JPS60228531A - Aromatic polyester carbonate - Google Patents

Abstract

PURPOSE:A low-cost aromatic polyester carbonate excellent in heat resistance, mechanical properties, electrical properties, dimensional stability, etc., having a specified reduced viscosity and a specified constitution of molar ratios among six kinds of structural units. CONSTITUTION:Two kinds of diphenols [e.g., 2,2-bis(4-hydroxyphenyl)propane and 2,2-bis(4-hydroxyl-3,5-dibromophenyl)propane] are dissolved in an aprotic organic solvent (e.g., methylene chloride). To this solution is added an organic base (e.g., pyridine) as an acid acceptor in an amount of at least 2mol per mol of the diphenols, and the resulting solution is reacted with phthaloyl chloride and phosgene to obtain a polymer in which the molar ratios among the structural units of formulas I -VI (wherein R<1-32> are each H or a hydrocarbyl group, X<1-8> are halogen atoms) are as follows: ( I +III+V):(II+IV+VI)=10-90:90-10, ( I +II):(III+IV+V+VI)=10-90:90-10, (III+IV):(V+VI)=90-10:10-90, and the reduced viscosity [as measured in a phenol/tetrachloroethane mixture (1:1 by weight) at 30 deg.C]>=0.1dl/g.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to aromatic polyester carbonates.

[Prior art]

The method of producing a polyaromatic polyester by the Kai Tsukuda polymerization method by mixing an organic solvent solution of a mixture of terephthalic acid dichloride and in7thalic acid dichloride with an alkaline aqueous solution of bisphenol A has been well known for a long time, and is heat resistant. Therefore, it is not necessarily preferable.

On the other hand, polyether sulfone produced by reacting bisphenol S (4t, y'-dihydroxydiphenyl sulfone) with alkali gold base Q*4 t'-dichlorodiphenyl sulfone has excellent heat resistance in terms of softness. [Problems to be Solved by the Invention] In view of these points, the present inventors have conducted extensive studies and have developed a method for inexpensively producing aromatic polyester carbonate with excellent irI heat resistance. I found out.

[Means for solving problems]

That is, the gist of the present invention is a 111 dangerous unit (I) represented by the following structural unit general formula [l] (wherein R1 to RIG represent a hydrocarbon group or a hydrogen atom).

An m-structural unit (It) represented by the general formula (ID (in the formula, R11 and R20 represent a hydrocarbon group or a hydrogen atom).

A structural unit (■) represented by the general formula [■] (wherein R2+-R'' represents a hydrocarbon group or a hydrogen atom, and XI and X4 represent a halogen atom).

A structural unit (■) represented by the general formula [■] (in the formula, 127 to R32 represent a hydrogen atom spanning a hydrocarbon group, and X5 to x8 represent a halogen atom).

General formula [Vl 1 Structural unit (V) represented by

General formula [v1] 1 In the structural unit (Vl) represented by.

When consisting of structural units (1) to (IV), the ah unit (
I) + (In): (II) 10 (Iv) nomo h ratio i
1io:y.

~90:10 acid structural unit (1) + (II):
The molar ratio of (III) + (■) is 10:riθ~ri0:10
In the case of structural units (I) to (Vl), structural unit (1) + (III) + (V): (n)
The molar ratio of 10 (IV) + (Vl) is /θ:90-90
: 10 and #), structural unit (1) + (It) : (
III) + (IV) + (V) + (Vt)tD
The molar ratio is /θ: riθ to ri02/θ, the structural unit (I
I) molar ratio of 10 (N'): fl) + (Vl) θ; /θ ~ /θ: 90, reduced viscosity ηsp /
0 is θ, 7di/? These aromatic polyester carbonates are as follows.

To explain the present invention in more detail, the method for producing aromatic polyester carbonate generally involves
Both the condensation method and the melt α-ray method are possible, but interfacial polycondensation and solution polycondensation easily yield polymers with a high degree of polymerization, but melt polycondensation requires the reaction temperature to be 900°C or higher. It solidifies during the process, and in order to obtain a polymer with a high degree of polymerization, it is necessary to carry out polymerization at 300°C or higher, or to carry out subsequent polymerization in the liquid phase. For this reason, it is advisable to use solution polymerization or interfacial polymerization, which can be easily polymerized even at room temperature.

Therefore, the aromatic polyester carbonate of the present invention is composed of terephthalic acid chloride or/and isophthalic acid chloride, phosgene, and the general formula [■] RM R36R42R40.
Bisphenols represented by Rse (in the formula, R33 to R'' represent a hydrocarbon group or a hydrogen atom) and the general formula [■] (in the formula, R43 to R48 represent a hydrocarbon group or a hydrogen atom, and X9 to XI2 represent a halogen atom) It is carried out by reacting with diphenols represented by ) or by further reacting in combination with phenolphthalein.

The reaction method is carried out by solution polymerization reaction or interfacial polymerization reaction. In the case of general I/C solution polymerization, it is carried out in the presence of a tertiary amine as an acid acceptor, and in the case of interfacial polymerization, diphenols and phenolphthalein represented by the general formulas [■] and [■] are Used as an alkaline aqueous solution. In this case, 1st polymerization catalyst is tertiary amine amine, 4th is ammonium compound, and 4th is polymerization catalyst.
Any catalyst used as an interfacial polymerization catalyst, such as a tlH phosphonium compound, can be used. Also thio (l
Of course, a reducing agent such as ift acid soda may be present.

Specific examples of diphenols represented by the general formula [■] include 2. ．． 2-bis(4t-hydroxyphenyl)propane, bis(p-hydroxyphenyl)methane,
Corbis(terhydroxyphenyl)butane, /, /-
Bis(couhydroxyphenyl)butane S/,/-bis(4t-hydroxyphenyl)ethane, J,, 2-
Bis(4t-hydroxy3-methylphenyl)propane, J, 2-bis(4t-hydroxyphenyl)pentane, 2. ．． Examples include 2-bis(4t-hydroxy 3.!dimethylphenyl)propane. Further, these materials may be used alone or in combination, but 2,2-bis(4t-hydroxyphenyl)propane is most preferred from the viewpoint of cost.

Those represented by the general formula [■] include co, 2-bis-(4t-hydroxy 3.!-dibromophenyl)propane, 2. J-bis(4t-hydroxy 3,j-dichlorophenyl)propane, 2,2-bis(4t-
hydroxy (3-chloro-mono-bromophenyl)propane,
-, Corbis(4t-hydroxy3,zdifluorophenyl)propane, 2,2-bis(4t-hydroxy31
! cyiodophenyl)propane, 2,2bis(4t-
Hydroxy i,t dibromophenyl)butane, 2.
．． 2bis(4t-hydroxy31!-dibromophenyl)methane, 2. ．． 2-bis(terhydroxy 3J dibromo-/,6 dimethylphenyl)propane, cobis(4t-hydroxy 3.j dichlorophenyl)pentane 1.2. ．． Examples include 2-bis(Z-hydroxy, i,j dichloro/-methylphenyl)propane.

In addition, these may be used alone or in combination, but from the viewpoint of cost, J, 2-bis (4t-hydroxy 3.
, Cocose (y-hydroxy 3゜! dichlorophenyl)
Flopane is most preferred.

The diphenols represented by the general formulas [■] and [■] and phenolphthalein may be mixed and subjected to the reaction, or may be subjected to the reaction separately.

When using the dienols represented by [■] and [To], the molar ratio of [W):[Vll is /θ;
It can be used at any ratio of θ:/θ, and also [■], [
■] and [V] of the pledge using phenolphthalein.
l] : [■] +7 The molar ratio of enolphthalein is /
It can be used at any ratio between θ:90 and θ:10, and l
]: What is the molar ratio of phenolphthalein? θ
: Can be used in any ratio of 10. Also, considering the moldability of the polymer, what is the molar ratio of [■] and [■] when using diphenols represented by [■] and [To]? 0: j
It is preferable to use it at a ratio of O to 90:/θ, [■
], [■], and when using phenolphthalein, considering the moldability of the polymer, the molar ratio of [■] = [■] + phenolphthalein is! θ: -10~ri θ: 1
It is preferable to use a ratio of 0. Further, in consideration of the water absorption rate of the molded product, [■] it is preferable that the molar ratio of niphenolphthalein is 10:90 to 90:io. Therefore, in a polymer consisting of structural units (1) to (vl), the molar ratio of rVn) : C■] + phenolphthale [vW is! θ: jθ~ri θ: 10 and tomorrow: phenolphthalein molar ratio 10: riO~ri θ: 10
It is particularly preferable to If phenolphthalein is used in combination with [■1] without [■], a polymer that satisfies both WIr thermal properties and water absorption cannot be obtained.

The acid chloride used in the present invention is terephthalic acid dichloride and isophthalic acid chloride, and the amount used is terephthalic acid dichloride in a molar ratio of 3 to 3.
It is preferable to contain 0 mol or more in terms of stability.

The molar ratio of the acid chloride and phosgene used is /θ: θ to 0:10, but especially 30:2.
It is preferable to use the ratio of θ to 70:3θ.

Moreover, when carrying out the present invention by solution polymerization, generally.

Diphenols are placed in an aprotic organic solvent,
The reaction is carried out by using an organic base in the solvent in an amount more than twice the molar amount of the dienol and adding acid chloride and phosgene. Methods such as 6 may also be used, and the temperature may be particularly controlled 1
There is no m1t Fi, but it is usually 0℃~! Performed at θ°C.

Examples of non-flotic organic solvents used in the present invention include methylene chloride, dicyclized ethylene, chloroform, /,'/
, Kourtrikshiroetan, /, /, Ko.

-, tetrachloroethane, carbon tetrachloride, benzene.

Toluene, xylene, dimethylacetamide.

Dimethylformamide, N-metelcopytetraridone, dimethylsulfoxide, tetramethylthiourea, chlorobenzene, pyridine, quinoline, isoquinoline, orthodichlorobenzene.

α-Chloronaphthalene, anisole, etc. are preferred, but any aprotic organic solvent can be used, and these K are not particularly limited. Furthermore, the organic bases used as acid acceptors in the present invention include: Pyridine, triethylamine.

Tri-n-butylamine, quinoline, inquinoline, morpholine, α-picoline, β-picoline.

r-picoline, 3. ! -lutidine, 3.4t-lutidine, 2. Examples include tartidine, 2,6-lutidine, co-,3-lutidine, co-,j-lutidine, 2,4t,4-coli-4dine, and dimethylaniline, but any tertiary amine can be used. However, it is not particularly limited to these.

Isolation of the polymer is carried out by conventional methods, such as rewashing in an organic solvent such as a lower alcohol or a lower ketone, or precipitation by distilling off the reaction solvent after washing with water. This is done by rinsing the ridges again and drying them.

Furthermore, the aromatic polyester carbonate obtained according to the present invention has many advantages. In other words, tensile strength consists of strength, mechanical properties such as tensile modulus, heat resistance, temperature at which thermal contact begins, and atmospheric properties.

Excellent dimensional stability, moisture absorption, low water content, transparent,
It has good moldability and is useful as a molding material and film.

〔Example〕

The present invention will be explained in detail below with reference to Examples.

Note that all reduced viscosities (η5p1
0) was measured at 30° C. with a 0% by weight polymer solution in phenol/tetrachloroethane (30710 weight ratio).

Example/ A solution of 23.7 f of dehydrated methylene chloride <100-1 dehydrated pyridine was prepared in a /l stirring tank equipped with a flat stirring blade and Z baffles, and 6.37 F phenol was added to this. Phthalein, λ of 10Jr2, Cobisu(Kucht4xie3.!-dibromophenyl)propane, 2. of /3,71. Dissolve the cobis-(terhydroxyphenyl)propane. Separately dehydrated methylene chloride 1o
o-ni/0. / j Prepare a solution in which terephthalic acid dichloride of f is dissolved.

The above phenolphthalein, λ, 2-bis-(terhydroxy-3,j-dibutetramophenyl)propane, 2. ．．
Rapidly adding the above solution of terephthalic acid dichloride to a solution of 2-bis-(4t-"hydroxyphenyl)propane at room temperature while vigorously stirring with jOr, p, rn,
Continue stirring for 60 minutes at room temperature.

Inhale phosgene gas into the above reaction solution at a speed of ¥06//min, and stop inhaling phosgene gas when the reaction solution turns yellow at the peak of about 30 minutes. After stirring for a minute, add methanol! After adding the mixture and stirring for another 1 minute to confirm that there is no phosgene in the solution, the stirring is stopped and the reaction solution is taken out.

The taken out reaction solution is vigorously stirred and placed in an aqueous N-hydrochloric acid solution. After 75 minutes, stirring is stopped and the aqueous phase and methylene chloride phase are separated. Next, the separated methylene chloride phase was added to 0. /N
Pour into an aqueous hydrochloric acid solution and separate after stirring in the same manner. Next, the separated methylene chloride phase was placed in water and the same operation was carried out once, and the resulting methylene chloride solution was dropped into warm methanol to precipitate the polymer as a powder, and after further washing with methanol, 7. Vacuum dry at 2Q°C.

Phenol of this polymer: tetrachloroethane (/:
/) η8p10 measured at 3Q℃ with ot7tu into the mixed solution
was 8 ordl/l.

A load of 20kfl/- was applied to the test piece.
2,j 'C The temperature at which the temperature rises in 7 minutes and begins to rapidly deform (
HDT) was measured and found to be 222°C.

The test piece had ηsp/a of θ, 4tΩ/f.

Its engineering R spectrum is 30!0.30 θ.

/400. /! 1. θ, absorption of benzene nucleus at /600t1n-dish, absorption of carbonyl of terephthalate ester at /74tOcm-', /774. There is absorption of the 2-chton ring of phenolphthalein on -1, θ on 29th O5/4t, /3? There was an absorption of methyl groups of bisphenol A and tetrabromobisphenol A in θ, //6θ sub-1 (Figure C-/) The elemental analysis values of the obtained polymer are as shown below, and the amount charged was This agrees with the calculated value based on the molar ratio when /θOchi reacts.

(3HBr Calculated value (%) 6Q, wa! 3.6θ θ, 4tj Actual value (%) 60.9/ J, jg, 20.riO This polymer is expressed in terms of the ratio of structural units.

(1)+(nl)+(V): (n)+(N)+(V
l) = 3s: Bu! (1) +(If): (1)
+ (IV) + (V) + (VD = revised: 3j (I
n) + ([V) : (V) + (VD = to
: t.

Met.

Example λ While dissolving terephthalic acid dichloride in methylene chloride, p-tart and butylphenol were added as a molecular weight regulator at 0.00%.
The same preparation reaction as in Example 1 was carried out except that 3F was added.

The obtained polymer had a η8p10 of θ and a value of Odt/l, and the water absorption rate of the pressed piece was 0.29% by weight.

HDT* is 210°C and η5p10 of the test piece is 0.
417 di/l ``t's.

Example 3 Without using phenolphthalein, 2. As a result of carrying out the same polishing reaction as in Example 1 except that the amount of J-bis(terhydroxy-3,j-dibromophenyl)propane charged was changed to 74f, the ηepia of the obtained polymer was
is 0f3dl/f, HDT* is 2.20℃, and η5p10 of the test piece is θ, ? It was tdl/f.

, and the water absorption rate of the pressed piece was θ, 23 times t.

The engineering R Suiktor of this polymer is 3 ozo.

3θ+20. /400. /, P2O, /100 cm
-' absorption of benzene nucleus, /74tOcm-' absorption of carbonyl of K terephthalate ester? , Jri J-0,
There was absorption of the methyl groups of bisphenol A and tetrabromobisphenol A at /4160°/3J'O11//60 cm-'. (Figure 2) Expressing the polymer with the ratio of structural units as (1) + (
m): (II) + (IV) 36: 6! (
I) + (II) two (II) + (IV) =
Pi ζj: 3-Go.

Comparative Example / 1. Preparation 1 reaction was carried out in the same manner as in Example 1, except that the amount of phenolphthalein charged was changed to 74 tf using copis(hydroxy-3,j-dibromophenyl)furopane. .

Get the letter you want u'v-no IF3p/Cha, 0. ? 9
It was dJ/l. The water absorption rate of the pressed piece was as high as 0.6.2% by weight. Further, HDT* was 2.26°C, η5p10 of the test piece was o, and tr4tcu7t.

[Effect of the invention] As described above, according to the method of the present invention, the water absorption rate is
It is possible to obtain an aromatic polyester carbonate that has excellent physical properties such as starting temperature and is easily molded.

[Brief explanation of drawings]

Figure-/ is Example/ and Figure 1 is the red lA#J of the nine polymers obtained in Example 3! This is an absorption spectrum. Applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent Attorney: Yo Hase - Others/Names

Claims (2)

[Claims] (1) Structural unit (I) represented by the general formula [■] (in the formula, R1 and RIG represent a hydrocarbon group or a hydrogen atom). A structural unit (■) represented by the general formula [13 (in the formula, R11 and RWo represent a hydrocarbon group or a hydrogen atom). A structural unit (■) represented by the general formula [111] (in the formula, Htt to Hza represent a hydrocarbon group or a hydrogen atom, and gl and X4 represent a halogen atom). A structural unit (I%l) represented by the general formula [B] (in the formula, R2? to Ra2 represent a hydrocarbon group or a hydrogen atom, and x5 to XI represent a halogen atom). A structural moiety (■) represented by the general formula [■] 11. In the structural unit (Vl) represented by general formula [VI) 1 . When consisting of structural units (1) to (IV), the structural unit (
1) + (III) : (II) + (IV) O molar ratio / o: riO ~ riO: /θ ash oak unit (1
) + (It): Cm) + (IV) Nomolar ratio is 10:90 to 90:10, structural units (1) to (V
l), the structural unit (I) + (Wi)
+ (V) : (II) + (1%') + (Vl)
If the molar ratio of
The molar ratio of V) + (Vl) is /θ: riθ~902/θ
Adashi, structural unit (1) + (IV) : (V) +
The molar ratio of (VI) is θ: 10 to 10:90, and in phenol and sodium chloroethane/:/ (weight ratio),
Reduced viscosity ηF3p10 measured at 30°C is 0.1417
Aromatic polyester carbonate having a molecular weight of 9 or more. (2) When consisting of structural units (1) to (IV), structural unit (1) + (II[) : (It) + (IV)
The molar ratio of 3θ near 0 to 7θ 230 is the structural unit (
■) + (1) II (Ill) + (IV) molar ratio is jO
:jO~riθ; 10, structure unit (1)~(Vl)
When the structural unit consists of (1) + (III) + (
V) :(II) 10(IV) +(Vl) (7) Mol JtJEj o Near o ~70:30 aashi,''
Structural unit (I) + (It) two (It) + (PI)
The molar ratio of +(V) + (Vl) is! 0:30-90 2/θ Ash, @ unit (■) 10 (Iy): (v)
+ The aromatic polyester carbonate according to claim 1, wherein the molar ratio of (Vl) is 10: θ to θ:/θ.