JPS6134054A - Aromatic polyester composition - Google Patents

Abstract

PURPOSE:An aromatic polyester composition which shows an improvement in flowability in processing thereby achieving an object of improving the moldability, prepared by mixing two or more aromatic polyesters having different ratios of bisphenol monomer components. CONSTITUTION:The titled composition comprises two or more aromatic polyester copolymers each of which consists of the structural units shown by formula A (where the carbonyl groups are at the meta or para position to each other), formula B (where the O atoms each are at the meta or para position to the SO2 group), and formula C (where the O atoms each are at the meta or para position to X; X is a 1-10C divalent hydrocarbon group, O, CO, S, SO or SO2; a is 0 or 1; R1-4 each are H, a 1-8C hydrocarbon group or a halogen; not all R1-4 are H when X is SO2 and a is 1), satisfies the conditions of formulas I, II, and III, and has a different nB/nC ratio from each other (nA, nB, and nC respectively are the numbers of the structural units of formulas A, B, and C existing in a copolymer).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an aromatic polyester composition that has excellent thermal stability and moldability.

[Conventional technology]

Aromatic polyesters produced from terephthalic acid, isophthalic acid, or their derivatives, and bisphenols or their derivatives have poor mechanical properties such as tensile strength and bending strength, and thermal properties such as heat distortion temperature and thermal decomposition temperature. It is known that these resins have excellent performance in various physical properties such as electrical properties and electrical properties.

In particular, compared to aliphatic polyesters such as polyethylene terephthalate, the thermal properties are greatly improved.
It also has significantly better heat resistance than polycarbonate resin.

However, in recent years, the performance required of resins has become even more stringent, and even better heat resistance has become necessary. Particularly in some cases, heat resistance that allows immersion in a solder bath is required. In order to satisfy such heat resistance requirements, conventionally known 2,2
- Aromatic polyesters using only bis(4-hydroxyphenyl)propane are insufficient, and the present inventors have developed aromatic polyesters containing bis(4-hydroxythunyl) sulfone residues in the polymer structural units. It has been found that polyester is preferred. However, aromatic polyesters having such excellent heat resistance naturally have poor melt processability, which often causes problems in practical use. Therefore, there is a strong desire to obtain an aromatic polyester that retains its original heat resistance, maintains sufficient moldability, and does not pose any practical difficulties, but this cannot be achieved using conventional technology. It was difficult.

[Problem that the invention seeks to solve]

The object of the present invention is to obtain an aromatic polyester having excellent heat resistance and sufficient moldability.

[Means for solving problems]

The present invention relates to the following general formulas (A), (B) and (C).
[However, in the above formula, the carbonyl groups in 2A are in the meta or para position to each other, the oxygen atom in 2B is in the meta or para position to the S02 group, and the oxygen atom in 2 It is in meta or para position with respect to X. X in 2〇 is a divalent hydrocarbon group having 1 to 10 carbon atoms, o, co
, s, so or SO2, and a is O or 1.

R1-R4 each represent hydrogen, a hydrocarbon group having 1 to 8 carbon atoms, or a rogen atom, and may be the same or different, but when X is 802 and a is 1, all of R1-R4 are present at the same time. It's not hydrogen. ] In a polymer consisting of structural units represented by , the number of each structural unit in the polymer is ′rtAli, ? Lc.

Then, 7La/'rLh = 0.04~1.067jc/n
, x = O, 04~t , 06 cutlet, ('7La+
7Lc, )/ffi = 0.99 to 1.10 of the aromatic polyester copolymer '7i-8/? Lc,
This is an aromatic polyester copolymer composition consisting of two or more types having different ratios.

The aromatic polyester copolymer constituting the composition of the present invention is composed of structural units represented by the above general formulas (A), (B) and (C), and in particular: te/'? It is characterized by being composed of two or more types of copolymers having different Lc ratios.

In order to improve the fluidity and moldability of the polymer, (B
It is well known that copolymers can be produced by changing the composition of the structural units of ) and (C), but it is difficult to balance heat resistance and processability, and one must sacrifice the performance of one Must be. However, it has become clear that by combining two or more different copolymers of 71e/x, a polymer composition with improved heat resistance and moldability can be obtained. That is, two or more types of 7L B
/'71c, a polymer consisting of copolymers with different ratios is
Although there is no difference in heat resistance compared to a homogeneous copolymer corresponding to the average composition, it has been confirmed that fluidity is clearly improved, making it a highly practical composition.

Examples of the dicarboxylic acid component corresponding to the structural unit of formula (A) include isophthalic acid and terephthalic acid or derivatives thereof. These may be used alone or as a mixture of two or more.

When the isophthalic acid component and the terephthalic acid component are used in combination, the molar ratio of the former to the latter is in the range of 5:95 to 95:5, preferably in the range of 30 nia 0 to 70:30.

Examples of the dicarboxylic acid derivatives include dichloride and diester. When a diester is used, raw materials constituting the ester include lower aliphatic alcohols having 1 to 10 carbon atoms and phenols having 6 to 18 carbon atoms. Specific examples of diesters include dimethyl terephthalate, dimethyl ino-7 tallate, diethyl iso-7
tallate, diethyl terephthalate, diisopropylisophthalate, diropropyl terephthalate, diisobutyl isophthalate, diphenyl isophthalate, diphenyl terephthalate, dibenzylisophthalate,
Examples include dibenzitaterephthalate. Also, 2
Mixed diesters and monoesters (half-esters) esterified with a seed alcohol can also be used.

The bisphenol component corresponding to the structural unit of formula (B) of the present invention is bis(hydroxyphenyl)sulfone M, bis(4-hydroxyphenyl)sulfone, bis(
Examples include 3-hydroxyphenyl) sulfone and 3-hydroxyphenyl-4-hydroxyphenyl sulfone.

These bis(hydroxyphenyl)sulfones can be used either as a single structure or as a mixture of isomers. Particularly preferred is bis(4-hydroxyphenyl)sulfo/C-al.

The above bis(hydroxyphenyl)sulfones may be subjected to reactions with hydroxyl groups or as various derivatives such as salts with alkali metals or alkaline earth metals or esters with aliphatic or aromatic carboxylic acids. be. The most suitable one is selected depending on the method and form of the polymerization reaction.

In the present invention, as a bisphenol component corresponding to the structural unit of formula (C), the following general formula I (in the formula
, R1, R2, R3, and R4 are as described above, and bistubonols represented by the following are used.

Specific examples of bisphenols represented by formula (■) include 2,2-bis(4-hydroxyphenyl)furopane,
Bis(4-hydroquinphenyl)methane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2
．． 2-bis(3-chloro-4-hydroxyphenyl)furopane, 1゜1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)
Isobutane, 1,1-bis(4-hydroxyphenyl)
diphenylmethane, 2,2-bis(3,5-dimethyl-
4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, bis(4-
hydroxyphenyl) ether, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfoxide, his(3,5-dimethyl-4-hydroxyphenyl) sulfite, his(3,5-dimethyl-
4-hydroxyphenyl) sulfone, 4,4-dihydroxybiphenyl, 3,3,5,5-tetramethyl-4,
4-dihydroquinopiphenyl, 2,2-bis(3,5-
dibromo-4-hydroxyphenyl)propane, bis(
4-hydroxyphenyl)ketone, 2,2-bis(3,
5-diphenyl-4-hydroxyphenyl)propane,
■, 1-bis(4-hydroquinphenyl) 1-phenylethane, bis(3-hydroxyphenyl) sulfide,
Examples include bis(3-hydroxyphenyl) sulfone, 3.3-dihydroxybiphenyl, bis(3-hydroxyphenyl) ether, and 3-hydroxyphenyl-4-hydroxyphenyl ether, which may be used alone or as a mixture of two or more types. It can also be used as

< is 2,2-bis(4-hydroquinphenyl)
Propane, bis(4-hydroxyphenyl)methane, 2
, 2-bis(3,5-dimethyl-4-hydroxyphenyl)furopane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(3,5--)methyl-4-hydroxyphenyl ) sulfone, 4°4-dihydroxybiphenyl, 3,3,5.
Examples include 5-tetramethyl 4,4-dihydroxyphenyl and bis(4-hydroxytunyl)ketone.

In order to produce the polymer used in the present invention, the above-mentioned bis(hydroxyphenyl)sulfones and bisphenols of formula (2) are used, and the amounts used are as follows.

The amount of bis(hydroxyphenyl)sulfones used for the dicarboxylic acid component is 0 per mole of dicarboxylic acid.
．． The amount ranges from 0.04 to 1.06 mol, preferably from 0.10 to 1.0 mol, particularly preferably from 0.15 to 0.96 mol.

In addition, the amount of bisphenols of formula (■) to be used with respect to the dicarboxylic acid component is from 0.04 to 1 mole of dicarboxylic acid.
The range is 1.06 mol, preferably 0.10 to 1.0 mol, particularly preferably 0.15 to 0.9 mol.

Salani, bis(hydroquinphenyl) sulfones and formula■
The total amount of bisphenols is in the range of 0.90 to 1.10 mol per 1 mol of the dicarboxylic acid component.

If the amount of bis(hydroxyphenyl) sulfones (formula 1) of bisphenols used is outside the above range, the properties of the resulting polymer will deteriorate.

Regarding bis(hydroxyphenyl)sulfones, if the bis(hydroxyphenyl)sulfone residue strength per dicarboxylic acid residue in the polymer is less than 0.04, the heat resistance will be poor, and conversely it will be 1.06. If more than one component is present, problems may occur in the moldability of the polymer, the transparency and toughness of the molded product, etc.

Regarding bisphenols (2), the bisphenol residue per dicarboxylic acid residue in the polymer is
If the number is less than 0.04, the moldability of the polymer, the toughness of the molded product, the transparency, etc. are likely to be insufficient;
If the number exceeds 0.06, the property against heat will deteriorate.

The polyester used in the present invention preferably has a logarithmic viscosity ηinh of 0.2 to 2.0, preferably 0.3 to 0.8, as determined by the measuring method described below.

There are no particular restrictions on the method for producing the copolymer constituting the composition of the present invention, and any known method can be applied. Typical examples of polymerization methods include the following methods.

That is, bis(hydroxyphenyl) sulfones and bistunols of formula (2) are dissolved in an aqueous phase together with an alkali metal hydroxide, and inphthaloyl chloride and/or terephthaloyl chloride are dissolved in a water-insoluble organic solvent. , an interfacial polymerization method in which both phases are mixed and reacted; bis(hydroxytunyl) sulfones, bisphenols of formula I, isophthaloyl chloride and/or terephthaloyl chloride are made into a homogeneous organic solvent solution, and the second phase is used as a dehydrochlorination agent. Solution polymerization method carried out in the coexistence of tertiary amines, etc.; typical examples include melt polymerization method in which diester of isophthalic acid and/or terephthalic acid, bis(hydroxyphenyl) sulfones and bisphenols of the formula (■) are melt-reacted. This is a great method.

As mentioned above, there are no particular restrictions on the actual method of preparing the composition of the present invention from copolymers obtained by various methods. Two or more types of copolymers may be mixed as a powder and extruded into pellets, or after being mixed as a solution of the copolymer in an organic solvent, it may be used as it is, or it may be precipitated and used as a powder. Furthermore, it can be made into pellets and then injection molded to form a molded product.

When trying to obtain a polymer corresponding to the average composition of the composition of the present invention with a single copolymer, heat resistance and processability (flowability)
In particular, the fluidity is insufficient compared to the heat resistance.

However, compositions made of copolymers of two or more types, such as the composition of the present invention, tend to have significantly improved fluidity, and especially in resins used in fields where heat resistance is required, fluidity is significantly improved. Improving properties has a major impact on practicality.

In addition to the components already mentioned, the composition of the present invention or the copolymer constituting it can contain one or more of the following reactive components or mixed components.

That is, monohydric phenols and alcohols are used not only to adjust the molecular weight but also to form stable terminal groups and further improve the stability of the polymer. Examples of specific compounds include phenol, 0-phenylphenol, p-phenylphenol, β-naphthol, p-
cumylphenol, m-cumylphenol, p-t-j
Thylphenol, 2,6-dimethylphenol, isopropyl alcohol, t-butyl alcohol, n-decyl alcohol, n-octyl alcohol 2, m-cresol, 0-cresol, 2,6-di-butyl-4-methylphenol , fluorine-substituted aliphatic alcohols, and the like.

Furthermore, various stabilizers can be included for the purpose of further increasing the stability of the composition of the present invention and preventing discoloration. Examples of specific compounds include phosphorous acid, diethyl phosphite,
Diphenyl phosphite, triethyl phosphite, tricresyl phosphite, trioctyl phosphite, tridecyl phosphite, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-ethyl) (phenyl) benzotriazole, pyrogallol, organotin mercaptide compounds, dithionite) triphosphorous acid, polyphenylene, activated anthracene, lower polyesters of bistunols, triphosphorous acid obtained by the reaction of bistunols or dialcohols with phosphorus trichloride. Examples include ester polymers. these are,
Generally, it can be present in the polymer in an amount of 0.01 to 5%.

Although the composition of the present invention is heat resistant,
The viscosity does not become excessive when melted, and the processability is good, but
Furthermore, for the purpose of lowering the viscosity during melting as necessary,
Tricresyl phosphate, triphenyl phosphate, triethyl phosphate, tricresyl phosphite, trioctyl phosphite, dioctyl phthalate, dinonyl phthalate, calcium stearate, magnesium stearate, two molecules of bisphenols and succinic acid, adipic acid or cepatine. It is also possible to add esters with one molecule of each acid.

These are usually from 0.1 to 0.1 based on the total weight of the polymer.
It can be present in a range of 30%.

The composition of the present invention can be molded into a desired product using conventional molding methods and conditions. That is,
Compression molding, extrusion molding, and injection molding are fully possible within the capabilities of conventionally used molding machines.
Moreover, the desired molded product can be obtained in a desirable state without cloudiness or cracks.

The molding processing conditions for the composition of the present invention are shown in examples of extrusion and injection molding.The molding temperature ranges from 250 to 400°C, preferably from 280 to 380'C.

There are no restrictions on the size, shape, etc. of the molded product, and in addition to ordinary molded products, various products such as films, sheet-like products, and parts with precise microstructures can be easily molded.

It is also possible to produce a film using a casting method using the composition of the present invention as a solution, resulting in a film that is transparent, tough, and heat resistant like an extruded film.

〔Example〕

Hereinafter, the present invention will be explained in detail in Examples.

The logarithmic viscosity ηinh in the following examples was determined by the following formula using a mixed solvent of phenol/tetrachloroethane (weight ratio 6/4) at 0.59/old solution.

(In the above formula, tl is the flow time of the polymer solution, t2 is the flow time of only the solvent, and C is the polymer solution concentration ('
;'/di). ) Production Example 1 Bis(4-hydroxyphenyl) sulpone 1.0. Of
'9 (40 mol), 2,2-bis(4-hydroginphenyl)propane 2.28 to 9 (10 mol) and p-
A reaction tank was charged with 0.3 kg (2 mol) of tert-butyA/7xnol, and 51.2 kg of an aqueous solution of 8-IJ hydroxide was added thereto, dissolved with stirring, and cooled to 10°C.

A stream of N2 was passed through the solution for 30 minutes and 20 g of cetyltrimethylammonium bromide was added. Mixture of isophthaloyl chloride and terephthaloyl chloride (1:1) 10.2 kl? (5.0 mol) in dichloromethane 8
The solution dissolved in 01 was added all at once into the stirred reaction vessel, and stirring was continued for 1 hour.

After adding 41 parts of IN hydrochloric acid aqueous solution, 501 parts of water was added, stirred and left to stand, and the upper layer was extracted and separated.

The washed polymer solution layer was supplied to a precipitation tank containing stirring methanol to precipitate the polymer. The colorless polymer thus precipitated was separated, further washed with methanol, and dried to obtain a polymer powder weighing 18.0 kg (referred to as Polymer A).

The obtained polymer has ηinh of 0.58, and NMR
Bis(4-hydroxyphenyl)sulfone residue and 2.2-bis(4-
The abundance ratio of hydroxyphenyl) furonokun residues is 4:1
Met.

Production Examples 2 to 8 The same procedure as Production Example 1 was carried out, except that bis(4-hydroxyphenyl)sulfone, 2゜2-bis(4-hydroxyphenyl)furopane and monophenols were used as shown in Table-1. Polymer powder shown in Table 1 was obtained.

Example 1 Polymer powder A obtained in Production Example 1 2.4 kl? and 1.6 kg of the polymer powder F obtained in Production Example 6 were mixed in a blender, and after drying at 150°C for 3 hours,
It was subjected to an extruder and extruded into pellets at 330°C. Measure the melt index of the obtained transparent pellet (Toyo Seiki, Melt Indexer-1320°G2
．． 16 kg/Cl1) t, the above pellets were molded into an injection molding machine (Arprug, Hydronica A220H).
The material was molded and its tensile strength, elongation, heat distortion temperature, etc. were measured.
The results are summarized in Table 2.

Comparative Examples 1 and 2.3 Polymer powder A obtained in Production Example 1 Polymer powder F obtained in Production Example 6, and polymer powder obtained in Production Example 3 with the same monomer ratio as the composition of the Example C was individually extruded and injection molded in the same manner as in Example 1, and the results shown in Table 2 were obtained.

As is clear from Table 2, Polymer A of Comparative Example 1 alone has excellent heat resistance as represented by the heat distortion temperature, but Polymer F of Comparative Example 2 has poor fluidity and, on the contrary, Good properties, but poor heat resistance. In the case of the polymer having the composition of Example 1, both heat resistance and fluidity showed good values, indicating that it was well-balanced and highly practical. Polymer C, which is a copolymer having a bisphenol composition similar to that of Example 1, does not have improved fluidity compared to the polymer of Example 1.

Examples 2 to 5 Polymers B to E, G obtained in Production Examples 2 to 5, 7.8,
Using H, mixing pelletization and injection molding were carried out as shown in Table 3 in the same manner as in Example 1, and the results shown in Table 3 were obtained. It was confirmed that all of them had good values for both heat resistance and fluidity, and were well-balanced and highly practical.

Table-3 1) 320°G, 2.16kl? Measurement with PeV throat Production Examples 9 to 17 It was carried out in the same manner as Production Example 1 except that bis(4-hydroxyphenyl)sulfone and other bisphenols were used as shown in Table-4. A polymer powder of Tako-Q was obtained.

Examples 6-11 Polymer A and ■ obtained in Production Examples 1 and 9-17
~Q with the composition shown in Table 5, mixed in the same manner as in Example 1,
Pelletization and injection molding were performed, and the results shown in Table 5 were obtained. All of them were confirmed to be highly practical with a good balance of heat resistance and fluidity.

〔Effect of the invention〕

In the present invention, by mixing two or more types of aromatic polyesters with different bisphenol monomer composition ratios, processing fluidity is improved without impairing the mechanical properties and thermal properties possessed by aromatic polyesters, and molding which has been a problem in the past has been improved. Improved processability has been achieved, and its industrial value is considerable.

Claims (1)

[Claims] 1) The following general formulas (A), (B) and (C) ▲ Numerical formula,
There are chemical formulas, tables, etc. ▼ (A) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (B) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (C) [However, in the above formula, the carbonyl group in formula A is Oxygen atoms in formula B are in meta or para position to each other, SO_
In formula C, the oxygen atom is in meta or para position to X. X in formula C is a divalent hydrocarbon group having 1 to 10 carbon atoms, O, C
Indicates O, S, SO or SO_2, and a is 0 or 1. R_1 to R_4 are each hydrogen and carbon number 1 to 8
represents a hydrocarbon group or a halogen atom, which may be the same or different, but when X is SO_2 and a is 1, R_1~
Not all of R_4 are hydrogen at the same time. ] A copolymer consisting of structural units represented by: n_A, n_B, n_C
Then, n_B/n_A=0.04-1.06 n_C/n_A=0.04-1.06 and (n_B+n_C)/n_A=0.99-1.1
n_B/n of the aromatic polyester copolymer represented by 0
An aromatic polyester copolymer composition consisting of two or more types having different _C ratios.