JPS63120729A - Aromatic polymer of good impact resistance - Google Patents

Abstract

PURPOSE:To form an aromatic polymer excellent in flow, heat resistance and impact resistance, by combining three specified kinds of structural units. CONSTITUTION:This aromatic polymer consists of structural units I-III represented by formulas I-III, wherein structural units I amount to 40-90mol% based on the total, structural units (II+III) amount to 60-10mol% based on the total and the ratio of structural units (III) to structural units (II+III) is 1-40mol%. In the formulas I-III, X is at least two groups selected from the groups of the formula IV, V and VI, Y is at least one group selected from among -OXO- and groups of formulas VII and VIII and Z is a group of formula IX or X, provided that a combination in which Y is -OXO- and Z is a group of formula IX is excluded.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to an aromatic polymer that can be melt-molded at temperatures below 400°C and can provide molded products having excellent fluidity, heat resistance, and impact resistance. be.

<Conventional technology> In recent years, the demand for higher performance plastics has been increasing, and many polymers with various new performances have been developed and put on the market. Optically anisotropic liquid crystal polymers have attracted attention because of their excellent mechanical properties.

Fully aromatic polyesters are widely known as such liquid crystal polymers, and for example, homopolymers and copolymers of p-hydroxybenzoic acid are known. However, this p
-Hydroxybenzoic acid homopolymers and copolymers often have too high a melting point and have poor melt flow properties. For this reason, methods of copolymerizing p-hydroxybenzoic acid with various components to lower its melting point have been investigated. method (published patent publication 1986-5002
No. 15), a method of copolymerizing p-hydroxybenzoic acid with 2,6-hydroxynaphthalene and terephthalic acid (Japanese Unexamined Patent Publication No. 54-50594), and a method of copolymerizing p-hydroxybenzoic acid with 2,6-hydroxyanthraquinone. and terephthalic acid (U.S. Pat. No. 4,224,433)
), p-hydroxybenzoic acid, 4,47-dihydroxybiphenyl, terephthalic acid, and isophthalic acid.
Method of combining
6), a method of copolymerizing p-hydroxybenzoic acid with phenylhydroquinone and terephthalic acid (US Pat. No. 4,238,600), a method of copolymerizing p-hydroxybenzoic acid with nuclear-substituted phenylhydroquinone, hydroquinone, etc. (U.S. Pat. No. 4,153,779) and the like have been proposed.

<The melting point that the invention seeks to solve> However, although many of the aromatic polyesters obtained by these methods have a relatively low melting point of 400°C or less, they may have insufficient fluidity or lack heat resistance or impact resistance. However, it is desired to have even better fluidity, higher heat resistance, and higher impact.

Among these, polyesters composed of p-oxybenzoic acid, 4,4'-dihydroxybiphenyl, terephthalic acid, and isophthalic acid have relatively good heat resistance, but have poor fluidity during polymerization. is defective;
It was also found that it is difficult to polymerize only by melt polymerization, and that the impact resistance is not necessarily sufficient. On the other hand, p-
It was found that a polyester composed of oxybenzoic acid, 2,6-hydroxynaphthalene, and terephthalic acid has relatively good fluidity and impact resistance, but poor heat resistance. Therefore, the object of the present invention is to obtain an aromatic polyester having excellent fluidity, impact resistance, and heat resistance.

<Means for Solving the Problems> As a result of intensive studies to achieve the above object, the present inventors found that p-hydroxybenzoic acid, t-butylhydroquinone, 4,4'-dihydroxybiphenyl, 2,6- An aromatic polyester consisting of two or more selected from hydroxynaphthalene and terephthalic acid,
It has been discovered that an aromatic polyester or an aromatic polyester amide obtained by copolymerizing one or more selected from p-7 minophenol and p-phinylene diamine with terephthalic acid and/or isophthalic acid satisfies the above object,
The present invention has been accomplished.

That is, the present invention consists of the following structural units (2), the structural unit (I) is 40 to 90 mol% of the total, and the structural unit ((
A fragrance with good impact resistance, characterized in that In + (lli')) constitutes 60 to 10 mol% of the total and the structural unit (][l/l[) + (I0) is 1 to 40 mol%. The present invention provides a group of polymers.

Two or more groups selected from H3, Y excludes -OXO-1 combinations. ) In the aromatic polymer of the present invention, the above structural unit (I) is a structural unit of a polyester produced from p-hydroxybenzoic acid, and the above structural unit (] is] t-butylhydroquinone, 4'-dihydroxybiphenyl, 2. Structural units of polyester produced from two or more selected from 6-hydroxynaphthalene and terephthalic acid, structural unit I is t-butylhydroquinone, 4,4'-dihydroxybiphenyl, 2,6-hydroxynaphthalene, p
- Indicates a structural unit of a polyester or polyester amide produced from one or more glues selected from aminophenol and p-phenylenediamine and terephthalic acid and/or isophthalic acid, preferably a polyester amide composed of p-aminophenol and terephthalic acid. Alternatively, it is a structural unit of a polyester consisting of the aromatic dihydroxy compound and isophthalic acid (excluding combinations having the same structure as structural unit (I')).

It is essential that the above structural unit CI) accounts for 40 to 90 mol% of the total, and the structural unit CI) accounts for 90 to 100 of the total.
If the amount is 0 to 40 mol %, the fluidity is poor and it is difficult to achieve the object of the present invention, and the most preferable composition is 60 to 80 mol % in the structural unit.

CH.

It is preferable that the content is 20 to 80 mol%.

On the other hand, (ID/l1l)+([)) is 1 to 40 mol%, preferably 5 to 30 mol%.

Further, a composition in which the heat distortion temperature (I8,56#/d) of the injection molded article obtained from the polymer having the above structural unit is 150° C. or higher is preferable.

The aromatic polymer of the present invention can be produced according to conventional polycondensation of polyester or polyester amide, and there are no particular restrictions on the production method, but typical production methods include the following methods (I) to (4). It will be done.

(I) Diacylated products of aromatic dihydroxy compounds such as p-acetoxybenzoic acid and t-butylhydroquinone diacetate), 4.4'-diacetoxybiphenyl, and 2.6-diacedoxynaphthalene, and p-acetoxyacetate class A method of producing by deacetic acid polycondensation reaction from an acylated product such as p-anilide or p-phenylenebisacetamide and an aromatic dicarboxylic acid such as terephthalic acid.

(2) Aromatic dihydroxy compounds such as p-oxybenzoic acid, t-butylhydroquinone, 4,4'-dihydroxybiphenyl, 2,6-cyhydroxynaphthalene, p-aminophenol, p-phenylenediamine, etc., and terephthalic acid, etc. A method for producing aromatic dicarboxylic acid and acetic anhydride or diphenyl carbonate by acetic acid removal or phenol removal polycondensation reaction. However, 2.6
- It is preferable to use a diacetylated product of only hydroxynaphthalene.

(3) Phenyl ester of p-oxybenzoic acid and t
- Removal of diphenyl esters of aromatic dihydroxy compounds such as butylhydroquinone, 4,4'-dihydroxybiphenyl, and 2,6-dihydroxynaphthalene, p-aminophenol, p-phenylenediamine, and aromatic dicarboxylic acids such as terephthalic acid. A method of manufacturing by phenol polycondensation.

Typical catalysts used in the polycondensation reaction are metal compounds such as stannous acetate, tetrabutyl titanate, lead acetate, antimony dioxide, magnesium, sodium acetate, potassium acetate, and trisodium phosphate. Although it is not necessarily necessary to use it during acetic acid depolycondensation, it is sometimes preferable to add a small amount when polyesteramide is used.

Logarithmic viscosity of the aromatic polymer of the present invention (0,1 f/di
e (measured at 60° C. in pentafluorophenol) is preferably LO to 8.0, particularly preferably 2.0 to 6.0.

Furthermore, the melt viscosity of the aromatic polymer of the present invention is 10 to 15
．． 000 poise is preferred, especially 500 to ooo
Poise is preferred.

Note that this melt viscosity is a value measured using a Koka type flow tester under the conditions of (liquid crystal starting temperature +50°C) and a slip rate of 3000 (I7 seconds).

In addition, when carrying out the polycondensation of the aromatic poly of the present invention=#≠≠1, in addition to the components constituting the above-mentioned (I)--, 2,6-dicarboxynaphthalene, 4,4'-diphenyl dicarboxylic Carboxylic acid, 2.2'-diphenyldicarboxylic acid, 1.2
-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 1,2-bis(2-chlorophenoxy)ethane-4,
Aromatic dicarboxylic acids such as 4'-dicarboxylic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, hydroquinone, bisphenol A1 bisphenol S, resorcinol, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, etc. aromatic dihydroxy compound, m-oxybenzoic acid, 2,
Aromatic oxycarboxylic acids such as 6-oxynaphthoic acid and p-aminobenzoic acid may be further copolymerized within a small proportion that does not impair the purpose of the present invention.

The aromatic polymer of the present invention thus formed has a melting point of 400°C.
It can be subjected to ordinary melt molding such as extrusion molding, injection molding, compression molding, and blow molding, and can be processed into fibers, films, three-dimensional molded products, containers, hoses, etc.

During molding, reinforcing agents such as glass fiber, carbon fiber, and asbestos, fillers, nucleating agents, pigments, antioxidants, stabilizers, plasticizers, lubricants, mold release agents, and flame retardants are added to the aromatic polymer of the present invention. Additives such as and other thermoplastic resins can be added to impart desired properties to the molded article.

Note that the strength of the thus obtained molded article can be increased by heat treatment, and the elastic modulus can also be increased in many cases.

This heat treatment can be carried out by heat treating the molded article in an inert atmosphere (for example nitrogen, argon helium or water vapor) or in an oxygen-containing atmosphere (for example air) or under reduced pressure at a temperature below the melting point of the polymer. This heat treatment may or may not be under tension and can be carried out for several tens of minutes to several days.

The molded article obtained from the novel aromatic polymer of the present invention is
Due to its parallel molecular arrangement, it has good optical anisotropy and heat resistance, and has extremely excellent mechanical properties and fluidity.

<Example> The present invention will be explained in more detail with reference to Examples below.

Example 1 P-acetoxybenzoic acid 5L89F (
28,8XlO mol), t-butylhydroquinone diacetate 9.311 (3,72xlθ mol), 4
, 4'-diacetoxybiphenyl 20.22F (7
, 48XlO mol), terephthalic acid 16.61F (I
0, QXlO mol), isophthalic acid L99f (L2x
10 mol) was charged and acetic acid depolymerization was carried out under the following conditions.

First, the reaction was carried out at 250 to 340°C for 3.2 hours in a nitrogen gas atmosphere, then the pressure was reduced to 1.0 flHg, and then the pressure was reduced to 340 to 340°C.
Polycondensation reaction was carried out at 365°C for 0.8 hours to obtain a brown polymer. Further, 5 patch polymerization was carried out under the same conditions, and the polymer was pulverized using a pulverizer manufactured by Horai Co., Ltd. The theoretical structural formula of this polymer is as follows, and the elemental analysis results of the polyester showed good agreement with the theoretical values as shown in Table 1.

l/m/n=72/9.3/18.7 1/ (m+n) =7 2/2 8m 7 n
= 3.3 / 6.7 [Isophthalic acid/(Terephthalic acid + Isophthalic acid)) =
10.7 mol% Calculated from Table 1.

The logarithmic viscosity of this polyester was measured in pentafluorophenol (0.1 f/dJ concentration, 60°C) and was 4.1 (I6/f).

Also, place this polyester on the sample stage of a polarizing microscope,
When the optical anisotropy was confirmed by raising the temperature, it showed good optical anisotropy at 308° C. or higher.

This polyester was subjected to a custom Nestal injection molding machine, Promat 40/25 (manufactured by Custom Heavy Industries Co., Ltd.), under the conditions of a cylinder temperature of 360°C and a mold temperature of 30°C.
'Thickness XI/2' width x 5' length test piece and l/8
A mold notch impact test piece with a length of 2' thick x 2 l/2' was prepared. This test piece was tested at strain rate Iff/
When the bending elastic modulus was measured under the conditions of 50 fl and a span distance of 50 fl, it was 14 GPa. The Izot impact value (mold notch) showed a high value of 30 kg@car/01. In addition, when the heat distortion temperature of the 1/8# thick test piece was measured using a heat distortion measuring device manufactured by Toyo Seiki Co., Ltd., it was found to have excellent heat resistance of 232°C (I8,56#/d).

The melt viscosity of this polymer is 360°C and the shear rate is 30.
00 (I/sec) and 2200 poise, indicating good fluidity.

Example 2 P-acetoxybenzoic acid 5189f (2
g, 8xlQ mol), t-butylhydroquinone diacetate 9.26fc3.7XIO mol), 4
, 4'-diacetoxybiphenyl 14.87F (5,
5×10-mol) 1p-acetoxyacetanilide3.
861 (2, QXlo-'' mol), terephthalic acid 18.61F (I12XIO mol) and sodium acetate 0.2F were charged, and acetic acid depolymerization was carried out under the following conditions.

First, the reaction was carried out at 250 to 350°C for 3.0 hours in a nitrogen gas atmosphere, then the pressure was reduced to 0.8 ffHg, and the reaction was carried out for 3.0 hours under reduced pressure.
Polycondensation reaction was carried out by heating at 50 to 360°C for 0.8 hours to obtain a brown polymer. Further, 5 patch polymerization was carried out under the same conditions, and the polymer was pulverized using a pulverizer manufactured by Horai Co., Ltd. The theoretical structural formula of this polymer is as follows, and the elemental analysis results of the polyesteramide showed good agreement with the theoretical values as shown in Table 2.

1/m/n10-7 2/9.3/1 3.715t!
/ (m+n+o) =7 2/28m/n
Tomi 5.7 / 4.3o7 (m+n+o) w
17.8 (mol%) Calculated from N (%).

The logarithmic viscosity of this polyesteramide was measured in pentafluorophenol (0.1 f/dl concentration, 60°C) and was found to be 3.2 dl/y. - Also, this polyesteramide showed good optical anisotropy at 312°C or higher.

This polyesteramide was molded at a cylinder temperature of 360°C in the same manner as in Example 1, and its mechanical properties and thermal properties were evaluated. The flexural modulus was 16 GPa, and the isot impact value (mold notch) was as high as 34.9 cm/cN. showed that. The heat distortion temperature is 251'c (I8,56
ky7d)

The melt viscosity of this polymer is 360°C and the sliding speed is 30.
The fluidity was good with 4700 voids at 0.00 (I/sec).

Examples 3-10. Comparative Examples 1 to 5 In a round bottom flask, p-oxybenzoic acid (I), t-butylhydroquinone (I), 4,4'-dihydroxypiphenyl I, 2,6-diacedoxynaphthalene, p
-7 minophenol (V3. p-phenic acid (II+)
I+IV+V+VI) = (I'1l-NTI[)
(mole) using the composition shown in Table 3, and then adding 95% acetic anhydride (m+2X (I+IN+V1))
The acetic acid depolymerization was carried out under the following conditions. In Examples 2 to 8, sodium acetate 1. This was done by adding Of.

First, the mixture was reacted for 2 hours at 130 to 275°C under a nitrogen gas atmosphere, and then further reacted for 3 hours at 275 to 360°C.

After that, the pressure was reduced to below L OflHg, and the temperature was further increased to 360°C for 1
The mixture was heated for ~2 hours to perform a polycondensation reaction to obtain a brown polymer.

To measure the liquid crystal initiation temperature and logarithmic viscosity of this polymer, injection molding was performed at liquid crystal initiation temperature + 50°C), and the Izo impact value (mold notch) and heat distortion temperature (I8,56kq) were measured.
ici) was measured.

As is clear from Examples 3 to 10, it can be seen that the polymers of the present invention have excellent impact resistance and heat resistance. On the other hand, polymers other than those used in the invention had heat resistance lower than 145°C (Comparative Examples 1 and 3) and impact resistance of 21°C.
It can be seen that kQDl/CM (Comparative Example 2.6) was poorer than that of the present invention, and the fluidity during polymerization was poor (Comparative Example 4.5).

In addition, the melt viscosity of the polymers of Examples 3 to 0 was 1000 to 5000 voids at a temperature of (liquid crystal starting temperature + 50°C) and a sliding speed of 300 G (I/sec), and had good fluidity. The polymer of Example 6 had poor fluidity of 12,000 poise.

<Effects of the Invention> The aromatic polymer of the present invention can be melt-molded at temperatures below 400°C, and has good fluidity, heat resistance, and impact resistance represented by Izod impact strength. Can be used for precision molded products.

Claims (1)

[Claims] Structural unit (I) consisting of the following structural units (I) to (III)
) is 40 to 90 mol% of the total, and the structural unit [(II) + (I
II)] constitutes 60 to 10 mol% of the total structural unit (I
An aromatic polymer with good impact resistance, characterized in that II)/[(II)+(III)] is 1 to 40 mol%. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・(III) (In the formula, X is two or more groups selected from ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , Y is -OXO
Z
indicates ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. However, this excludes combinations where Y is -OXO- and Z is ▲There are mathematical formulas, chemical formulas, tables, etc.▼)