JPS5815529A - Alternate copolymer ester carbonate resin - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to linear copolymer esters containing linear carboxylate groups such as carbonate groups.

Polycarbonate resins are known for being tough and hard and have moderately high softening temperatures. US Patent 3,
Bisphenol-A as described in 028,365
Diol polycarbonates are of particular interest. On the other hand, polyesters such as those derived from terephthalic acid, isophthalic acid and/or 1,4-butanediol are known as molding resins with high softening temperatures but low impact strengths.

In the past, random linear copolymers containing ester and carbonate linkages have been made to obtain polymers with heat deflection temperatures that are generally higher than these carbonate properties.

For example, US Pat. No. 3,169,121 + 3,549,
57013.053,810+3. ．． See 030,331 and 3.220°976. Unfortunately, however, the desired heat deflection properties are often not as high as necessary for many applications. More importantly, increased heat flexibility is achieved only by sacrificing almost all of the high impact resistance that is characteristic of polycarbonate resins.

In view of the above-mentioned drawbacks of conventional polyesters, polycarbonates and their copolymers, it is possible to use the same or similar monomer materials so that improved thermal resistance is obtained without sacrificing any impact resistance. It is highly desirable to provide a polymer.

The present invention is based on the general formula (wherein each R is independently an aromatic hydrocarbylene or an inert group-substituted aromatic hydrocarbylene, 11 is phenylene or an inert group-substituted phenylene, and X is 0,0
The present invention relates to normally solid alternating copolyestercarbonates containing repeating units having a number of repeating units (in number from 5 to 10), characterized in that R is meta-phenylene or inert group-substituted meta-phenylene.

For purposes of this invention, an inert substituent is one or more substituents that are inert to the condensation reaction used to make the copolymer. Hydrocarbylene is a primarily hydrocarbon divalent group containing hydrocarbon groups linked by 1 as well as aromatic and/or aliphatic hydrocarbon diradicals.

The alternating copolymer is first reacted with an excess of two hydrocarbylenes and an isophthaloyl halide, and then by reacting the resulting dihydroxy ester product with phosgene or a similar compound capable of forming a carbonate bond with a diol. It is advantageous to be made. Advantageously, the first reaction is carried out in the presence of a hydrogen chloride acceptor such as pyridine. The second reaction is typically carried out using conditions common to the reaction of phosgene with simple diols to form polycarbonates. The two-step reaction to make the alternating copolymer can be represented by:

(wherein R, R and , has transparency, solubility and strength.

It is all the more surprising that such alternating polymers made from inphthaloyl halide exhibit high impact strength and improved processability compared to similar alternating polymers made from terephthaloyl chloride. Should. The alternating copolymers of this invention, particularly their resinous alternating copolymers, are therefore useful in many applications in which polycarbonates, polyesters, and copolymers thereof are commonly used. % such alternating copolymers are useful for making transparent and tough films and molded articles with high heat resistance. In addition, such alternating copolymers A
The BS resin styrene/acrylonitrile copolymer and other polymers such as high impact polystyrene can be mixed to obtain a product mixture, and/or the alternating copolymer can be combined with reinforcing materials such as glass fibers.

The dihydric hydrocarbylenes used to make the alternating copolymers of this invention are primarily hydrocarbon compounds containing at least two alcoholic hydroxyl groups, including a phenolic hydroxyl group. Aliphatic diols including glycols and alicyclic diols, aromatic diols including alkaryl diols, aromatic diols with heterocyclic groups such as divalent phenols and phenolphthalein are included in the divalent hydrocarbylenes. It will be done. Among the divalent hydrocarbylenes, divalent phenol is preferred.

The dihydric phenols preferably used to make the alternating copolymers of the invention are advantageously aromatic compounds having aromatic hydrocarbylene groups optionally aromatically bonded to two hydroxyl groups.

Most preferably, the dihydric phenol is an aromatic diol represented by the general formula. In that general formula, A is an aromatic group such as phenylene, biphenylene, naphthalene and anthracenylene. E is also methylene, ethylene, ethylidene, propylene, glohyritene, impropylidene, butylene, □
alkylene or alkylidene, such as butylidene, imbutylidene, amylene, inamilene, amylidene and imbutylidene; or E is a cycloalkylene such as cyclopentylene or cyclohexylene; Bonds; carbonyl bonds; tertiary nitrogen groups or silicone-containing bonds such as silane or siloxy.

m is a replaceable number from 0 to A, p is a replaceable number from 0 to E, t is at least 1, S is 0 or 1, and U is 0 or more . Examples of such dihydric phenols are 2゜2-bis(4-hydroxyphenyl)propane [bisphenol-A], bis(
4-hydroxyphenyl)methane; 1,1-bis(4-
Hydroxyphenyl)ethane and U.S. Pat. No. 3,16
Contains the dihydroxy aromatic ethers listed in Column 2, line 60 to Column 3, line 55 of No. 9,121.

general formula (In the formula, the aromatic ring is, for example, ■ in addition to the hydroxyl group substituent.

F + CI + Br l I + NO2+
Also suitable are dihydric phenols having an ar p ar'-dihydroxytrityl nucleus, represented by or containing substituents such as alkyl, acyl, carboxylate ester or sulfonate ester.

Typical diols containing &r+ ar'-dihydroxytrityl cores include phenolphthalein core compounds as described in USP 3,036,036, phenolsulfonephthalein as described in US Patent No. 3,036,037+ Nuclear compound 1114? 3.036,0
phthalidene core compounds as described in U.S. Pat. No. 3,036,038; fluorescene core compounds as described in U.S. Pat.
phenolphthalimidene core compounds corresponding to the phenolphthalein core compounds described in No. 036. Among the above-mentioned dihydric phenols, bis(ar-hydroxyphenyl)alkylidene, particularly bisphenol A and phenolphthalein, are preferred, and bisphenol A is also preferred.

In the preparation of the alternating copolymers of this invention, inphthaloyl halides are suitably used. However, it is also preferred that the inphthaloyl halide is isophthaloyl chloride, with isophthaloyl bromide and in7-thaloyl iodide being suitable, but inferior to isophthaloyl chloride. In place of isophthaloyl chloride there may also be inert substituted derivatives of isophthaloyl halide in which the inert substituent is hydrocarbyl or halohydrocarbyl such as halo, alkyl or aryl. The in7-taroyl halide was prepared under the conditions described in "Polymers", Volume 27, [Condensation of Monomers JJ, by Stijl and T. W. Cambubel, pp. 509-514], Interscience, 1972. are made by reacting the desired isophthalic acid with thionyl halide or other thionyl halides in an aromatic solvent. Examples of diacids include inphthalic acid and halo derivatives.

The alternating copolymer contains isophthalic acid and its halo derivative.

Advantageously, the alternating copolymer is made in a two-step process, ie by first reacting excess divalent hydrocarbylene with isophthaloyl halide in the presence of a hydrogen chloride acceptor such as pyridine. The dihydroxy ester intermediate produced by this reaction is then reacted with phosgene or other agent that forms the desired carbonate linkage. Both steps of the process are carried out under an inert atmosphere, such as nitrogen, with the reactants dissolved in one or more solvents with which the reactants are generally miscible. . Although the concentration of the reactant in the solvent is not a particularly necessary requirement, preferably the concentration of divalent hydrocarbylene is between 2 and 10% by weight, based on the total weight of monomer and solvent, and the isophthalocarbon The concentration of ylhalide is between 1 and 5 parts by weight. In the second step of the reaction, the concentration of ester intermediate is preferably 3-15% by weight based on the total weight of ester intermediate and solvent. Preferably, the solutions of the various reactants are mutually miscible throughout. However, it is sufficient if such solutions are partially miscible, ie at least 10% by weight. Examples of suitable solvents are methylene chloride, chloroform, sym-tetrachloroethane, 1. , ],.

]2-trichloroethane and cis-1,2-dichloroethylene.

The molar ratio of divalent hydrocarbylene to isophthaloyl halide can be relatively varied depending on the desired ester to carbonate in the alternating copolymer. Generally, the molar ratio of divalent hydrocarbylene to inphthaloyl halide is 2.
Preference is given to 1:1 to t1:i, more preferably 21:1 to 1.3:1.

The molar ratio of dihydroxy ester intermediate to phosgene is 1.
1-1:1.2, preferably l:1.01-1:1.0
It is 8.

Although pyridine is the preferred hydrogen chloride acceptor used in the first step of this invention, other suitable acceptors include other amines such as triethylamine, N,N-dimethylaniline and N,N-dimethylcyclohexylamine. Contains bases. Advantageously, such acceptor is used in an amount sufficient to complex the dissociated hydrogen chloride and to catalyze both steps of the process.

The actual concentration of receptor will vary depending on the desired molecular weight since high concentrations of the receptor will result in high molecular weight copolymers. Furthermore, at a constant terminator concentration, high monomer concentrations form high molecular weight copolymers. Therefore, the heptamer concentration will vary depending on the desired molecular weight. Preferably, the weight average molecular weight (M
w) to make a copolymer with 100 to 160
A molar amount is used, preferably an amount of 120 to 140 molar. At such receptor concentrations, the monomer concentration is preferably from 3 to 15% by weight, and most preferably from 5 to 15% by weight.
12 weight.

In carrying out the two-step process, the divalent hydrocarbylene and isophthaloyl are combined in any manner, preferably into a solution of the divalent hydrocarbylene and hydrogen chloride acceptor in a suitable solvent with stirring. Combined by adding dissolved or dissolved isophthaloyl halide. Although stirring speed is not a necessary condition,
50 to 500 rpm, preferably 150 rpm
A stirring speed of ~300 rpm is maintained. Although the reaction temperature is not a necessary requirement, the reaction temperature of the first step is kept in the range of 10-35°C, most preferably 19-25°C. Reaction pressure is likewise not a necessary requirement.

However, normally atmospheric to elevated pressures are conveniently used.

The ester intermediate is usually formed under these conditions 1 to 10 minutes after addition of the inphthaloyl halide. Although the ester intermediate can be recovered and purified before the second step of the process, it is generally not desirable to do so.

Accordingly, the reaction mixture described above containing the ester intermediate is converted to the desired copolymer by bubbling phosgene or other suitable carbonate-forming reactant into the reaction mixture.

The reaction mixture contains a monohydric phenol or other suitable chain terminator to effect the desired adjustment of the molecular weight of the resulting copolymer. The amount of chain terminator used varies depending on the potency of the terminator and the desired molecular weight;
Advantageous amounts of terminator are typically 1 based on the ester intermediate.
-10 molti, preferably 2 to 7 molti. Although not a necessary requirement, the reaction temperature in the second step is preferably 10 to 35°C, more preferably 2 to 2°C.
It is in the range of 7°C. As in the first step, the reaction pressure is usually from atmospheric pressure to increased pressure for convenience. The alternating copolymer is formed under these conditions 1 to 10 minutes after phosgene addition.

In both steps of the foregoing method, the reaction mixture is sufficiently agitated to effect intimate contact of the reactants and the desired thermal transfer throughout the reaction medium. After completion of the second step of the process, the desired alternating copolymer is easily recovered from the reaction medium by conventional techniques as demonstrated in the Examples below. Alternating copolymers derived from bisphenol-A and isophthalyl chloride are preferred because of their ease of manufacture and inexpensive starting materials.

The alternating copolymers of this invention have the general formula where Y and 2 are the usual end groups for independent polyesters or polycarbonates, R, R' and X are as defined above and n is from 5 to 300. Obviously, Y is a hydrocarbyl such as alkyl, aryl or aralkyl.
OR- (inhibitor R2 and R are as defined above)
including.

Alternating copolymers with repeating units have the general formula (where Y is -OH or 0COR2 1 2 is -R2 or -ROH,
Preferably 0.05 to 3 and 1 and R+ Rlr
R2 and n are as defined above. Preferred alternating copolymers are those in which Y is 10COR2, 2 is 1ζ and 1R is hydrocarbyl, such as alkyl, aryl, alkaryl, cycloalkyl or aralkyl; n is 5 to 300, preferably 10 to 200 and most Preferably 30-100
It is expressed by a general formula such as . For purposes of this invention, hydrocarbyl is a monovalent hydrocarbon group. In the most preferred alternating copolymer, Y is -〇〇OR2 1 2 is -R (R is H3).R is a weight average molecular weight of 20,000 or more, although the molecular weight of the alternating copolymer of this invention is not a particularly necessary requirement. (Mw determined by gel permeation chromatography using a bisphenol-A polycarbonate calibration curve)
Alternating copolymers with It has been discovered that alternating copolymers having relatively high molecular weights, eg, Mw from at least 25,000 to 60,000, exhibit the most desirable physical properties of molding resins. 25,000
Mw in the range ~40,000 and Mw/ from 1.5 to 5
Alternating copolymers with Mn (Mn being the number average molecular weight) are also preferred for this purpose.

The following examples illustrate the invention and do not limit its scope. All parts and percentages are by weight unless otherwise indicated.

In one step of the two-step process, bisphenol-A
751.0? (3,29 mol), methylene chloride 7,938 mol and pyridine 676.6c/-(8,
554 mol) was placed in a 12-1 (liter) flask. When stirring was started and a clear solution of bisphenol was obtained, isophthaloyl chloride 333.93P
(1,645 mol) at a temperature of 19 to 25 °C and 25
Addition was continued over a period of 7 minutes with continuous stirring at 0 rpm. After the isophthaloyl addition, stirring was continued for an additional 10 minutes before the second step began.

In the second step, the above reaction solution containing the ester intermediate is treated with 12.35 p (0,082 mol) of p-tert-butylphenol as chain terminator. The resulting solution was stirred at 175 rpm and 175.7y-(1,584 mol) of phosgene was added between 22 and 2
Phosgene was added to the liquid reaction solution for 56 minutes by bubbling into the liquid reaction solution at a temperature of 5°C.

The resulting polymer product was recovered from the reaction mixture by the following method; excess pyridine was neutralized by addition of 1.5-3.3 HCl, ON. After phase separation, the methylene chloride solution of the polymer was washed successively with HCI and water, and the phases were separated after each wash.

After the final wash, a methylene chloride solution of the polymer was added to a cation exchange resin (sulfonic acid type, 500-600
A clear, mostly colorless solution was obtained. The polymer product was separated by slowly adding 1 volume of the methylene chloride solution to 5 volumes of hexane with rapid stirring.

The resulting white fibers were separated by filtration, dried in air for 24 hours, and then dried in vacuum at 120°C for 48 hours, with an intrinsic viscosity of about 0.51 dl/11 (25
9oo, 1F! - (theoretical amount of 89.3 h) was obtained.

Analysis of the polymer by IR, NMR and elemental analysis revealed that it is an alternating copolymer represented by the structural formula.

The copolymer with repeating units had an ester:carbonate ratio of 2:1. Compression molded test bars of this alternating copolymer (sample AI) were molded at 300 °C and
．． 32 crn thickness) were physically tested and the results are shown in Table I.

For comparison, random copolymers with the same molecular weight and ester:carbonate ratio of 2;1 were prepared in U.S. Pat.
169,121 (Examples 3.10 and 11) by phosgenation of a mixture of bisphenol-A and isophthalic acid. The recovered random copolymer had an intrinsic viscosity (measured in CH2Cl, at 25 DEG C. and 0.5 de/dl) of about 0.51 #/p. Compression molded test bar of this copolymer (sample mA) (molded at 300°C, 3.211II11
Tests were made for the physical properties of (thickness) and the results are shown in Table ■. The intrinsic viscosity of the polymer is 25
Measured in methylene chloride at 0.5 P/dl.

Vicat softening point was determined by A, STM D-1525. Izond impact strength was measured by ASTM D-256. Transparency and haze are ASTM D-
1003. Yellowness index is ASTMD
-1925.

Table 1 Copolymer type Alternating Random Intrinsic viscosity, dVy-0,510,51 Biforce softening point, °C 180 164 Permeability% 85.3 71.3 Haze
H 4.1
80.1 Yellowness Index 13.2
21.8 As shown by the data in Table 1, certain reciprocal copolymers are superior to random copolymers in terms of heat resistance, impact strength, and transparency.

Examples 2 and 3 and Comparative Operations B and C Following the general procedure of Example 1, copolymers were prepared from bisphenol to A
(BA), isophthaloyl chloride (IPC) and phosgene at ester:carbonate molar ratios of 2:1 (Example 2) and 3:1 (Example 3). For comparison, copolymers were prepared with bisphenol-A1 terephthaloyl chloride (
IPC) and phosgene. These samples were injection molded using a Nuva U-nr3ogs machine with control brakes, inks, and a Procel Sentry Model 750 Oyohi Floss recorder. The following molding conditions were used: Palace zone -316°C; Nozzle - 304℃, mold part - 121℃, injection time - 10 seconds,
Total cycle time - 45 seconds, feed rate settling - 2,5, tensile specimen and runner limits - 2000 psi (13,
79 MPa) and a single-step injection mold, 4000 ps at the end of its molded tensile specimen for processability comparison.
The injection pressure required to obtain a pressure of i (27,58 MPa) was determined. The physical properties and processability of the injection molded samples with a thickness of 3.2 m are shown in Table 3.

The weight average molecular weight Mw is determined using a polystyrene calibration curve.
Determined by gel permeation chromatography. The weight average molecular weight determined using the polystyrene calibration curve was divided by 1.7 to correct the molecular weight corresponding to the weight average molecular weight determined using the bisphenol-A calibration curve. Tensile strength at creation, tensile strength at break, elongation at creation, elongation at break, and tensile modulus are ASTM D
-638.

Table ■ Example 2 Aromatic diol BA diacid chloride IPC ester:
Carbonate molar ratio 2:1 Intrinsic viscosity dl/f/-0,55 Mw 55
, 8o2 Biforce - Softening Point ℃ 1
Stretching degree when generating 80% 7.0
6 Elongation at breakage % 53.8 Transparency % 87.1
Cloudy degree %
4.3 Yellowness Index 8.4 Comparison Operation B Example 3 Comparison Operation CBA
BA B
ATPCIPCTPC 2:] 3:i 3:10
．． 50 0.51 0.5355
．． 162 51. ．． 918 50,61
0197 182 2038.4
7 6.83 8.9434.5
4.8.8 38.884.5
86.6 87.44.5
2.9 3,010.3
15,7 As shown in Table 15.3, the alternating 7-talate copolymer is
It has better physical properties, especially impact strength and workability, than talate cobolima.

Examples 4-9 Following the method of the Examples, other alternating copolymers were made using isophthaloyl chloride and aromatic diols as shown in Table 1. These copolymers were compression molded (C) or injection molded (I).

Physical properties are shown in Table ■. In Example 7 the aromatic diol feed was phenolphthalein (pp) 1
Each mole contained 1 mole of bisphenol-A (BA).

Claims (1)

[Claims] General formula (wherein each R is independently aromatic hydrocarbylene or inert group-substituted hydrocarbylene, R1 is phenylene or inert group-substituted phenylene, and X is 0.05 ~1
A normally solid alternating copolymer ester carbonate having a repeating unit of 0), wherein R is meta-phenylene or inert group-substituted meta-phenylene.