JPS6042419A - Aromatic polyester - Google Patents

Abstract

PURPOSE:An aromatic polyester excellent in heat resistance and mechanical properties, and capable of being produced in an industrially advantageous manner, comprising specified two kinds of structural units and having a specified reduced viscosity. CONSTITUTION:A polyester comprising structural units of formulas I and II in a molar ratio of 95:5-5:95. The reduced viscosity etasp/C is at least 0.1dl/g when it is determined at 30 deg.C in a phenol/tetrachloroethane (1:1)mixture and a concentration of 1.0g/dl. In these formulas, R<1>-R<16> are each H, a halogen atom, hydrocarbyl group, or alkoxyl, A is O, S, sulfonyl, carbonyl, alkylene, or alkylidene, and R<17>-R<24> are each H, a halogen atom, hydrocarbyl group, or alkoxyl. Especially, the case where R<1>-R<16> are each H, and R<17>-R<24> are each H is desirable.

Description

[Detailed description of the invention] The present invention relates to aromatic polyesters.

The method of producing aromatic polyester by an interfacial bonding method by mixing an organic solvent solution of a mixture of terephthalic acid dichloride and isophthalic acid dichloride and an alkaline aqueous solution of bisphenol A has been well known for a long time, but it is not necessarily preferable from the viewpoint of heat resistance. .

On the other hand, polyether sulfone produced by reacting bisphenol s (+, +'-dihydroxydiphenyl sulfone) with alkali gold x salt +, p'-dichlorodiphenyl sulfone has relatively good heat resistance but is expensive. is high.

In view of the disadvantages, the present inventors conducted intensive studies and found a method for industrially advantageous production of an aromatic polyester having even higher heat resistance.

That is, the gist of the present invention is the following general formulas (1) and (1
1) Two types of structural units (in the formula, R1-B11 are hydrogen atoms) have 10 gene atoms.

hydrocarbon group or alkoxy group) and general formula (
AI) (wherein A represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylene group, an alkylidene group, or none, and R17 represents a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group) Structural unit (I)
: Structural unit (II) has a molar ratio of qs:s to 5:9S
In the ratio of phenol:tetrachloroethane;/:
1 of the mixed solution at a concentration of 1. o The reduced viscosity ηmp/C measured at 30°C at y-7at is 0. /at/f or more.

To explain the present invention in more detail, in the forefoot general formulas CI) and (II) of the aromatic polyester of the present invention, R
' to R'6 are hydrogen atoms, and R17 to R' are preferably hydrogen atoms or halogen atoms, and more preferably hydrogen atoms. In addition, in the front leg general formula (n), A is an alkylene group, an alkylidene group, A sulfonyl group is preferred, and an alkylidene group is particularly preferred.

In general, interfacial polycondensation, solution polycondensation, and melt polycondensation are all possible methods for producing aromatic polyesters, but interfacial polycondensation, solution polycondensation, and other methods easily produce highly polymerized polyesters. 300 to obtain the next polymer.
It is necessary to raise the temperature to above ℃ or to perform solid phase polymerization subsequently. In addition, in the case of solution polymerization, it is necessary to use a solution* that dissolves the mixture of bisphenols and amines, isophthalic acid halide, and the polymer produced, but in the case of interfacial polycondensation, it is necessary to use a solvent that dissolves isophthalic acid halide and the polymer. Since it is also possible to use interfacial polycondensation, it is advisable to use interfacial polycondensation.

Thus, the aromatic polyester of the present invention is prepared by combining an organic solvent solution of isophthalic acid civalide with the general formula (1) (wherein R15 to B40 are hydrogen atoms) and 10 gene atoms.

(represents a hydrocarbon group or alkoxy group) and general formula (
IV) (wherein B represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylene group, an alkylidene group, or none, and 141 to R' represent a hydrogen atom, a halogen atom, an alkoxy group, or a hydrocarbon group) ) is suitably produced by an interfacial polycondensation method using an alkaline aqueous solution of bisphenols.

To explain in more detail, the organic solvent used for inphthalic acid sybaride is one that is incompatible with water. Specifically, halogenated hydrocarbons such as methylene chloride, ethylene dichloride, and chloroform, toluene, and benzene can be used. is 1. The solvent for the produced polyester is preferably methylene chloride, l,-1 dichloroethane,
/, /, trichloroethane, /, /, 2-tetrachloroethane, etc. are used. The acid chloride concentration of this solution varies depending on reaction conditions, solubility in organic solvents, etc., but is usually 2 to 30% by weight. Furthermore, since acid chloride is hydrolyzed by water, it is desirable that the amount of water in the organic solvent be small.

Among the bisphenols used in the method of the present invention, those represented by the general formula (1) include 9,9-bis(41-hydroxyphenyl)fluorene! , 9-
Bis(terhydroxy-3-methylphenyl)fluorene, 9,9-bis(tei-hydroxy-3-chlorophenyl)fluorene, wow 9-bis(41-hydroxy-3
-bromophenyl)fluorene, 9,9-bis(terhydroxy-3-fluoro)fluorene, 9,9-bis(
4t-hydroxy-comethylphenyl)fluorene,
Wow 9'-bis(lI-hydroxy-3-methoxyphenyl)fluorene, ? ,? -bis(+-hydroxy-3
, j-dimethylphenyl)fluorene, 9,9-bis(
terhydroxy-3,5-dichlorophenyl)fluorene, Wau-Davis (Hiro-hydroxy-3,5-dibromophenyl)fluorene, Wau-9-bis(4-hydroxy-7enyl)/, 1,3. G, j, A,? , Zaoctachlorofluorene, ? , q-bis(p-hydroxyphenyl)co, 3゜tsuru7tetrachlorofluorene, etc., but are not necessarily limited to these. They may also be used as a mixture. Among these, from the point of view of cost, 91 Terbis (cou-hydroxyphenyl)
Fluorene is the most preferred.

A specific example of the hisphenols represented by the general formula (IV) used in the present invention is λl cocoa (4!-hi)
“Roxyphenyl) Flopuff 1,2..2-bis(4!
-Hydroxy-3,A;-dimethylphenyl)propane, co,corbis(terhydroxy-3+ j-dichlorophenyl)-furopane,co,copis(terhydroxy-J-methylphenyl)propane, co-2-bis(terhydroxy- 3-chlorophenyl)-furopane, bis(
terhydroxyphenyl)-methane, bis(terhydroxy-,?,!-dimethylphenyl)-methane, bis(4I-hydroxy-J,s-dichlorophenyl)-methane, bis(cuhydroxy-3,s-dibutyromophenyl) )-methane, i,i-his(cuhydroxyphenyl)cyclohexane q,t,tl-dihydroxydiphenylbis(4t-hydroxyphenyl)-ketone, bis(cuhydroxy-3°S-dimethylphenyl)
-ketone, bis(terhydroxy-3,, t-dichlorophenyl)-ketone, bis(4t-hydroxyphenyl) sulfide, bis(guhydroxy-3-chlorophenyl)-sulfide, bis(4I-human"roxy 3°s- dichlorophenyl)-sulfide, his-(couhydroxyphenyl)-sulfone, bis(terhydroxy-3,s-dichlorophenyl)ether, *,<t'dihydroxypiphenyl, etc. However, from the viewpoint of cost, co-, λ-bis(couhydroxyphenyl)propane and hibis(terhydroxyphenyl)-sulfone are preferred.

Most preferred is 2-bis(4t-hydroxyphenyl)propane.

The bisphenols represented by these general formulas (ゎ and (1v)) may be mixed and subjected to the reaction, or may be subjected to the reaction separately, but they are subjected to the reaction as an alkaline aqueous solution. It is used as an alkaline aqueous solution of −/j weight −.As the alkali, NaOH, K
Oh.

It is sufficient to mix 2CO3, Na2CO3, etc. with LIOH in an amount equal to or more than twice the mole of bisphenol f44. In addition, in order to increase the solubility of bispheno-Jl/, alcohols such as isopropanol, ethanol, or cyclic ethers such as tetrahydrofuran may be present. There is no particular restriction on the molar ratio of (IN): (IV)
−? s: shiishi s:qs is implemented.

As mentioned above, interfacial polycondensation occurs through contact between an organic solvent solution of isophthalic acid civalide and an alkaline aqueous solution of bisphenols represented by general formulas (1) and (IV). You may add alkaline aqueous solutions of the same type, or vice versa.
Furthermore, both may be supplied simultaneously, or the reaction may be batchwise or continuous, but since the two phases are not compatible with each other, it is best to use a stirring tank with screw-type impellers to disperse them as uniformly as possible. The Faudler type and turbine type are particularly preferred. It goes without saying that it is preferable to strengthen the stirring by providing a baffle plate if necessary. In the case of a continuous system, it is preferable to use a pipeline mixer. The reaction temperature is below SOC, preferably -S to 1IOC for a period of S minutes to 3 hours.

In addition, tertiary amines, chlorinated ammonium compounds, tertiary phosphonium salts, etc. can be used as catalysts during polymerization reactions.
[a Any catalyst used as a M4 can be used, but as a catalyst, the following general formula (V) ~ <
W) It is preferable to use at least one compound selected from the following.

General formula (V) (wherein Ra, R11111, R111, Hn and R4 are hydrogen atoms 4 tkZ 7 ""t'" group Thea') -H4O-R5a, FL'51, Ra2 and Ra3 at least l ke is an alkyl group, B114.RH! and B111l are alkyl groups having carbon number/- or less, and XI is a hydroxyl group or a halogen atom. R″g and H60 are hydrogen atoms or alkyl groups, R61-R6*, H63,
H64, R611 and R6& are alkyl groups and Yl
is a hydroxyl group or a halogen atom) (In the formula, H67 is an alkyl group having 3 to 2 carbon atoms, and R6B Ref (provided that the sum of the carbon numbers of H67, R6a and B10 is 7 to 36, and zl is a hydroxyl group or a 210-gen atom) represented by the general formula (Vllll) (in the formula s R" -R11, R72-B?3 and 174
is a hydrogen atom or an alkyl group, and R? l is an alkyl group.

A compound represented by the general formula (+X) (wherein, R76, R??, H?8, H2O and R80) is an aryl group or an aralkyl group, and
is a hydrogen atom or an alkyl group, and R81 is an alkyl group.

an aryl group or an aralkyl group, and Y2 is a 1 rogen atom or a hydroxyl group) represented by general formula (X) (wherein, Bat -HI12r, RF211, R"
', It! It is an alkyl group with R prime number j to +70, and R82, R62', and R82#.

TL82''') The sum of charcoal wa is 7.2~70 zl
is a hydroxyl group or a halogen atom) (wherein, BU is an alkyl group, benzyl group, or phenyl group, and XB is a hydroxyl group or a halogen atom)
A compound represented by the general formula (XID (wherein, R8' is an alkyl group, a benzyl group, or a phenyl group, and X' is a hydroxyl group or a , 38M and R@0 are alkyl groups, n is 1-5
, x5 is a hydroxyl group or )/logen atom) General formula (XIV) A compound represented by a hydroxyl group or a halogen atom.

The amount of catalyst used during the polymerization is 000/-20 parts by weight, preferably αoos-s parts by weight, based on 700 parts by weight of the resulting polymer (assuming 100% reaction).

The polymerization may also be carried out under pressure in a stirring tank.

Usually selected from the temperature range of -50 to SOC.

Following the polymerization reaction, an aqueous phase containing alkali chloride salts is separated from an organic solvent phase in which the aromatic polyester is dissolved. This separation is performed by static liquid separation or mechanical separation using a centrifuge or the like. If necessary, it is also possible to wash the polymer layer with alkaline water, acidic water, water, or the like. Polymer is isolated from organic solvent solution
In doing so, any known isolation method may be used. If necessary, the polymer is further washed with organic solvents such as methanol, ethanol, acetone, hexane, xylene, etc.

The aromatic polyester obtained according to the invention has many advantages. That is, tensile strength 1 bending strength, tensile modulus,
The curve has mechanical properties such as elastic modulus, heat resistance, thermal decomposition onset temperature, electrical properties 1 Dimensional stability [corrosion, moisture absorption, low water absorption rate, transparency, good moldability, and can be used as a molding material] Useful as a film.

Hereinafter, the present invention will be explained in more detail using examples. Dissolve 0.02bf'4f of sodium sulfide, further add Inbronomol?, td)l, 9
,9-bis(Hiro-hydroxyphenyl)fluorene lA
Dissolve 20jf (0.0/2 mol). Separately 10 liters of water
0ml of sodium hydroxide! / J f, sodium hydrosulfide θ04E Of, co, Corbis (t-hydroxyphenyl) propane 4! ／ ／
I (0,0/1 mol) solution # and isophthalic acid dichloride & 97fP in metelenko chloride O0go
'ff: Dissolved solution yir: Prepare.

Add 0.0 Jfl-7'f of benzyltributylammonium chloride as a catalyst to Juso Hinoki and stir if 0.
While vigorously stirring the solution of 9.9-bis(4-hydroxyphenyl)fluorene at 0 r, p, m,
Rapidly add the above inphthalic acid dichloride solution in methylene chloride.

Next, an alkaline water bath solution of 2-bis(Hiro-hydroxyphenyl)propane is rapidly added.

, 2C for an additional hour.

The methylene chloride phase and the aqueous phase will separate when the stirring is stopped and the aqueous phase is separated.The aqueous phase is removed, and the methylene chloride phase is added to ethanol to precipitate the polymer, which is then washed 3 times with boiling water and heated to /20C.
Dry with.

This polymer's phenol:tetrachloroethane:y(/
: / )<7) Lta17@p/C measured at 30C at 10 f/at for a mixed adult cow was 0.73 at7 f.

When this polymer was pressed with Co10C, a transparent and strong pressed piece was obtained. In addition, using a parallel plate blast meter made by Toyo Seiki, the test piece was 2 OK! /, Apply a load of 7cm, 2,! The temperature was raised at a rate of C/min and the temperature (HDT) at which deformation suddenly started was measured. ! It was C.

Its IR spectrum is 3θ60, 3θ3θ, /1,03
゜/! 10, /300 (absorption of benzene nucleus at 771-', 1qlI.

(Absorption of carbonyl of inphthalate ester on 5n-', aqso, hatll!r, 13KO, //
4! There was absorption of methyl groups into bisphenol at rcm-' (Figure 7).The elemental analysis values of the obtained polymer are as follows and agree with the calculated values at this molar ratio.

C (%) H (%) Calculated value 79.1.3 'At,! f Actual value? Ltco lAs Hiro Example - Hiro Bisphenol A and 9.9-bis(4L-hydroxyphenyl)fluorene (FDP) with a lid of 0.03
Implementation 9 except that the molar ratio of mom and its usage area was changed.
It was carried out in the same manner as No. 111.

The results of 7 are shown in Table 1.

Dragon -l

[Brief explanation of drawings]

Figure 1 shows the infrared absorption spectrum of the polymer obtained in Example 1. Patent applicant Mitsubishi Chemical Industries, Ltd. Agent Patent attorney Hase - 1 other person - 1:

Claims (3)

[Claims] (1) General formula (1) The structural unit represented by the general formula (fl) (wherein A represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkyref group, an alkylidene group, or none, BIT
〜RK represents a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group), and the structural unit (■):structural unit (11) has a molar ratio of de5:5 to s:qs. 3 at a concentration of 10 f-/dt in a mixed solution of phenol:tetrachloroethane-/:/
Reduced viscosity 1 m p/C measured at θC is 0. / d
Aromatic polyester having a ratio of t/p or more. (2) The aromatic polyester according to claim 1, wherein in the general formula (I), R16 is a hydrogen atom. (3) The aromatic polyester according to claim 1, wherein in the general formula (II), 117 to R2' are hydrogen atoms.