JPH024822A - Polyester of cyclohexanedicarboxylic acid - Google Patents

Abstract

PURPOSE:To obtain the subject liquid-crystalline polymer moldable by melt- molding and having excellent mechanical properties, heat-resistance and chemical resistance by polycondensing cyclohexanedicarboxylic acid with a specific aromatic diol. CONSTITUTION:The objective polymer can be produced by charging (A) a cyclohexanedicarboxylic acid giving the structural unit of formula I, (B) 2,2-bis(4- hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane giving the structural unit of formula II and (C) an aromatic diol giving the structural unit of formula III [R<1> is group of formula IV (X is H, methyl, etc.)] in the form of e.g., a diacetate into a reaction vessel and reacting the components at 150-360 deg.C.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to cyclohexanedicarboxylic acid and 2.2bis(4
-Hydroxyphenyl)-1,1,1゜33.3-hexafluoroglopane-containing liquid crystalline polyester that can be melt-molded at 300°C or less and exhibits excellent mechanical properties, heat resistance, and chemical resistance. Relating to polymers.

[Conventional technology]

In recent years, materials with poor heat resistance, rigidity, or chemical resistance, that is, thermoplastic resins, have been required for general-purpose thermoplastic resin molded products such as fibers, films, and molded products.

Aromatic polyesters (hereinafter referred to as fully aromatic polyesters) produced by condensation polymerization from aromatic dicarboxylic acids and aromatic diols satisfy the above-mentioned physical requirements to some extent.

JP-A-63-63710 describes at least one aromatic hydroxycarboxylic acid or a reactive structure capable of forming an ester thereof, and a spiro-type dihydric phenol, an aromatic dihydric phenol, or a reactive structure capable of forming an ester thereof. Derivatives and fully aromatic polyesters derived from at least one aromatic dicarboxylic acid or its ester-forming reactive derivatives are described. and this is 4
Novel polyesters are disclosed that are melt moldable at temperatures below 0.000C and provide molded articles and fibers exhibiting excellent mechanical properties and optical anisotropy.

Furthermore, JP-A-61-28059 also discloses a nonwoven product made of a melt-processable wholly aromatic polyester capable of forming an anisotropic melt phase.

On the other hand, a copolymer produced from polyethylene terephthalate and ace-1-xybenzoic acid is known as a liquid crystalline polymer.

[Problem to be solved by the invention]

The wholly aromatic polyester satisfies the physical requirements mentioned above to some extent, but on the other hand, it is insoluble as a material and has many problems in its moldability. Further, a copolymer produced from polyethylene terephthalate and acetoxybenzoic acid is not preferable in terms of heat resistance because it has an insufficient heat distortion temperature of 70 to 80°C.

An object of the present invention is to provide a liquid crystalline polyester polymer that has excellent mechanical properties, chemical resistance, and heat resistance, and can be melt-molded at 300''C or less.

[Means to solve the problem]

The liquid crystal polyester polymer of the present invention contains the following structural unit (I) having a melting point of 300°C or less, and the structural unit (II)
) (I[[) A liquid crystalline polyester of cyclohexanedicarboxylic acid and one or two selected from [].

(trans form and cis form, abbreviated as 0 0 c-ODA)...
-(I) Indicates a group, methyl group, and chlorine. ) The present invention also provides the following structural unit (
IV) is a polyester of cyclohexanedicarboxylic acid.

0-R"-C0...(IV)) The present invention also provides a polyester of cyclohexanedicarboxylic acid, which is obtained by adding the following structural units to the above-mentioned structural units.

10F3) ・・・・・・(n) represents, )・・・・・・(I
) The liquid crystalline polyester polymer of the present invention may be added to conventional polymers without any particular limitation, but a typical manufacturing method is as follows.

t -CDA, c -CDA and bis-AF diacetate, and/or hydroquinone diacetate derivative, acetoxybenzoic acid and aromatic dicarboxylic acid as needed were placed in a reaction vessel and heated at 150°C for 220 minutes in a nitrogen stream. Then, the temperature was raised to 280°C over 30 minutes to 18
Perform the reaction for 0 minutes.

Then, the temperature was raised to 360°C over 160 minutes, and at this temperature, the reaction was carried out for 60 minutes under reduced pressure of 31111111 (L).
Produce the desired polymer.

In this polycondensation reaction, stannous acid, tetrabutyl titanate, lead acetate, antimony trioxide, etc. may be used as a catalyst.

The melting point of the polyester polymer thus produced is 3
It can be used in general extrusion molding and compression molding at temperatures below 00°C.

〔Example〕

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples in any way.

(Example 1) [4-Hydroxybenzoic acid/2,2-bis(4hydroxyphenyl)-1,1,1,3,3,3hexafluoropropane/phenylhydroquinone/trans-1,4-cyclohexanecarvone Acid] Production of copolymer.

4-acetoxybenzoic acid 1.80g (10+onol
), 2, 2-bis(4-acetoxyphenyl) L
L 1,3,3.3-hexafluoropropane1.
05g (2,5nnol), phenylhydroquinone diacetate 2.02g (7,5ml), trans-1,4-cyclohexanedicarboxylic acid 1,72g
(10 mnol) was charged into a reactor, and 15 mnol was charged in a nitrogen stream.
After heating at 0℃ for 20 minutes, heat to 280℃ for 30 minutes.
The reaction was carried out at 280°C for 180 minutes.

The temperature was increased to 360°C for an additional 160 minutes, then 36°C.
The reaction was carried out for 60 minutes at 0°C under reduced pressure of 3 nllHg using a vacuum pump to obtain a light brown polymer.

This polymer was dissolved in P-chlorophenol 5000111 at room temperature, and then purified by reprecipitation with methanol. The resulting precipitate was boiled twice with methanol and then vacuum-dried.

The yield was 3.53 g (yield 75.9%), and the intrinsic viscosity at 50° C. of a 0.5 g/dl solution of P-chlorophenol was 0.86 dl/g.

The thermal decomposition of this polymer was analyzed using DSC (DSC manufactured by Seiko Electronics Co., Ltd.).
-200 type) and Mettler FP-800 type thermo system using an LA microscope, the glass transition point (Tg) was 168°C1 Melting point (Tm): 241 ~
274°C, and showed a liquid crystal phase up to 300'C or higher.

(Examples 2 to 5) Hereinafter, in exactly the same manner as in Example 1, 2,2-bis(4-
By varying the molar ratio of (acetoxyphenyl)-1,1,1,33,3-hexafluoropropane (abbreviated as Bis-AP) and phenylhydroquinone diacetate (abbreviated as Ph-HQ), 4-acetoxybenzoic acid (abbreviated as PHB) 1,80g (101111o1),) Lance-
A polymerization reaction of 1.72 g (10 u+ol) of 1,4-cyclohexanedicarboxylic acid (abbreviated as t-CDA) was carried out, and the results of measuring the physical properties of the obtained polymer are shown in Table 1 together with the results of Example 1.

Note) (PHB) (Bis-AF) (Ph-HQ
) (t-CDA)PHB and -CDA were both blended with IQn+nol.

■ Intrinsic viscosity, P-chlorophenol 0.5g/
The old solution was measured at 50°C.

■ Tg glass transition point ■ Tm: melting point'TC-LC' solid-liquid crystal point ■ "L
C-1' liquid crystal cyclotropic liquid point (Example 6) In exactly the same manner as in Example 1, 7 units of ρ-acetoxyamine,
Incense 1t20.9g (51nol), 2,2-bis(4acetoxyphenyl)-1,1,1,3,3゜3-
Hexafluorogloban 2.10g (5uol) - Phenylhydroquinone diacetate 1.35g (511
1101) When 1.72 g (10 nmol) of trans-1,4-cyclohexanecarboxylic acid was subjected to a polymerization reaction, a polymer was obtained with a yield of 72.3%. P-chlorophenol 0.5g/d! The solution had an intrinsic viscosity of 0.48 dl/g at 50°C. The glass transition point of this polymer is 105°C, the melting point is 228°C to 245°C,
No liquid crystallinity was exhibited.

(Examples 7 to 10) In Example 6, the amount of 4-acetoxybenzoic acid charged was varied, and 2,2-bis(4acetoxyphenyl)-1,1,1,3,3, 3 Hexafluorogloban 2. 10 g (5 uol), phenylhydroquinone diacetate 1.35 g (511101), trans-1,4-cyclohexanedicarboxylic acid 1.72 g <
10 tliol) was carried out, and the results of measuring the physical properties of the obtained polymer are shown in Table 2 together with the results of Example 6.

(Table (remarks) (PH8) (Bis-AF) (Ph-HQ) (t-CDA) Bis-
AF and Ph-HQ are 5111101 and t-CD respectively
A was blended with 10+Hlol.

(2) Intrinsic viscosity was measured at 50°C in a solution of 0.5 g/d1 of P-chlorophenol. (2) There was an undissolved component, so measurements were taken at each house.

■ Tg Niglass transition point ■ Tm: Melting point (Example 11) [4-hydroxybenzoic acid/2,2-bis(4hydroxyphenyl)-1,1,1,3,3,3hexafluoropropane/chloro Production of a copolymer of hydroquinone/trans-1,4-cyclohexanedicarboxylic acid.

In exactly the same manner as in Example 1, 0.9 (5 viol) of 4-acetoxybenzoic acid, 2.2-bis(4-acetoxyphenyl)-1,1,1,3,3,3-hexafluoroprobacillus, 2. 10 g (51Iu++ol), chlorohydroxythiaceta-1-1, 35g (5ilot)
When 1.72 g (10 roraol) of l-lance-1,4-cyclohexanedicarboxylic acid was subjected to a polymerization reaction, 3.30 g (yield 72.3%) of a heavy product was obtained. P-ri tetralophenol 0.5g/d+ solution,
The intrinsic viscosity at 50°C was 1.51 dl/g. The glass transition point of this polymer is 105°C, and the melting point is 288°C.
~>300°C, and showed a liquid crystal phase up to 300°C or higher.

(Examples 12-13) In exactly the same manner as in Example 1, 1.80 g (10 nu++ol) of 4-acetoxybenzoic acid and 1.72+r (1(l) trans-1°4-cyclohexanedicarboxylic acid
lol), 2,2-bis(4-acetoxyphenyl)
-1,1,1-3,3,3-hexafluoropropane 1
．． 05g (2,5+nol) and 1.71g chlorohydroquinone diacetate (7,5ranol), or 2,2-bis(4-acetoxyphenyl)-1,1
, 1-3,3,3-hexafluoropropane2. 10
g (5nnol), methylhydroquinone diacetate 1. A polymerization reaction was carried out at 14 g (5 nvol), and the results of measuring the physical properties of the obtained polymer are shown in Table 3 together with the results of Example 11.

(Remarks) (PHB) (Bis-AF) (CI-HQ) (Me-HQ) (t-ODA) PHB and t-CDA are each 10n+nol, Bis-
AF, CI-HQ, and Me-HQ were each blended with the nalo l in the table.

(2) Intrinsic viscosity was measured at 50°C using a P-chlorophenol 0.5g/d1 solution.

■ Tg Niglass transition point ■ Tm: melting point, T: transition from crystal to liquid crystal C → [
C Dotted ■ T: Transition point from liquid crystal to isotropic liquid LC→■ (Examples 14 to 17) 4-acetoxybenzoic acid (PHB), m-acetoxybenzoic acid (MHB), 2.2-bis( 4-acetoxyphenyl)-1,1,1,3,3,3-hexafluoropropane (Bis-AP), phenylhydroquinone diacetate (P h -HQ), chlorohydroquinone diacetate (CJi-IQ) Cyacetate component consisting of terephthalic acid (TPA), isophthalic acid (TPA)
, trans-1,4-cyclohexanedicarboxylic acid (t
CDA) and a dicarboxylic acid component consisting of cis-trans (mixture)-1,4-cyclohexanedicarboxylic acid (ODA) in various combinations and polymerization reaction performed in exactly the same manner as in Example 1. Table 4 shows the results of measuring the physical properties of the objects.

〔Effect of the invention〕

Conventional wholly aromatic polyester satisfies the requirements for heat resistance, rigidity, and chemical resistance to some extent, but as a material it is insoluble and
It is infusible and has many problems with moldability.

The polyester of the present invention has excellent RIiiili properties, heat resistance, and chemical resistance, and is melt moldable at 300'C or less.

Claims (1)

[Claims] 1. Contains the following structural unit (I), and contains the structural unit (II) (II
A polyester of cyclohexanedicarboxylic acid comprising one or two selected from I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(trans form, cis form)...(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) -O-R^1-O −・・・・・・(III) (However, R^1 has ▲mathematical formulas, chemical formulas, tables, etc.▼,
X represents hydrogen, phenyl group, methyl group, or chlorine. ) 2. In addition to the structural unit of claim 1, the following structural unit (I
V) cyclohexanedicarboxylic acid polyester. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
(IV) (However, R^2 represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼.) 3. In the structural unit of claim 1 or 2. A polyester of cyclohexanedicarboxylic acid further containing the following structural unit (V). ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
(V) (However, R^3 represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼.)