromatic polyester with a higher degree of polymerization.

The method of the present invention essentially includes all of the embodiments described above.

In the method of the present invention, 0.05 to 2 biscyclic iminoesters are added per equivalent of terminal hydroxyl group of the aromatic polyester used.
It is preferably used in a molar ratio, and more preferably in a 0.1 to 1 molar ratio.

According to the research of the present invention, by the method of the present invention.

Approximately 70% of the total hydroxyl groups of commonly used aromatic polyesters
For example, polyethylene terebutanoate and typical bis-cyclic imino esters show that up to N can contribute to the bond Nz between terminal hydroxyl groups using sufficient reaction time and an optimal amount of bis-cyclic imino ester2. ,2'-bis(3,
This was confirmed by reaction with l-benzoxazin-4-one).

CD) Embodiments of the present invention As described above, the essence of the present invention is to react the hydroxyl group at the end of the molecular chain of an aromatic polyester with a biscyclic iminoester to produce a substantially fine aromatic polyester with a higher degree of monomerization. The purpose is to manufacture.

Thus, one embodiment using the reaction of the present invention is 'C'.

01 A method using an aromatic polyester and a bis-cyclic imino ester as they are as one reaction raw material, (21 A method using a thermoplastic resin containing an aromatic polyester and a bis-cyclic imino ester in an unreacted state and/or in the form of an end-blocking agent) and (3) converting the aromatic polyester into a terminal hydroxyl group such as the terminal carboxyl group by reacting the aromatic polyester with a low carboxylating agent that reacts with the terminal carboxyl group to produce a terminal hydroxyl group. At the same time, the reaction of the present invention for bonding the terminal hydroxyl groups of the aromatic polyester was carried out in step 5.
, a method using an aromatic polyester having a terminal carboxyl group, a low carboxylating agent, and a biscyclic iminoester as reaction raw materials.

There is. These embodiments will be described below.

(11 Embodiments As already described in Kell J, aromatic polynisder and biscyclic iminoester are reacted in a molten state in a polymerization reactor; a melt molding machine; This is a method for producing an aromatic polyester having a higher degree of i, or a molded product made of the same, by reacting the polyester.

This embodiment is a typical example of the method of the present invention and is as already explained.

Moreover, in this actual embodiment, the aromatic polyester and the bis-lumped iminoester are premixed.

It also includes an embodiment in which the resulting mixture is reacted in a molten state in a melting machine.

In such premixing, the bis-lump iminoester is used in an amount equal to or more than the equivalent mole of the terminal hydroxyl group of the polyester to be mixed, and the melt mixing time is set appropriately. Achievement 1- can be achieved by making clauses.

According to the research of the unexploded kJA＠, such a mixture requires a mixing temperature (T,'C) and a mixing time (t +
It has been clarified through many experiments that this can be achieved by determining 5econd).

10I t ≦-0,008T + 4.8 preferably.

More preferably log t≦−0,008′l′+4.4.

1i+g t≦-(1,008T+4.2, log i≦-0,008T+4.0)?
/106.9 polymer, preferably 20 eq/10'
1 polymer one or more, more preferably 30 eq/10'
Premixed polymers containing one or more 11 polymers can be obtained.

The content of cyclic imino ester groups in the obtained premixed polymer is 1. For example, in the case of polyethylene terephthalate, the premixed polymer is bath-dissolved in benzyl alcohol containing about 20μ of water at 210°C for 2 minutes, and phenol red is added as an indicator solution. From the titration lid (X) which was neutralized and titrated with Nfi9-terbenzyl alcohol bath solution, the premixed polymer was bath-dissolved in a phenol/tetrachloroethane mixed solution, and detrapromophenolphthalene slue was used as an indicator liquid. ．． Based on the value (X-Y) obtained by subtracting the titration voltage obtained by neutralization titration with I N caustic soda-benzylfurfur bath solution,
It can be determined by extrapolating from a calibration curve prepared in advance.

Embodiment No. 121 According to this embodiment, the biscyclic iminoester used in the reaction is contained in a thermoplastic resin in an unreacted state or in the form of an end-blocking agent, and the thermoplastic resin and the aromatic polyester are melted. , a reaction between aromatic polyester α molecular chain terminal hydroxyl groups with a cyclic iminoester, and containing the thermoplastic resin, 1
It is possible to produce aromatic polyester or molded products thereof with a higher degree of purity.

Therefore, in this method, a thermoplastic resin containing a large amount of cyclic iminoester groups capable of reacting with the terminal hydroxyl group of the aromatic polyester is produced in advance, and a predetermined amount of this resin is mixed with the aromatic polyester according to the membership fee. . It is suitably used in a method called the so-called masterbatch method.

Thermoplastic resins include, for example, aromatic polyesters having an aromatic dicarboxylic acid as the main acid component and alkylene glycol as the main glycol component, as well as other aromatic polyesters having an aromatic dicarboxylic acid as the main acid component and alkylene glycol as the main acid component. Aliphatic polyester, polycarbonate, polyamide as the main glycol component.

Polyolefins, polyethers, polysulfones, etc. can be used.

Examples of the aliphatic dicarboxylic acids and alkylene glycols include the same ones as mentioned above,
Also, for example, 2,2-bis(4-hydroxyphenyl)
Polycarbonate derived from propane or 1,1-bis(4-hydroxyphenyl)cyclohexane;
Polyethylene, polypropylene-polystyrene-poly(
Trimethylpentene-1) fathom polyolefin; polyC
Examples include polyamides such as carbamide and polyhexamethylene diambamide; and polyethers such as polyoxyethylene glycol and polyoxytetramethylene glycol.

When producing a master polyester in which a biscyclic iminoester is contained in an aromatic polyester or an aliphatic polyester, preferably an aromatic polyester, the aromatic polyester contains terminal water l! li! When the group is 1'''f, the bis-bulk imino ester can react with the terminal hydroxyl group, so generally the bis-bulk imino ester is contained in an unreacted state and only the core or one iminoester ring has the terminal hydroxyl group. Reaction with R & 1 - Therefore, some of the dirt/varnish 1 is present in the terminal state of reaction, in the form of a so-called end-capping agent, thus reacting with the bis-bulky iminoester. It is important to mix the aromatic polyester or the U aliphatic polyester.
The bis-cyclic iminonis del was added once a month, and the melting and mixing time could be adjusted too slowly.

Such mixing is preferably performed under the premixing conditions described above.

When using a thermoplastic resin other than polyester, if the thermoplastic resin has a terminal hydroxyl group that can react with the biscyclic iminoester, both can be mixed in the same manner as described above. On the other hand, if the core thermoplastic resin does not contain hydroxyl groups, a master polymer containing the biscyclic iminoester in an unreacted state can be obtained more easily.

'lf1 made by Master Polymer is manufactured using a melt molding machine.
It is preferable to carry out the reaction under normal pressure to increased pressure in an inert atmosphere.

The master polymer prepared by (2) is used in a proportion containing a predetermined amount of cyclic iminoester, and is preferably treated with an aromatic polyester having a terminal hydroxyl group at a temperature equal to or higher than the melting point of the aromatic polyester and the master polymer. By carrying out the reaction of the present invention in a bath melt-mixing machine, a molded article consisting of an aromatic polyester having a higher degree of concentration is obtained.

When a thermoplastic resin other than an aromatic polyester is used as the master polymer, the resulting molded product made of the aromatic polyester or the like having a higher degree of 1 is a thermoplastic resin other than the aromatic polyester. It will contain.

Generally, in the method of the present invention using a master polymer, it is desirable that the master polymer contains 4N bulk iminoester rings, preferably in an amount of 0.1]111 parts or less of the master polymer based on the aromatic polyester 1ifl+iiMK.

The content m of the bis-lump iminoester is 1, for example, M EJ
ffi sex hr fat rc about 3 to about] 00]! 1t
c) o, even about 4 to about 50 [-%, especially about 5 to about 30
] i amount % is preferable.

(Actual & Embodiment 57) The reaction of the present invention is used to bond the terminal hydroxyl groups of an aromatic polyester to each other.

Therefore, a madder aromatic polyester with a wood end hydroxyl group concentration can be said to be a desirable raw material in the present invention, but in general, in substantially linear polyesters, the terminal group cap depends on the degree of polymerization, and It is difficult to obtain a polyester containing all hydroxyl groups.

According to this embodiment of the invention, the fiber-forming material is therefore obtained from an aromatic polyester raw material having a degree of polymerization of the order of 1 for film-forming properties, such as an intrinsic viscosity of at least 0.3.
By converting the carboxyl end of the aromatic polyester into water to increase the concentration of hydroxyl groups, a method is provided in which the reaction of the present invention can be carried out more rapidly.

In this embodiment of the present invention, the terminal carboxyl group is removed. A substantially powdery, fiber-forming or film-forming aromatic polyester is reacted with a hypocarboxylating agent and a biscyclic iminoester which reacts with the terminal carboxyl groups to form terminal hydroxyl groups. Do t.

Examples of the low-carboxylating agent that are already known include monoepoxy compounds or detoxic acid-type low-carboxylating agents that react with carboxyl groups to BQ carbon dioxide to produce hydroxyl A. .

Examples of such monoepoxy compounds include primary compounds.

N-glycidyl phthalimide, N-glycidyl-4-methylphthalimide, N-glycidyl-4,5-dimethylphthalimide, N-glycidyl-3-methylphthalimide, N-glycidyl-3,6-dimethylphthalimide,
N-glycidyl-4-ethoxyphthalimide, N-glycidyl-4-lyphthalimide, N-glycidyl-4-ethoxyphthalimide
4,5-dichlorophthalimide, N-glycidyl-3,
4,5,6-titranoromphthalimide.

N-glycidyl-4-n-7'thyl-5-pmuphthalimide, N-glycidyl succinimide.

N-glycidylhexahydrophthalimide, N-dagrindyl-12,3,6-titrahydrophthalimide, N
-glycidylmaleimide, N-glycidyl-α, β
-dimethylsuccinimide.

N-glycidyl-α-ethylsuccinimide.

N-glycidyl-α-probylsuccinimide N-glycidylbenzamide, N-glycidyl-p-methylbenzamide, N-glycidylnaphthamide F + N-glycidylsteramide, N-methyl-4,5-epoxycyclohexane -1,2-dicarboxylic acid imide IN-ethyl-4,5-! Boxycyclohexane-1,2-dicarboxylic acid imide, N-phenyl-4,5-epoxycyclohexane-1,2-dicarboxylic acid imide, N-naphthyl-4,5-epoxycylic I:ll\xane-1,2- Dicarboxylic acid imide IN-)dyl-3-methyl=4,5-
Epoxycyclohexane-1,2-dicarboxylic acid imide, orphenylphenol glycidyl ether, lauryl glycidyl ether, 2-methyloctyl glycidyl ether.

These can be used alone or in combination of two or more.

Generally, such monoepoxy compounds are present in an amount of 0.1 to 101% by weight, preferably 0.2 to 5% by weight based on the aromatic polyester.
It is used in an amount of 0.3 to 3 fiJI%, more preferably 0.3 to 3 fiJI%.

Also, as a de-acid type low carboxylating agent.

For example, alkylene carbonates such as ethylene carbonate, dialkyl esters of oxalic acid such as diethyl oxalate, polyfulkylene oxalates such as polyethine oxalate, polyalkylene malonates such as polyethine oxalate, etc. .

These acid-reducing acid-type low carboxylating agents are US-based t! F
No. 3637910, No. 37]4125 and Pr.
I No. 3787370, each @ Hosho, and its appropriate usage amount is also described.

These specifications I are adopted as documents in the present invention.

According to this embodiment of the present invention, when a monoepoxy compound is used, the aromatic polyester can be first reacted with the monoepoxy compound and then reacted with the bis-lump iminoester; It is also possible to add an epoxy compound and a biscyclic imino ester to allow the reaction of the monoepoxy compound and the carboxyl group and the bonding reaction of the human μgyl group to proceed in parallel. The advantage of the reaction with monoepoxy compounds is that no volatile by-products are formed and the reaction can therefore be carried out under normal to elevated pressure, for example in an I11 melt molding machine.

In addition, when using a decarboxylation type hypocarboxylating agent,
After the aromatic polyester and the decarburized IM type low carboxylating agent are reacted, thereby substantially completing the low carboxylation reaction, a biscyclic imino ester is then added to the reaction system to carry out a reaction to bond the terminal hydroxyl groups. is desirable. Therefore, even if two of the inventive transfusions are used, the lower carboxylation reaction is preferably carried out under reduced pressure, preferably in an X-coating reactor, as is well known.

As detailed above, according to the present invention, an aromatic polyester having a polymerization degree of a certain degree can be rapidly produced from an aromatic polyester having fixed terminal hydroxyl groups.

Therefore, the method of the present invention does not in any way limit the degree of polymerization of the aromatic polyester produced; however, if the method of the present invention has a is 0.72σ, and from ritetramethylene terephthalate, the intrinsic viscosity is 1.2 at 240°C with a reaction time of 2 minutes.
Polytetramethylene terephthalate of 4 is obtained 'r'L
As can be seen from the above, the method of the present invention is preferably applicable to a method for producing a 1 degree aromatic polyester.

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited by the Examples.

In addition, in the fruiting example, S represents ]I lid part, and the terminal hydroxyl group and carboxyl group of the aromatic polynisder are determined by the method L Makromol of A, Con1x.

Chem, 26 226 (]958)].

Actual Mi11-12 and Comparative Examples] Intrinsic viscosity (L72. Total terminal group cap 988 and terminal hydroxyl group 7f!: 'M-f polytetramethylene terephthalate chip (hot air drying at 140°C for 2 hours) 1 () 0 parts, the predetermined it of the biscyclic iminoester shown in Table 1 is added to V
Mix using a mold planner, then this mixture 1111
! I was melt-extruded using an extruder under the conditions of polymer temperature and average residence time shown in Table 1. Table 1 shows the intrinsic viscosity of the obtained polymer.

Is there a comparison in Table 1? As a comparison, the intrinsic viscosity of the 7' polymer obtained when the biscyclic iminoester is completely extruded into polytetramethylene terephthalate without applying any electric power is also shown.

From the results shown in Table 1 below, it can be seen that the biscyclic iminoester reacts with the polyester during melt extrusion and clearly improves the degree of polymerization of 7 in a short time.

Examples 13 to 21 and Comparative Example 2000,000,000 Limiting viscosity U, 51. Kibata water eR of 988% white on all bases
Polyethylene terephthalate Tyrano (16)
A predetermined amount of the biscyclic imino ester shown in Table 2 was mixed with 100 parts (dried with hot air at 0°C for 2 hours) using a V-type lunder, and then the resulting mixture was heated using an extruder at a temperature of about 265°C. Melt extrusion was performed at the average residence time shown in Table 2. Table 2 shows the intrinsic viscosity of the polymer after extrusion.As a comparative example, polyethylene terephthalate was bath-melt extruded under the same conditions as above without adding any bis-bulk iminoester. The results are also shown in Table 2.

In addition, regarding each of the polyethylene terephthalate with a high degree of polymerization obtained in Example 17 (& limiting viscosity 1.151) and the polyethylene terephthalate (1, limiting viscosity 0.49) obtained in Comparative Example 2. , gel beam emission chromatography (gelpoamaaaLion ch
When the molecular weight distribution was measured by chromatography), the value of Mw / Mn (Mw is the heavy electric average molecular weight, Mn is the number semiuniform molecular weight) was as follows.
The polymer of Comparative Example 2 was 2.9, and the polymer of Comparative Example 2 was 2.9.
8, and the high 1 by using cyclic imino ester
It has become clear that this is due to a reaction such as consolidation or branching, and is not an I process.

Example 22 100 parts of chips of polyethylene terephthalate (limiting viscosity: 4fO, 54) containing 15 mol% of isophthalic acid based on the total acid components were melted in a bath at 260°C in a nitrogen stream with heating and stirring. This bath melt polymer (intrinsic viscosity 0.51
) was added with 1.5 parts of 6.6'-bis(2-methyl-4H,3,1-benzoxazin-4-one) and stirred to react. The intrinsic viscosity of the polymer is 0.5 minutes after addition.
58. 0.6111 in the bale for 10 minutes and 0.6 after another 30 minutes
It rose to 3.

Example 23 A glass reactor equipped with a temperature needle and a distillation device was charged with 38.4 parts of dimethyl terephthalate, 27.0 parts of tetramethylene glycol, and 0.014 parts of tetrabutyl titanate as a catalyst.

The temperature of the reaction mixture was maintained at 220° C. or below, and the transesterification reaction was carried out to an esterification rate of 80%. Next, after purging the inside of the reactor with nitrogen, the III reactant was transferred to a 1 reactor equipped with a stirrer and a vacuum #W unit, and heated at 240°C with a heating medium at normal pressure for 15 minutes at about 20 tmkg.
The polymerization reaction was carried out for 15 minutes under a reduced pressure of VcO and 51IJH9 for 40 minutes. Here, the reaction system was brought to normal pressure with a nitrogen stream, and 2.8
-dimethyl-4H16H-benzo(1,2-d: 5
．． 4-a') BisCI+3] 0.44 part of ogisazine-4,6-dione was added, and the reaction was further stirred. Polytetramethylene terephthalate, whose intrinsic viscosity was 0.54 when saturated, became 0.66 after 2 minutes, 0.82 after 5 minutes,
After a further 15 minutes, a high 1 degree polymer having an intrinsic viscosity of 0.84 was obtained.

Example 24 & Limiting viscosity O, S 3. 100 parts of polytetramethylene terephthalate having terminal hydroxyl groups of 983% of the total terminal group density were melted in a reaction kettle at 245° C. under a stream of IITAC gas, and then 2.2'-p-phenylene bis(3,1
-benzoxazin-4-one) was added thereto, and the mixture was reacted with stirring. After 2 minutes, the intrinsic viscosity of polytetramethylene terephthalate was 1.02, and after another 5 minutes, it was 1.02.
．． 13, which has almost reached the equilibrium value. Thereafter, the mixture was exposed to fire for 30 minutes, but the fllt viscosity was 1.12 and hardly changed.

Example 25 100 parts of polyhexamethylene terephthalate having an intrinsic viscosity of 0.64 and terminal hydroxyl groups of 985% of all terminal groups was melted in a polymerization reactor at 230°C under a stream of wood gas, and then 2+2' p- 722renbis(5(4H)
- 12,730.7 parts of oxa were added and reacted with stirring. The intrinsic viscosity of the polymer is 1.0 after 2 minutes. Ol, 1.12 after 5 minutes, 1.15 after 10 minutes. This reaction was further progressed, but the intrinsic viscosity remained almost unchanged.

Indeed Example 26 Polytetramethylene terephthalate 100 having an intrinsic viscosity of 0.75 and 8296 terminal hydroxyl groups per total terminal cap.
1 part was melted in a reaction vessel at 245°C (nitrogen gas stream), and then 2,2'-bis(3°1-benzoxazine-
After 3 minutes of reaction, the fdl and limiting viscosity of the polyester increased to 1.22.

Examples 27 to 30 and Comparative Example 3 545.8 parts of dimethyl terephthalate and 90.8 parts of polyoxytetramethylene glycol (polyoxybutramethylene 60 parts in the produced polyester
% by weight) and tetrabutoxy titanate 0.0
Charge 25 parts and heat to 180°C to 220°C to distill off the methanol produced as a result of the reaction.
After the release of methanol, the temperature was raised to 240°C and the reaction was carried out at normal pressure for 30 minutes.Then, the reaction was carried out for 30 minutes under vacuum with a piece of absolute specificity of 301 m and 11 g.
When one cup of M9 was carried out under vacuum for 100 minutes, the reduced viscosity (ap/e) of the polymer was 1.12.

The polyester elastomer thus obtained was made into chips, dried for 1 fL, and then tri-blended with a predetermined amount of the bisoxazinone compound shown in Table 3 below.
Bath melt extrusion was carried out with an average distillation time of about 3 minutes. Table 3 shows the reduced viscosity of the obtained extruded polymer. It should be noted that there was virtually no coloration on this heath.

Table 3 In addition, as a comparative example, the polymerization ratio ηap/c obtained when the same procedure as above was performed except that no bisoxazinone compound was added is also shown in Table 3.These results show that bisoxazinone does not react with polyester during extrusion. Reacts with the elastomer and significantly increases its degree in a short period of time.
I can see that you are thinking about it.

Examples 91131-34 and Comparative Example 4 In a reactor similar to Examples 27-30, 97.0 parts of dimethyl terephthalate, 67.5 parts of tetramethylene glycol, 71.8 parts of polyoxytetramethylene glycol with an average molecular weight of 1500, and titanium tetra Nodoxide 0.
Except that 117 parts were charged and the high vacuum reaction time was further increased to 120 minutes.

Indeed, vap/co+9 was reacted similarly to Examples 27-3o.
Polyester elastomer jk No. 8 was obtained. Next, the polypolymer was chipped, dried, and triblended with a predetermined amount of the bisoxazolone compound shown in Table 4 below using a V-type slurender.
℃, and the average extrusion time was about 3 minutes. The obtained polymer yap/e1 is shown in Table 4.

As a comparative example, Table 4 also shows the results obtained when the same procedure as above was carried out except that all bisoxacilone was not added.

Table 4 Examples 35 to 37 and Comparative Power 5 In the same reactor as Examples 27 to 30, 174.6 parts of dimethyl terephthalate, 23.0 parts of dimethyl sebaque b
M + 135 sl of tetramethylene glycol 95 parts of polyoxybutramethylene glycol with an average molecular weight of 1000 and 0.1 part of titanium tetrabutoxide were charged, and the reaction was otherwise carried out in the same manner as in Examples 27 to 30, and yap/
A polyester elastomer with c 1.02 was obtained. Next, a predetermined amount of bisbenzooxazinone shown in Table 5 below was added to the underarm polymer at an absolute pressure of 1. By 245℃ under reduced pressure
The reaction was carried out under stirring for 10 minutes. η of the obtained polymer
sp/c] is shown in Table 5.

For comparison, the results of the same procedure as above except that bisbenzoxazinone was not added are also shown in Table 5 below.
Shown below.

Table 5 Examples 38 to 41 and Comparative Example 6 Intrinsic viscosity 0.50, terminal force lupogyl group 20 equivalent fi/
10! 1 part of N-glycidyl phthalimide was added as a monoepoxy compound to 100 parts of polyethylene terephthalate, and the reaction was stirred at 280°C for 5 minutes in a nitrogen gas stream. Made me react. The intrinsic viscosity and terminal carboxyl group of the obtained polymer are shown in Table 6.

Table 6 Table 6 also shows, as a comparative example, the results obtained in the same manner as above except that all monoepoxy compounds and bisoxazinone compounds were not added.

Table 6 shows that the monoepoxy compound and the bisoxazinone compound react with the molten polyester, reducing the terminal carboxyl group equivalent in a short time and significantly increasing the degree of polymerization.

Examples 42 to 44 and Comparative Example 7 A predetermined amount of the monoepoxy compound shown in Table 7 below was added to 100 parts of polytetramethylene terephthalate having an intrinsic viscosity of 0.72 and a terminal carboxyl group value of 46, and the mixture was heated in a stream of elementary gas. The reaction was carried out at 240'C for 5 minutes. Then, a predetermined amount of the bisoxacilone compound shown in Table 7 below was added,
Made me react. Table 7 shows the intrinsic viscosity and terminal carboxyl group equivalent of the obtained polymer.

In addition, Table 1 also lists, as a comparative example, the results obtained in the same manner as above except that no monoepoxy compound or bisoxacilone compound was added.

Table 7 shows that the monoepoxy compound and the bisoxazon compound react with polytetramethylene glycol under bath melting to reduce the terminal carboxyl group equivalent of the polyester, and furthermore, to significantly increase the degree of polymerization in a short period of time.

Intrinsic viscosity (1,511) Added 1 part of N-glycidyl phthalimide and 1 part of 2,2'-bis(3,1-benzoxazin-4-one) to polyethylene terephthalate toog having a terminal carboxyl group equivalent of 28. Then, the reaction was carried out at 280° C. in a stream of elementary gas.The intrinsic viscosity of the polymer in reaction #IO was 0.84.The amount of terminal carboxyl groups im was 13 equivalents/10·l.

Examples 46 to 48 and Comparative Example 8 Intrinsic viscosity 0.61. Carboxyl terminal group amount 33 equivalents/1
0@II polyethylene terephthalate 960M about 2
ii in a polymerization pot at 80℃! Melt under a bulk air current, then add 9.6 parts of polyethylene oxalate with an average degree of polymerization of 2, and mix under normal pressure with a kneading pressure of about 1 and 19 Oml.
The reaction was carried out under stirring for 5 minutes to obtain a polymer having an intrinsic viscosity of 0.59 and a carboxyl end group amount of 3 equivalents/10"ll. The polymer was then formed into chips, and after drying, 100 parts of the biscyclic iminoester shown in Table 8 was added. A predetermined amount of the polymer was tri-blended and extruded from an extruder at approximately 280°C with an average residence time of 3 minutes.Table 8 shows the physical properties of the polymer.
Shown below.

For comparison, Table 8 also shows the results when the same procedure as for upper sweetfish was carried out except that no biscyclic iminoester was added.
Shown below.

Table 8 Examples 49 to 53 and Comparative Example 9 Intrinsic viscosity 0.73, carboxyl terminal group amount 36 drawing amount/
10”g polytetramethylene terephthalate 1.00
0 part was polymerized and melted at about 245°C under an oxygen stream, and then 1 part of polyethylene malonate with an intrinsic viscosity of 0.16 was melted.
0 parts, and then about 1.011 Jt1 for 5 minutes under normal pressure.
The reaction was carried out with stirring for 15 minutes under reduced pressure of
, carboxyl powder 61114 st/ 1 (1”
jl noho y ma'ni get. Next, the polymer was made into chips, and after drying, a predetermined amount of the biscyclic imino ester shown in 3119 was triblended to 100 parts, and about 2
It was extruded from an extruder at 45°C for an average oil time of 2 minutes.

The properties of the obtained polymer are shown in Table 9. Table 9 also shows the results of a 1° comparative example in which the same procedure as that of Kamiayu and Oka was carried out except that no biscyclic iminoester was added.

Table 9 87-Example 54 Polyethylene terephthalate) (&Ia viscosity [0,57, carboxyl terminal group amount 2 tons @ / ] 0'Jl)] 0
After drying, the mixture was melted in a bath at about 280° C. Next, 3 parts of ethylene carbonate was added and reacted with stirring for 10 minutes under normal pressure and then for 30 minutes under reduced pressure of about 0.5×9. At this time, the intrinsic viscosity of the polymer is 0.59. The carboxyl terminal group cap was 6/10·I. Next, when 1.2 parts of 2,2'-bis(3,1-benzoxazin-4-one) was added and reacted with stirring under a nitrogen atmosphere, the polymer's concentration rapidly increased and the intrinsic viscosity increased. The maximum value was 1.18 after 2 minutes, 1.21 after 3.5 minutes, and 1.18 after 15 minutes.

Examples 55 to 57 and Comparative Example 10 & Limiting viscosity 0.49, terminal carboxyl group amount 6 equivalents 71
100 parts of 0M+ polyethylene terephthalate was triblended with 2,2'-bis(3,1-benzoxazin-4-one) as shown in Table 10 below, and then added using an extruder as specified in the table. Pellets were obtained by extrusion and bath melt kneading at the same temperature and average extrusion time. Table 10 shows the bulk iminoester groups of the Samurai 11 polymer pellets.

Next, the pellet was subjected to injection temperature 295°C after IIt-1#.

It was created and molded in about 1 minute cycle. Table 10 shows the intrinsic viscosity of the Samurai Lahata molded product.

For comparison, starting polyethylene terephthalate was directly molded under the same conditions as above. The results are also shown in Table 1O.

Examples 58 to 6o and Comparative Examples 1 Polytetramethylene terephthalate block copolymer c copolymerized with polyoxytetramethylene glycol having an average molecular weight of about 2.000 and a limiting viscosity of 0.
73. Terminal carboxyl group amount 11 equivalents/l0JI) 10
A predetermined amount of the biscyclic imino ester compound shown in Table 11 below is triblended into 0 parts, and then molten water #! is prepared using an extruder at the temperature and average residence time shown in Table 11. The ginseng was extruded and pellets were obtained. The cyclic imino ester group equivalents of the obtained polymer pellets are shown in Table 1.

Next, after drying the Mukuro polymer pellets, the injection temperature is approximately 240℃.
, injection molded in a cycle of about 1 minute.

Table 11 shows the intrinsic viscosity of the molded product obtained.

For comparison, Nortsk copolymerized polytetramethylene terephthalate was directly molded for the first time under the same conditions as above. The results are also shown in Table 11.

Table 11 Examples 61 to 65 and Comparative Example 12 1! 12 K Indication L Tal Applicable 1111 Resin 100@
A predetermined amount of 2.2'-bis(31]-benzoxazin-4-one) was triblended, and the mixture was then heated using an extruder at the temperatures shown in Table 12 (resin temperature).
The mixture was melted and extruded into chips with an average residence time of about 1 minute.

Next, the amount shown in Table 13 of the master chip QJ thus obtained was triblended with 100 parts of polyethylene terephthalate having an intrinsic viscosity of [0.63], and after drying the mixture,
The polymer was extruded from a T-die into a sheet with a thickness of about 100 μm using an extruder at a temperature of about 270° C. and an average oil time of about 3 minutes. Table 13 shows the intrinsic viscosity of the obtained sheet.
Shown below.

For comparison, all of the above master chips (without addition,
A sheet was extruded from a polyethylene terephthalate T-die using an extruder in the same manner as above. The results are also listed in Table 13.

Table 13 shows that while the 1i limiting viscosity of the sheet of the comparative example is decreased, the intrinsic viscosity of the sheet obtained by the method of the present invention is significantly increased.

Table 12 Table 13 Example 66167 and Comparative Example 13 100 parts of the thermoplastic resin shown in Table 14 and the amount of 2*2'-p-phenylenebis[4,4-dimethyl-
5[4H)-Oxacylon] was triblended, and the mixture was melt-extruded using an extruder at the polymer temperature shown in Table 14 at an average oil quality time of about 1 minute to form chips to obtain master chips.

The amount of the obtained master chip shown in Table 15 was triblended with 100 parts of polytetramethylene terephthalate having an intrinsic viscosity of 0.71, and after drying, the polymer was heated at a temperature of about 250°C.
A sheet having a thickness of about 200 μm was obtained by melt extrusion from a T-die using an extruder under conditions of an average residence time of about 25 minutes. Table 15 shows the ultimate viscosity of the obtained sheet.

For comparison, Table 15 also shows the results when polytetramethylene terephthalate was melt-extruded under the same conditions as above without adding any master chips. Table 1
5, it can be seen that the sheet obtained by the method of the present invention has a significantly increased intrinsic viscosity.

Table 14 Table 15 Actual jmflJ 68 + 69Ahi ratio UN ] 4 (
tM phase JI response) 94kf11) Polymerization reaction of 960 parts of polyethylene terephthalate with an intrinsic viscosity of 0.65 and a carboxyl end group cap of 35 equivalents/1oay at about 280'C
Then, 9.6 parts of polyethylene oxalate having an average degree of polymerization of 2 was added, and the mixture was allowed to react under normal pressure with stirring for 15 minutes under a pressure of about 1.0 m1151.

a! Limiting viscosity 0.62, carboxyl end group amount 3 equivalents/
1 oey of polymer was obtained. Next, the polymer was formed into chips, dried, and then heated to a temperature of 280'C.

Melt-extruded from an extruder with an average residence time of about 3 minutes, intrinsic viscosity 0.60, carboxyl group 6 equivalents/10
6F with a thickness of about 300 fi (IJ comb) was obtained. The sheet was immersed in the xylem/#l solution of the cyclic imino ester compound shown in @16 and treated for 60 minutes at the boiling point of the same solvent. The sheet was impregnated with a cyclic iminoester. After drying, the sheet was heated at 230'C w.
Heat treatment was performed for 2 hours under IX atmosphere. Table 16 shows the fi@viscosity of the sheet after heat treatment.

For comparison, a sheet before the above impregnation treatment was heat treated in the same manner as above. The results are also listed in Table 16.

Iti From the table above, it can be seen that the degree of polymerization of the sheet impregnated with cyclic imino ester is significantly increased.

Practice 91770-72 Intrinsic viscosity 0.53, 2 to 100 parts polyethylene terephthalate chips with 85X terminal hydroxyl groups per total end
．． After tri-blending a predetermined amount of 2'-bis(3,1-benzoxa-, 9g-zin-4-one), 36 spinning holes with a diameter of 0.5 fins were created in a spinning tube having a heating area directly below the spinneret. A separate spinneret was installed, and the fm melt polymer was spun at a temperature of 300° C. and an average residence time of about 5 minutes to obtain an undrawn yarn. This undrawn yarn was heated at 90°C, with a magnification of 3.6.
First stage stretching at 0x, then temperature 200°C, 1x ratio 1.5
After the second stage drawing at 0 times, tension heat treatment was performed at a temperature of 220° C. to obtain a drawn yarn. Table 17 shows the intrinsic viscosity and strength of the drawn yarn obtained.

Table 17 -99F-

Claims (1)

[Scope of Claims] 1. Substantially linear, fiber-forming or Film-forming aromatic polyester is expressed by the following formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・〔I
] Here, Y is a divalent hydrocarbon group which may contain a heteroatom, and X is a divalent hydrocarbon group which has one or two ring member carbon atoms forming the iminoester ring, and which is non-containing under the reaction conditions. Reactive divalent hydrocarbon group. l is 0 or 1, or the following formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[II] Here, A is the following formula [II]-a ▲Mathematical formula, chemical formula, There are tables, etc.▼・・・・・・[II]
-a Here, R^2 is a monovalent hydrocarbon group. Or the following formula [II]-b ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[II]
-b Here, the definition of R^2 is the same as above, it is a group represented by, R is a tetravalent aromatic group which may contain a hetero atom, and R^1 is R^2 is the same or different monovalent hydrocarbon group, and is mixed with a biscyclic iminoester compound represented by in a melt molding machine at a temperature higher than the melting temperature of the aromatic polyester, and the molecular chains of the aromatic polyester are combined with terminal hydroxyl groups. 1. A method for producing a molded product made of aromatic polyester having a higher intrinsic viscosity, characterized by bonding by bonding. 2. The manufacturing method according to claim 1, wherein the biscyclic iminoester compound is used in a ratio of 0.05 to 2 moles per equivalent of the terminal hydroxyl group of the aromatic polyester. 3. The manufacturing method according to claim 2, wherein the biscyclic iminoester compound is used in a proportion of 0.1 to 1 mole per equivalent of the terminal hydroxyl group of the aromatic polyester. 4. The biscyclic iminoester compound has the above formula [I]
The manufacturing method according to claim 1, wherein X is an aromatic hydrocarbon group optionally substituted with a substituent that is non-reactive under molding conditions. 5. The biscyclic iminoester compound has the above formula [I]
The manufacturing method according to claim 4, wherein l=0, that is, two iminoester rings are directly bonded. 6. The manufacturing method according to claim 1, wherein the aromatic polyester to be bonded to the biscyclic iminoester compound has a hydroxyl group in 50 mol% or more of all terminal groups. 7. The manufacturing method according to claim 1, wherein the aromatic polyester is polyethylene terephthalate. 8. A substantially linear fiber-forming or film-forming aromatic polyester having a terminal hydroxyl group, containing terephthalic acid as the main acid component and alkylene glycol having 3 to 6 carbon atoms as the main glycol component. 0.1 to 1 mole per equivalent of terminal hydroxyl group of aromatic polyester, 2,
2'-bis(3,1-benzoxazin-4-one),
2,2'-p-phenylene-bis[4,4-dimethyl-
5(4H)-oxazolone], 2,2'-m-phenylene-bis[4,4-dimethyl-5(4H)-oxazolone], 2,2'-p-phenylenebis[3,1-benzoxazine- 4-one], 2,2'-p-phenylenebis[4-isobutyl-5(4H)oxazolone], 2,
8-dimethyl-4H,6H-benzo(1,2-d:5,
4-d') bis(3,1)oxazine-4,6-dione, 2,7-dimethyl-4H,9H-benzo(1,2-d
:4,5-d')bis(1,3)oxazine-4,9-
dione and 6,6'-bis(2-methyl-4H-3,
1-benzoxazin-4-one) in a melt molding machine at a temperature higher than the melting temperature of the aromatic polyester, and the molecular chains of the aromatic polyester are combined with terminal hydroxyl groups. The manufacturing method according to claim 1, characterized in that the bonding is performed by: 9. The manufacturing method according to claim 8, wherein the aromatic polyester is polytetramethylene terephthalate. 10. The manufacturing method according to claim 1, wherein the molded product is in the form of fiber or film.