JPS6132332B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to bisphenol A/terephthalate/carbonate copolymers having the following characteristics:
i.e. bisphenol A in the product polymer.
(BPA):Terephthalic acid (TPA):The molar ratio of each bonding moiety of carbonate is 2:0.8:1.2 to 2:
1.3:0.7; conventional bisphenol A/terephthalate/with short average lengths of polyester segments and polycarbonate segments.
Highly low in nitrogen base and/or organic acid impurities characteristic of carbonate copolymers, the copolymers of the present invention are therefore melt processable; and other features that make the copolymers of the present invention uniquely useful. Properties. In particular, the copolymers of the present invention are useful for applications as bright and transparent sheets requiring high impact resistance, scratch and abrasion resistance, and/or high solvent resistance. The polymer exhibits melt processability, high tensile strength, high impact strength, and good clarity and colorlessness, approaching in these qualities to known commercial polycarbonates. As is without coating or modification, the polymer has the above properties as well as high resistance to abrasion and scratching, particularly under stress, including many common chemicals including hot water, carbon tetrachloride, toluene, gasoline, butyl acetate and acetone. High resistance when subjected to the action of solvents, high values of glass transition temperature (Tg) and relatively small difference between Tg and heat distortion temperature (HDT) and creep (elongation under prolonged loading) at high temperatures It is unique in its combination of high dimensional stability at high temperatures, reflected in low values of be. Polyester/carbonate copolymers have been the subject of prior research, including copolymers in which BPA is reacted with carbonate precursors and dibasic acids, particularly adipic acid and isophthalic acid. Some trials using terephthalic acid have been reported (U.S. Pat. No. 3,030,331, April 17, 1962, to Eugene P. Goldberg).
No. 3,169,121 of February 9, 1965,
as well as polymer preprints (Polymer
Preprints) 1964, Vol. 5, No. 1, pp. 233-238). The disclosure of U.S. Pat. No. 3,169,121 is very similar to U.S. Pat.
See No. 3169121. Two types of tests have been reported using BPA, TPA and phosgene. One reactant was BPA:TPA in a molar ratio of 2:1 in a stirred pyridine medium, into which phosgene was bubbled until the reaction mixture became viscous. Column 47−
Line 54 and Example 5). The other (Example 12) was the same except that half of the TPA was used, ie the molar ratio of BPA:TPA was 2:0.5. The only properties shown for the obtained polymers are intrinsic viscosity, softening temperature and tensile strength and elongation. In contrast, there are three examples using isophthalic acid (Examples 3, 10, and 11), each of which additionally reports the following properties: transfer molding temperature;
Thermal deformation, impact strength, weight loss (% at 230°C, 24 hours), flexural strength and hardness. The literature article (page 238) explains that tensile tests were performed on solution cast films, and impact and Tg tests were performed on transfer molded bars. (The Tg graph in Table 1 of the literature article is the same graph as the thermal deformation in the example of the Goldberg patent, and was measured by the intrusion method, which is also suitable for measuring thermal deformation.The measurement method is described in the literature. The article cites Goldberg's Journal of Polymer Science, in press, published in Journal of Polymer Science, Division C, No. 4, 1964, 707.
−It appears on page 730. (See pages 715-717). We have shown that BPA/TPA/carbonate copolymers made in a pyridine reaction medium as directed by Goldberg (1) have TP binding moieties whose composition does not correspond to the ratio of BPA:TPA reactants in the feedstock. (2) It is thermally unstable under the molding conditions, and molded products made from it have bubbles and discoloration, and the viscosity of the solution is lower than before molding. Number (I.
V.) was found to show significant deterioration. Accordingly, these polymers made in a pyridine reaction medium have yields of only about 1 to 2 ft-lb per inch of notch, as measured by conventional methods, compared to 12-16 ft-lb per inch of notch for commercially available polycarbonates. It only has Izod impact resistance. This degradation under molding conditions explains why Goldberg's patents and literature articles describe the molding temperature, impact resistance, heat distortion temperature, and glass transition temperature (Tg) (measured by the intrusion method) of his BPA/TPA/carbonate copolymers. This is thought to explain whether or not properties such as Goldberg does not report on these properties of BPA/TPA/carbonate copolymers that require exposure to high temperatures in the molding operation for measurements. The above-mentioned phenomena of low content of TP binding moieties in this polymer and degradation of this polymer under molding conditions may be due to some kind of interaction between terephthalic acid and pyridine in view of our investigation. . Thus, it is believed that the polymers made in the pure pyridine reaction medium contain on the order of 1% residual pyridine strongly bound in the polymer. We have also found that TPA modifies the structure of the Goldberg polymer to some extent and is incorporated into the chain in substantial amounts in the form of terephthalic anhydride linkages. According to one suggestion of the Goldberg patent
When terephthaloyl chloride (TPC) is used instead of TPA in the pyridine reaction medium, the resulting polymer still exhibits the above-mentioned drawbacks. Such intensive purification of conventional polymers results in improved properties such as impact resistance, but the resulting polymers according to Goldberg still have significant amounts of pyridine and acid impurities, and even after molding. It exhibited a poor color, the intrinsic viscosity still changed significantly after heating, and it was still far from having a high content of TP binding moieties in the polymer, such as the reactant mixture. In fact, we
Even when the TPA or TPC components are used in large excess, greater than a 2:1 molar ratio, the use of Goldberg's pyridine reaction medium reduces the molar ratio of BPA to TP binding moieties in the resulting polymer to 2:1. : We have found that it does not go higher than 0.8. The polymers of the present invention are melt processable bisphenol A/terephthalate/carbonate copolymers comprising: a BPA binding moiety in the product polymer;
i.e. (However, Me represents a methyl group) The terephthalate bonding moiety, i.e.

The molar ratio of [formula] is in the range between 2:0.8 and 2:1.3, and the formula Polycarbonate segments consisting of repeating carbonate bonding moieties (where Me represents a methyl group) are essentially very short, each not exceeding an average length of 2.5 molecular units, and a viscosity number (IV) of 0.6
range between dl/g and 1.5dl/g, Tg is 170℃
The relationship between Tg and IV is approximately given by the upwardly convex curve shown in Figure 1 of the accompanying drawings, and the difference between Tg and the heat distortion temperature according to ASTM D-648. does not exceed 15℃. The formula for Tg/IV for our polymer is Tg=192− as shown within the dotted curve in Figure 1.
(11.5/IV)±9. Here, the viscosity number of the above copolymer approximately corresponds to the following molecular weight viscosity number, dl/g molecular weight 0.6 12400 0.85 18145 1.1 23600 1.5 32800, and regarding the segment length of polycarbonate, the above formula, i.e. is equivalent to the segment length in units of one molecule. By "melt processability" we mean that our polymers do not change viscosity by more than 10% when compression molded for 10 minutes at 320°C to form platelets, and under purified nitrogen. When heated at 350°C for 30 minutes (in a sealed tube) and then dissolved in dichloromethane (DCM) to make a 2% (g/ml) solution, this polymer passed ASTM test D- using a 2 cm path length. 1925 means exhibiting a yellowness index not greater than 10. ("Viscosity number" is 25℃, concentration 0.5
It is given by the specific viscosity/concentration measured in ethylene tetrachloride:phenol in a weight ratio of 40:60 g/dl. Tg
is the so-called glass transition temperature, which can be determined by differential scanning calorimetry at 20°C/min in an argon atmosphere by melting the polymer powder, quenching it in liquid nitrogen, and reheating the polymer sample. Measure it. The yellowness index is measured using a Hunter D252P meter. ) The polymers of the present invention have an Izod impact resistance (ft-lb per inch of notch) at 25°C of at least 5
It is. The polymers of the present invention have a pyridine content not exceeding 200 ppm and substantially anhydride bonds.

Does not include [expression]. Here, "substantially free" means that the polyester/carbonate copolymer is not present in a significant amount that would adversely affect its physical properties. Goldberg (1) used acid chlorides instead of acids as reactants (U.S. Pat. No. 3,169,121, No. 11
column, lines 25-29), and (2) the use of an inert solvent in addition to pyridine (U.S. Pat. No. 3,030,331, No. 3).
column, lines 9-20) and widely disclosed them. However, he noted that any of these expedients, whether used alone or in combination, may affect the length of the ester and carbonate segments of the polymer or the BPA binding moiety in the resulting polymer: He does not disclose that molecular weight control would have any effect on the ratio of TP binding moieties or on the thermal properties such as melt processability, Tg and heat distortion temperature of the resulting polymer. The use of agents, especially their addition prior to phosgenation, is not suggested. The products of the invention combine TPC with a solution of BPA in pyridine/chlorinated organic solvent at a molar ratio of BPA/TPC in the reaction mixture of about 2:1, and carry out the BPA/TPC reaction at a temperature not higher than 35°C; This can be obtained by using a reaction medium containing pyridine in at least a small excess of the stoichiometric amount, but not more than a 14-fold excess, and which decreases as the concentration of the reactant increases. The theoretical amount is the amount of pyridine required to combine with the theoretical amount of hydrogen chloride resulting from the ester formation and carbonate formation involved in the polymer formation from the components BPA, TPC, and phosgene, i.e., 2 pyridine per mole of BPA. It is a mole. Therefore, at low concentrations of reactants, such as 10% by weight in the reaction medium, we can
28 moles of pyridine, based on pyridine, 1:
3 to 10:1 volume ratio of chlorinated organic solvents for the reactants such as chlorobenzene or 1,2-dichloroethane or especially dichloromethane (DCM). This organic solvent has a low molecular weight.
Dissolve BPA/terephthalate polyester,
And the final polymer can also be dissolved or colloidally dispersed. More specifically, the relationship between reactant concentration and DCM:pyridine ratio falls within the area below the limit curve of the attached FIG. 5. Afterwards we add phenolic compounds which serve as molecular weight control agents. The carbonate precursor phosgene is then introduced, then the phosgene addition is stopped, the system is purged with air or inert gas to remove unreacted phosgene, and when the product viscosity reaches the predetermined value. Additional amounts of phenolic compound are added to stop polymer chain growth. Molecular weight control agents that can be used include phenol, p-
Examples include tert-butylphenol and p-alpha-cumylphenol, but are not limited thereto.
It is suitable, but not necessary, to use the same compound as a chain terminator after purging to remove phosgene. Preferably, to reduce the amount of pyridine that must be recovered, the chlorinated solvent will be in at least a 2:1 volume ratio with the pyridine, and the weight of BPA+TPC in solution will be at least 10% of the solvent.
g/100ml. We currently consider DCM to be our most preferred solvent in terms of polymer yield and ease of removal. The total weight of BPA and TPC fed to the reaction can be as high as at least 35 g per 100 ml of solvent. However, when the monomer concentration is too high, the maximum viscosity number obtained will be undesirably low (when chlorinated solvents predominate) and the TP bound to the polymer will be substantially less than that of the feedstock (when pyridine when dominant). A suitable upper limit concentration of monomer for the production of the present polymer is as shown by the curve in the accompanying FIG. 5, and a suitable lower limit is shown by the straight line at a concentration of 10 g/ml. Preferably the temperature during the BPA/TPC reaction is maintained below 25°C. Active cooling means are commonly used for this purpose. After the BPA and TPC have reacted, the phosgenation reaction can be carried out adiabatically or with cooling only by heat loss to the environment. The temperature normally does not exceed 35°C. One reaction involved in ester formation is (1) And one reaction involved in carbonate formation is as follows. (2) BPA/TP esters react together many times with each other, thereby forming ester segments. BPA chloroformates interact to form block carbonate segments. will be allowed to form. It will be appreciated here that x and y are each often 3 or more, or that the reactions frequently alternate to form short segments in which mostly x and y are each equal to 1 or 2. If the reactant TPC enters the polymer in a lower ratio than the reactant carbonate (as always happens in clean pyridine medium according to our studies), then it is necessary that TPC and carbonate are each in the same ratio.
than when combined with BPA, i.e. in the polymer.
The BPA segment/carbonate segment will correspondingly have a greater average length than when the molar ratio of BPA binding moiety: TP binding moiety: carbonate binding moiety is 2:1:1. Furthermore, if the conditions used are favorable for making polymers of either type with segment lengths greater than 3 units on average, before making the other type, each component contains 2:
Both types of relatively long segments will be formed when reacting in a 1:1 ratio. The formation of mostly short segments, not exceeding an average of 2.5 carbonate units, as in the polymers of the invention, therefore depends on the order of addition of the components and their relative proportions in the reaction mixture as the reaction progresses. It will be appreciated that this will only occur under a favorable combination of reaction conditions including. Additionally, addition of chain length control agents at appropriate stages is usually necessary to obtain the desired viscosity number in the final polymer. The above combinations of reactants, reaction medium, proportions of reactants and order of steps are in our particular case:
The desired ratio of BPA binding moieties: TP binding moieties: carbonate binding moieties is 2:1:1 and relatively low ratios down to 2:0.8:1.2 and 2:1.3 (if reactant proportions are adjusted). :TP up to 0.7
having a relatively high proportion of bonding area in short segment lengths, viscosity number in the range 0.6 to 1.5 dl/g, Tg of at least 170°C, heat distortion temperature within 15°C of Tg, notch per inch at 25°C at least 5ft
It is suitable for making our melt processable polymers with an Izod impact resistance of -lb. 2:1 or higher molar ratio of BPA and TPC
More than 90% pure di(bisphenol A) terephthalate can be produced by purification of the low molecular weight polyester obtained by reacting the diester, and by phosgenation of this diester, virtually all of the ester segments and Polyester/carbonate copolymers in which all carbonate segments are each of a unique unit length, ie "alternating" polyester/carbonate copolymers, can be obtained. We have constructed such a copolymer and measured its properties. It can be seen that these properties closely approximate the 2:1:1 short segment length polyester/carbonate copolymers of the present invention. Certain combinations of properties that are meaningful as exhibiting properties approximating those of true alternating copolymers are: (1) a heat distortion temperature of at least 170°C, HDT (ASTM D-648
(2) a glass transition temperature Tg of at least 178 DEG C.) (as measured by deflection through the groove), and (3) an Izod impact resistance (ft-lb per inch of notch) of 6 or greater. In the attached drawings, the solid curve in Figure 1 is
The dashed curve represents the relationship between Tg and IV for our copolymer, which essentially has a composition with a 2:1:1 molar ratio of BPA, TP, and carbonate linking moieties, with the dashed curve representing a 2:1.3: 0.7 (upper) and 2:
A similar relationship is expressed for our copolymer of 0.8:1.2 (lower). The actual measurement points are ○ for the solid curve, and △ and □ for the compositions of 2:1.2:0.8 and 2:0.8:1.2, respectively. ×
The marked points are for the copolymer of Example 2 below, a true alternating copolymer of approximately 94% purity and a viscosity number of 1.47 dl/g. The points found for a copolymer with a purity of 92% as an alternating copolymer and a viscosity number of 1.23 dl/g, lower than the former, coincided with the curve of FIG. 1 at 185°C. In FIG. 1, the points marked a and b and marked with * represent the supplementary test of Example 5 of US Pat. No. 3,169,121, and the points c, d, and e marked with + are examples of the example of US Pat. No. 3,169,121. TPC with 1 operation
represents an experiment using . All such points (corresponding to experiments using clean pyridine as reaction medium) are well below the curve for our polymer, i.e., pure
Approximately 147° to Tg of BPA polycarbonate
towards a value of 150° C., which indicates relatively long polycarbonate segments in these resulting polymers, ie segments that are on average longer than 2.5 units in length. These points are 2:0.8: of the present invention.
Tg values as found experimentally for a BPA/TP/carbonate copolymer analyzed to have a lower content of TP binding moieties than in a 1.2 ratio polymer. Consistent with this, given these points, these polymers obtained in clean pyridine reaction medium have a BPA/TP/carbonate molar ratio of (a)
2:0.67:1.33, (b)2:0.77:1.23, (c)2:
0.55:1.45, (d)2:0.54:1.46, (e)2:0.29:1.71
It was analyzed that These copolymers have a viscosity number (a) of 0.82 (measured in one or two samples);
0.85, (b) 1.37, 1.38, (c) 1.48, (d) 1.55, (e) 2.76,
It was 2.72 dl/g. Figure 2 shows the infrared absorption ratio versus carbonate for wave numbers 1770 cm ^-1 and 1740 cm ^-2 (i.e. for carbonate CO groups and carboxylate CO groups).
A calibration curve obtained by plotting the composition expressed as a molar ratio of CO:ester CO is shown. The actual measurement points for this graph are a known amount of commercially available bisphenol A polycarbonate and a known amount of BPA/TP polyester (known by W. M. Airexn, Journal of Polymer Science, Vol. 40, pp. 399-406, 1959). (formed interfacially from bisphenol A and terephthaloyl chloride) obtained from a solution or dispersion in tetrachlorethylene,
It was determined by infrared measurements using a KBr crystal as a support. Since there is one carbonyl group for the carbonate bonding moiety and two carbonyl groups for the terephthalate bonding moiety, the value for the abscissa in Figure 2 (i.e., the X coordinate in the graph) is BPA/TP. /2 to obtain the corresponding number of moles of carbonate bonds per mole of terephthalate bonds in the carbonate copolymer.
Note that it must be doubled. Therefore, in Figure 2, the point (0.5) on the X-axis indicates a composition in which the ester and carbonate bonding moieties are in equimolar proportions, i.e., a 2:1:1 composition of BPA bonding portion: TP bonding portion: carbonate bonding portion. represents a copolymer with The calibration curve in Figure 2 is different from a straight line.
This actual calibration curve must therefore be determined in order to obtain reliable results for the carbonate:carboxylate molar ratio in BPA/TP/carbonate copolymers by infrared absorption methods. Figure 3 shows a typical differential scanning calorimeter (DSC) curve that found a Tg of 187°C. This curve has 325
The melting point in °C is also shown. Some of our polymers exhibit melting points when analyzed by DSC, while others do not. The viscosity of this particular polymer was 1.42 dl/g. FIG. 4 is a block flow diagram illustrating one method suitable for making the present polymer. Figure 5 shows the upper limit curve of monomer (BPA plus TPC) concentration (in grams per 100 ml of solvent) versus volume % of pyridine and DCM in the solvent mixture, which defines the preferred relationship for the production of polyester/carbonate copolymers of the present invention. This is a graph of (The conditions exemplified by Goldberg in this figure lie entirely on the vertical axis of coordinates, i.e. DCM = 0) Conditions above the curve and to the left will result in a product with a lower TP ratio than the feed; Conditions to the right at , result in an undesirably lowered intrinsic viscosity. Preferred polymers according to the invention lie essentially in the molar ratio range 2:0.9:1.1 to 2:1.2:0.8.
Consisting of BPA, TP and carbonate bonding parts, with a viscosity in the range of 0.6 to 1 dl/g, at least
It has a Tg of 178°C and an Izod impact resistance of at least 6 (ft-lb per inch of notch). These polymers possess excellent levels of the above properties as well as remarkable melt processability. Preferred process conditions for monomer concentration and DCM:pyridine ratio lie within the curve shown in FIG. The most preferred conditions are 10g/ml line, curve and
It lies within area A of FIG. 5, bounded by the 67% DCM/33% pyridine line (ie, the DCM:pyridine volume ratio is at least 2:1). EXAMPLES A complete description of specific embodiments of the invention and the best mode we contemplate for carrying out the invention follows. This description is to be construed in an illustrative rather than a restrictive sense. In this description, "parts" are by weight unless otherwise stated. EXAMPLE - Polymers with a molar ratio of 2:1:1 According to the flow diagram in FIG. send. This solution in a chlorinated hydrocarbon solvent such as dichloromethane (DCM) or chlorobenzene can be prepared at room temperature by stirring solid TPC into the solvent (purified by distillation). The appropriate weight ratio of TPC:DCM is 27.4
Number of copies: 224 copies. Since TPC reacts with moisture to form TPA, and for our purposes pure TPC is desired, all containers and piping must be clean and dry throughout operation, and before use. Must be flushed with dry air and nitrogen. Glass or glass-lined or PTEE-lined vessels and piping and stainless steel stirrers, centrifuges, and drying ovens are used throughout the operation. A dry nitrogen atmosphere is used.
All solvents are purified by distillation, all solutions are filtered until clear, and the final filter is suitably passed through a sintered glass filter. Similarly, a solution of 65.9 parts of chemical grade bisphenol A (BPA) is made up in 69 parts of pyridine. this
A BPA solution is supplied to a reaction vessel 5 with a jacket. It flows from the preparation tank and piping into reaction can 5 along with a metered amount of DCM solvent. Additional DCM
is added to reaction vessel 5 to form BPA:Pyridine:DCM.
The weight ratio is 65.9:69.0:562 parts. The TPC solution is sprayed by siphon action over a conical remover into the reaction vessel 5 - to avoid local high concentrations in the reaction mixture - just above the level of the vigorously stirred BPA solution. , that is 1
At a steady rate of about 125 pounds per hour, the temperature of the reaction mixture, which is cooled by circulating water into the jacket of reactor 5, remains below a maximum of 25°C. Then p-tert-butylphenol in DCM
1.34 parts by weight of the solution is added to the BPA/TPC reaction mixture to serve as a molecular weight control agent. Finally, the weighed phosgene from the storage tank 7 is evaporated in a heating can 9 and passed through a strainer 11 and then through a dip tube to remove any particles at a rate of about 9 pounds per hour, first under a partial vacuum. The mixture flows into the well-stirred reaction mixture in the reaction vessel 5 located below. The pressure approaches atmospheric pressure as phosgene is added. The temperature during this phosgenation can be about room temperature and no cooling is required. The mixture becomes viscous, and its viscosity number can be estimated from the viscosity of the reaction mixture measured with a Bruckfield viscometer, which can be periodically performed on samples and used as a guide for phosgene addition.
Maintain complete agitation by increasing the agitation speed to counteract the effects of viscosity. The amount of phosgene added is in excess of the amount theoretically required. The steam discharged from reaction can 5 is passed through an alkaline scrubber (not shown) to remove phosgene. When the viscosity of the reaction mixture reaches the predetermined level, the addition of phosgene is stopped and the vapor space in the reaction vessel 5 is purged with air or inert gas and discharged through a scrubber to remove the phosgene. DCM
2 parts of p-tert-butylphenol dissolved in the solution are added to react with the carboxychloride end groups;
It also reacts with any excess phosgene dissolved in the reaction mixture. The reaction mixture is stirred for 1 hour, then methanol (approximately 6.5 parts by weight) is added to ensure inactivation of any remaining carboxychloride groups and traces of phosgene in the solution. Immediately after the addition of methanol, the polymer is precipitated in a stirred tank 13, which contains 1800 ml of acetone in tank 13, which is equal to three times the volume of the polymerization reaction mixture.
This is done by adding the polymerization reaction mixture to the first portion very slowly (approximately 5 gallons per 5 to 10 minutes) with very good agitation. Stirring is continued after this initial addition to break up any lumps into small particles, and then the rest of the reaction mixture is added in small enough increments to maintain the small particle size of the precipitated polymer. The precipitated polymer is separated from the precipitation medium in centrifuge 15 and returned to tank 13 or sent to a separation tank where it undergoes the first of six acetone washes.
Acetone washing is carried out for 10 minutes with approximately 460 parts of acetone (approximately 1/4 of the amount used for precipitation). The washed polymer was recovered by centrifugation again and then 70
The first washing is done with approximately 580 parts of distilled water at -100°C. The centrifuged polymer is washed again with acetone and centrifuged as before. The polymer was then redissolved in 928 parts of DCM at approximately 30°C and sieved through a 316 stainless steel sieve.
Acetone as well through a 50 micron filter
1800 parts are passed into settling tank 13 containing 1800 parts. The second precipitation of the polymer is carried out in the same manner as the first. This is followed by a third acetone wash, a second hot water wash, and a fourth acetone wash. The final cycle of purification begins with a second redissolution in DCM as before, a third precipitation of the polymer in acetone, and each subsequent centrifugation. This is followed by a final sequence of a fifth acetone wash, centrifugation, a third hot water wash, centrifugation, and a final acetone wash and centrifugation. In color testing of compression molded polymers, we
We have found that two precipitation-wash cycles are sufficient to give our polymers good melt processability. Effluent solvent from centrifuge 15 is collected in a drum. And the polymer is dried in vacuum oven 17
, where the absolute pressure is 10~20mmHg, 100°~130
Dry for 16 hours at ℃. Steam from oven 17 is exhausted through a scrubber. A typical polymer made by the above procedure is
Compression molded at 320°C for 10 minutes into small plates approximately 1/16 to 1/8 inch thick. Polymers A and C were also successfully made into strands by injection molding and extrusion. Typical injection molding conditions are: rear temperature = 300℃, front temperature = 310℃, nozzle temperature = 280℃, injection pressure =
The temperature was 1600 psi, the molding temperature was 135°C, and the cycle time was 37 seconds. 1.5 inch, 1/8 diameter with 3 horsepower extruder
Typical extrusion conditions for a strand of
℃, die pressure = 3000 psi, extrusion rate = 16 lb/hr. The properties of such a polymer are as follows.

【table】

[Table] Anhydride bonding - virtually none Pyridine content was determined by dissolving the polymer powder in 2 ml of warm DCM, adding 0.4 ml of water and 1 drop of concentrated HCl, shaking thoroughly, separating the upper aqueous layer, and It is determined by adding a small amount of granular sodium carbonate to this aqueous solution until the evolution of CO ₂ is no longer observed, and analyzing the resulting aqueous solution for pyridine by gas chromatography. If anhydride linkages are present in substantial proportions in these polymers, the infrared spectra of such polymers are compared to terephthalic anhydride and the 2:1:1 ratio of the present invention.
This can be observed by comparing the spectrum with the BPA:TP:carbonate copolymer spectrum. Such polymer (1 g) was placed in a tube which was evacuated, flushed and sealed with high purity nitrogen, and then heated for 30 minutes in an aluminum block maintained at 350°C. The obtained sample was dissolved in dichloromethane. Table 2 below shows the test results for yellowness and solution viscosity.

[Table] Comparative product A is a copolymer made in the same manner as Example 5 of U.S. Pat. No. 3,169,121 (supra) except on a larger scale, in order to obtain more product (i.e. 450 g of BPA, 163 g of TPA). .6g and pyridine 4.7
use). Comparative B is similar to Example 1 of U.S. Pat. No. 3,169,121, but modified by adding TPC to the BPA/pyridine solution instead of adipyl chloride;
And the scale is BPA 400g, TPC 161.7g, pyridine 5
I used Comparative products A (Pfd) and B (Pfd) are products of comparative products A and B, respectively, and are the products of Example 3 below.
(i.e. triturated in DCM, dissolved, precipitated with methanol, triturated again in DCM, dissolved and precipitated with methanol, washed with methanol, filtered and dried). These comparative products and the copolymer of the present invention were
The properties shown in the table were examined and the following results were obtained.

【table】

TABLE A substantial proportion of anhydride linkages were observed in Comparative Polymer A (TPA) above by the method of comparing infrared spectra noted above in connection with Table 1. Made in the same way as Comparative B (TPC) above, but with the addition of a higher proportion of TPC to the clean BPA solution in pyridine.
Additional experiments were performed in an attempt to obtain the BPA:TP ratio. The BPA solution in these experiments was 41.2g BPA.
It contained. The resulting ratios, determined by infrared analysis, are shown in Table 4 below.

[Table] The molar ratio of BPA/TPC in the feedstock is 2:
When increased to 2, the product obtained was only 0.07
It only has an intrinsic viscosity of dl/g. The product was not analyzed as this low molecular weight product does not exhibit any useful properties. Below are more specific examples illustrating the preparation and some properties of our polymers. In each example, unless otherwise noted, the operation is essentially that of Example 1.
It is similar to Example 2A Alternating copolymer starting material 4.08 moles (931.2 g) BPA/pyridine
1200ml/DCM6000ml, superadded, TPC1.92mol (390.0g)/DCM2500ml, superadded Low molecular weight polyester (BPA terephthalate) for 16 hours at room temperature
Preparation 1: Wash with 480 g of 4% HCl water, then wash 4 times with water to adjust the pH to 4.5, and add AgNO ₃ to the washing water to the extent that a slight chloride precipitate can be seen. Washing removes pyridine as its hydrochloride salt. 2 Evaporate the organic phase to dryness. 3 Disperse the solid residue in 10 parts of methanol and filter. The polymer residue is separated (mostly polymers higher than diester). 4 Add water to the liquid until it becomes cloudy, then add 10% more water. Most of the liquid will be
It is BPA. Phosgenation 1 The solid residue from step (4) of the preparation is dissolved in DCM and phosgenated using excess phosgene. 2. When the solution becomes viscous, stop phosgenation and add 50 ml of methanol. Recovery The polyester/carbonate phosgenation product is recovered and purified as in Example 3 below. Identification of the solid residue from preparation step (4) 1 Analysis of the product (according to liquid chromatographic peak height for -OH per g) = 94.2
Weight percent is diester, ie di(BPA) terephthalate, 3.3% is BPA, and 2.5% is a polymer higher than di(BPA) ester. Characteristic viscosity number of polyester/carbonate from above identified diesters 1.47 dl/g Tg 192 °C BPA:TPA:carbonate bonding moieties (by IR) 2:1:1 Example 2B Polyester Prepolymer Study Polyester Prepolymer was formed similarly to Example 2A above, except that the temperature used was about 0° C. (as in Example 3 below). The entire product after separation from pyridine hydrochloride was subjected to high-pressure liquid phase absorption chromatography using a cyano-type moiety chemically bonded to an irregularly shaped silica gel substrate through Si-O-Si bonds. Analyzed by. For this purpose, the product was dissolved as a 0.1% solution in chemical grade chloroform (containing 1% ethanol as stabilizer). Separation of BPA and polyester into components is performed using sequentially higher grade polyesters of the formula (AB) _o A [where A represents bisphenol A, B represents a terephthalate bonding moiety, and n is an integer from 0]. were based on different ratios of hydroxyl groups in. The lower the ratio of hydroxyl groups, the longer the polyester will remain in the column. The results are shown in Table 5 below.

[Table] Example 3 Polymer with a molar ratio of 2:1:1 from low temperature production 931.2 g (4.08 mol) of bisphenol A in 1.2 pyridine + 6.0 CH ₂ Cl ₂ were filtered and cooled to 0°C. 390.0 g of terephthaloyl chloride in CH ₂ Cl ₂ 2.4
(1.92 mol) was added dropwise with stirring over a period of 16 hours. p-tert-butylphenol 14 in 50 ml of CH ₂ Cl ₂
g (0.09 mol) was added to this solution to serve as a molecular weight control agent. Then add 1.5 phosgene to the top of the reaction flask.
It was introduced with condensation at a rate of g/min. After about 4 hours at 20°-30° C. with vigorous stirring, when the solution became very viscous, 25 g of phenol in 100 ml of CH ₂ Cl ₂ was added to the reaction mixture to react with the chloroformate chain ends. The mixture was stirred for about 1 hour, then methanol
200ml was added to terminate any remaining active chain ends. The reaction mixture was poured into methanol 15 with stirring to precipitate a solid polymer. This was washed with methanol in a blender and passed through a fritted glass filter. crush the polymer
Redissolved in CH ₂ Cl ₂ (10), stirred the dissolution for 15 hours, and filtered the solution again to precipitate the polymer in methanol. Grind again, redissolve in CH ₂ Cl ₂ , precipitate a third time, and mix in a blender for 4 hours.
After washing twice, the polymer was filtered and vacuum dried (110℃
(18 hours at 170°C and 2 hours at 170°C) and sealed in a container. According to infrared analysis, this product copolymer is
The ratio of BPA binding part: TP binding part of the raw material is 2:
0.94 vs. 2:0.93. Various properties of this product were determined using standard laboratory methods for the above and similar products with the following results. Viscosity number (dl/g) = 0.89 Tg (°C) (DSC method) = 183° Heat distortion temperature (2.64psi) °C = 175° Density (g/ml) 1.206 Tensile properties Yield strength (psi) 9300 Modulus ( psi) 350000 Elongation at break (%) 25-40 Flexural properties Strength (psi) 12000 Modulus (psi) 300000 Izod impact resistance at 25°C (ft-lb/notch inch) = 8.3 Izod impact resistance at -40°C = 3.7 Taber abrasion test (weight loss) Cycle loss mg 250 1.9 500 4.4 1000 9.4 Scratch hardness by an abraser grooving tool with a load of 1000 g on the beam (load x 100/width of the generated groove mil)
= 2250 Roquewell hardness = M73, R124 Water absorption (24-hour water absorption weight %) = 0.2% Linear thermal expansion coefficient 6.6 x 10 ^-5 Tensile creep (elongation) at 3000psi and 100℃ is
It reached 2.5% in 500 hours. Using an air oven, prepare a 1/16″ thick C-type sample.
Tensile heat distortion temperature test (ASTM1637) at 50 psi and temperature increase rate of 2°C/min showed no elongation at 200°C;
Elongation started at 210°C and reached 50% elongation at 215°C. Commercially available polycarbonate similarly tested was
50% elongation was reached at 165°C. Dielectric strength (volts/mil) = 345-427 Temperature (°C) Dielectric constant Dissipation tangent (at 100Hz) 24 3.01 0.00103 40 3.05 0.00084 86 3.13 0.00094 140 3.25 0.00143 Comparative example A Lower limit of TPA binding part Operation is based on the BPA in the raw material : TPC molar ratio is 2.0:
0.8 and the chain terminator used instead of p-tert-butylphenol was p-alphaacumylphenol (0.1 mole each time). According to infrared analysis, the obtained polymer contains a molar ratio of BPA binding moieties: TP binding moieties: carbonate binding moieties of 2:0.77:1.23, i.e. lower and lower than the TPA proportion specified for our polymer. Ta. Its viscosity number (IV) was 0.86 dl/g. That Tg
is 174°C and HDT is 165°C, which is considerably lower than that typical for our 2:1:1 polymers with similar IV (Tg = approximately 180°C as shown in Figure 1). showed his sexuality. Its Izod impact resistance (ft-lb per inch of notch) at 25°C is 7
It was hot. Example 4 Upper Limit of TPA Binding Moiety The procedure was the same as in the comparative example above, except that the molar ratio of BPA:TPC in the raw materials was 2.0:1.2. According to infrared analysis, the obtained polymer had a molar ratio of BPA binding moieties to TP binding moieties of 2:1.2. The viscosity number was 0.72 dl/g and the Tg was 188°C. twenty five
The Izod impact resistance (ft·lb/notch inch) at °C was 6. 1 from the above polymer by compression molding at 320℃.
Two sheets were formed. According to % light transmission after standard turber abrasion operation. Scratch resistance tests comparing this sheet with sheets of the 2:1 polymer of the present invention and commercially available coated and uncoated polycarbonate sheets were as follows.

Table: Tests were carried out to study the abrasion resistance as a function of viscosity number (IV) on the polymers of the invention obtained using a starting BPA:TPC molar ratio of 2:1. The results are shown in Table 6 below.

【table】

Table: Instead of or in addition to TPC, other aromatic dicarboxylic acid chlorides can also be used with BPA to form polyester/carbonate copolymers, broadly similar to those described above. To be specific,
2,6-naphthalene dicarboxylic acid dichloride in place of TPC in essentially the procedure of Example 3 above is a polyester/carbonate copolymer with IV = 1.17 dl/g, Tg = 200°C, and excellent solvent resistance. give. 4,4'-Benzophenone dicarboxylic acid dichloride reacts with BPA in a similar manner (using acetone as a precipitant during isolation), giving IV = 1.79.
dl/g, Tg = 210°C, HDT = 190°C, giving a polyester/carbonate with an Izod impact resistance of 5 ft-lb per inch of notch.

[Brief explanation of the drawing]

Figure 1 is a graph showing the relationship between Tg and IV of the copolymer of the present invention, where the solid line is for a BPA.TP.carbonate molar ratio of 2:1:1, and the upper and lower broken lines are for the same molar ratio of 2:1:1. 1.3:0.7 and 2:0.8:1.2. FIG. 2 is a calibration curve obtained by plotting the ratio of infrared absorption at wave numbers 1770 cm ^-1 and 1740 cm ^-1 versus the composition expressed as the molar ratio of carbonate CO:ester CO. FIG. 3 is a typical differential scanning calorimetry graph for the copolymer of the present invention. FIG. 4 is a flow diagram for producing the copolymer of the present invention. FIG. 5 is a graph of the upper limit curve of monomer (BPA plus TPC) concentration versus volume percent of pyridine and DMC in the solvent mixture that defines the preferred relationship for the production of polyester/carbonate copolymers of the present invention.

Claims (1)

[Scope of Claims] 1. A bisphenol A/terephthalate/carbonate copolymer having the following characteristics: (1)(a) When compression molded at 320°C for 10 minutes to form platelets, the polymer has a weight The viscosity does not change by more than 10% when measured in a 40:60 ratio of ethane tetrachloride:phenol at 25°C at a concentration of 0.5 g/dl, and (b) when heated at 350°C for 30 minutes under purified nitrogen. , then melted in the sense that when dissolved as a 2% (g/ml) solution in methane dichloride, the polymer exhibits a yellowness index of less than 10 by ASTM Test No. D-1925 using a 2 cm channel. (2) In the resulting polymer, the bisphenol A binding moiety, i.e. (However, Me represents a methyl group) The molar ratio of the terephthalate bonding moiety, that is, [formula] is in the range of 2:0.8 to 2:1.3, and (3) in the produced polymer, the formula Polycarbonate segments consisting of repeating carbonate bonding moieties (where Me represents a methyl group) are essentially very short, each not exceeding an average of 2.5 molecular units in length; The measured viscosity number IV is 0.6~
170 by differential scanning calorimetry at 20°C/min in argon on quenched samples.
It has a glass transition temperature Tg in the range of °~194 °C,
The relationship between Tg and viscosity number IV is expressed by the formula Tg=1.92−
(11.5/IV) ±9, the difference between Tg and heat distortion temperature does not exceed 15°C as measured by ASTM Test No. D-648, and (5) Izod impact resistance (per inch of notch) at 25°C. ft-lb) is at least 5, (6) the pyridine content does not exceed 200 ppm, and there is substantially no anhydride bond, ie, [Formula]. 2 Essentially molar ratio 2:0.9:1.1 to 2:1.2:
Consists of 0.8 bisphenol A binding part, terephthalate binding part and carbonate binding part,
The viscosity number is in the range of 0.6-1 dl/g, the Tg is at least 178℃, and the heat distortion temperature is at least 170℃.
C. and has an Izod impact resistance of at least 6 ft-lb per inch of notch at 25 DEG C. 3. The polymer of claim 2, wherein at least about 90% by weight of the polymer chain consists of residues of bisphenol A diester of terephthalic acid alternating with carbonate bonds. 4 (1) Chlorinated solvent: Pyridine capable of dissolving the low molecular weight bisphenol A/terephthalate polyester in a volume ratio of 1:3 to 10:1 and dissolving or colloidally dispersing the final polymer. Terephthaloyl chloride and bisphenol A (BPA) as a solution in a reaction medium with a chlorinated organic solvent in a bisphenol A:terephthaloyl chloride molar ratio of about 2:1.
where the reaction medium is in at least a small excess of pyridine, but not more than a 14-fold excess, than the theoretically required amount of pyridine to combine with the stoichiometric amount of hydrogen chloride produced in the polymer formation. (2) The reaction between this terephthaloyl chloride and BPA is
(3) then add to the reaction mixture a phenolic compound that serves as a molecular weight control agent, (4) then introduce phosgene into the resulting reaction mixture, and (5) determine the expected concentration of the product. A method for producing a bisphenol A/terephthalate/carbonate copolymer, characterized in that the addition of phosgene is stopped when the desired viscosity is reached, and (6) an additional amount of a phenolic compound is added as a chain terminator. 5. The chlorinated organic solvent is dichloromethane, the dichloromethane is in a volume ratio of at least 2:1 with pyridine, and the total weight of bisphenol A and terephthaloyl chloride in the solution is at least 10 g per 100 ml, but the accompanying drawings The temperature during the reaction of terephthaloyl chloride and bisphenol A should not exceed the upper limit defined by the curve of FIG.
5. The method according to claim 4, wherein the temperature is maintained at no higher than .degree.