CA1208396A - Method for producing aromatic polyesters - Google Patents
Method for producing aromatic polyestersInfo
- Publication number
- CA1208396A CA1208396A CA000443144A CA443144A CA1208396A CA 1208396 A CA1208396 A CA 1208396A CA 000443144 A CA000443144 A CA 000443144A CA 443144 A CA443144 A CA 443144A CA 1208396 A CA1208396 A CA 1208396A
- Authority
- CA
- Canada
- Prior art keywords
- aromatic
- compound
- acid
- functional derivatives
- compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
- C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
Abstract
ABSTRACT OF THE DISCLOSURE:
In a method for producing aromatic polyesters having improved moldability by the polycondensation of A: one or more compounds selected from aromatic hydroxy-carboxylic acids and their functional derivatives, or A with B: one or more compounds selected from aromatic dicarboxylic acids and their functional derivatives and C: one or more compounds selected from aromatic diphenols and their functional derivatives, a method for producing aromatic polyesters which comprises, on said polycondensation, adding D: one or more compounds selected from the group consisting of aromatic trihydroxy compounds, aromatic dihydroxy-monocarboxylic acids, aromatic monohydroxydicarboxylic acids and their functional derivatives, to the reaction system in one portion or gradually, followed by bringing these compounds into reaction.
In a method for producing aromatic polyesters having improved moldability by the polycondensation of A: one or more compounds selected from aromatic hydroxy-carboxylic acids and their functional derivatives, or A with B: one or more compounds selected from aromatic dicarboxylic acids and their functional derivatives and C: one or more compounds selected from aromatic diphenols and their functional derivatives, a method for producing aromatic polyesters which comprises, on said polycondensation, adding D: one or more compounds selected from the group consisting of aromatic trihydroxy compounds, aromatic dihydroxy-monocarboxylic acids, aromatic monohydroxydicarboxylic acids and their functional derivatives, to the reaction system in one portion or gradually, followed by bringing these compounds into reaction.
Description
3~6i 1 The presont invention relates to a method for producing aromatic polyesters having excellent moldability as well as balanced properties.
An aromatic polyester has excellent properties based on its structure, and excels ail other resins, particularly, in thermal resistance. particularly, aromatic polyesters which are formed with p-hydroxybenzoic acid or its derivatives as a central component, can be used for compression molding, transfer molding, extrusion molding, injection molding, etc. and are superior in mechanical and electrical properties as well as thermal resistance and thermal stability, so that they are used in various fields such as machine parts, electric/electronic parts, automcbile parts, tablewares, etc.
But, the aromatic polyester has a problem that the molding condition is severe because of its excellent thermal resistance, and that the deterioration and coloration of polymer occur because of the molding temperature being high. Consequently, an improvement in the moldability has
An aromatic polyester has excellent properties based on its structure, and excels ail other resins, particularly, in thermal resistance. particularly, aromatic polyesters which are formed with p-hydroxybenzoic acid or its derivatives as a central component, can be used for compression molding, transfer molding, extrusion molding, injection molding, etc. and are superior in mechanical and electrical properties as well as thermal resistance and thermal stability, so that they are used in various fields such as machine parts, electric/electronic parts, automcbile parts, tablewares, etc.
But, the aromatic polyester has a problem that the molding condition is severe because of its excellent thermal resistance, and that the deterioration and coloration of polymer occur because of the molding temperature being high. Consequently, an improvement in the moldability has
2 n been demanded.
Further, the aromatic polyester like this has a property to easily orient in molding of large shear, for example, in injection molding, so that there are found problems such that: A difference in percent shrinkage on molding is produced between the machine direction (MD) and ~83~i 1 the transverse direction (TD~, the anisotropy of mechanical strength is also large, and when the molded product has a welded part, the strength of the part is low.
In order to solve the aforementioned problems inherent to the aromatic polyester, i.e. poor moldability and anisotropy on molding, various methods have so far been used. In order to improve the moldability, there is a method of blending with a resin of better flowability (good moldability), for example a method of blending with polyethylene terephthalate, polycarbonate, etc., followed by molding.
But, in a case wherein the aforementioned aromatic polyester formed with p-hydroxybenzoic acid or its derivatlve as a central component, for example those which are obtained from p hydroxybenzoic acid, terephthalic acid, isophthalic acid, dihydroxydiphenyl, etc., is mixed with polyethylene terephthalate and polycarbonate, followed by granulation and molding, when these steps are carried out in the temperature region in which said aromatic polyester is uniformalized, polyethylene tere-phthalate and polycarbonate inferior in thermal stability in this region are subject to thermal decomposition.
While when these steps are carried out in the temperature region in which these resins are stably uniformalized, the whole system of the composition does not turn uniform dispersion because of the insufficient flowability of the aromatic polyester. For uniformalizing the whole system, prolonging the residence time of the resin at every step
Further, the aromatic polyester like this has a property to easily orient in molding of large shear, for example, in injection molding, so that there are found problems such that: A difference in percent shrinkage on molding is produced between the machine direction (MD) and ~83~i 1 the transverse direction (TD~, the anisotropy of mechanical strength is also large, and when the molded product has a welded part, the strength of the part is low.
In order to solve the aforementioned problems inherent to the aromatic polyester, i.e. poor moldability and anisotropy on molding, various methods have so far been used. In order to improve the moldability, there is a method of blending with a resin of better flowability (good moldability), for example a method of blending with polyethylene terephthalate, polycarbonate, etc., followed by molding.
But, in a case wherein the aforementioned aromatic polyester formed with p-hydroxybenzoic acid or its derivatlve as a central component, for example those which are obtained from p hydroxybenzoic acid, terephthalic acid, isophthalic acid, dihydroxydiphenyl, etc., is mixed with polyethylene terephthalate and polycarbonate, followed by granulation and molding, when these steps are carried out in the temperature region in which said aromatic polyester is uniformalized, polyethylene tere-phthalate and polycarbonate inferior in thermal stability in this region are subject to thermal decomposition.
While when these steps are carried out in the temperature region in which these resins are stably uniformalized, the whole system of the composition does not turn uniform dispersion because of the insufficient flowability of the aromatic polyester. For uniformalizing the whole system, prolonging the residence time of the resin at every step
3~6 l is also possible, but the system is far from uniform dispersion. Also, for bringing the system to such state, long periods of time are required, which is not practical.
us another method, an improvement in moldability ar.d a reduction in anisotropv can also be achieved by introducing an aliphatic group such as ethylene glycol unit into the structure of the aromatic polyester, thereby decreasing the intermolecular coheslve force. In most cases, however, this brings about a reduction in thermal property to result in damaging the excellent property of the aromatic polyester.
In view of the present situation like this, the present inventors extensively studied to improve the moldability (flowability) of the aromatic polyester and inhibit the orientation on moiding, and as a result, found that this object can be attair:ed by imparting a branched structure to the aromatic polyester. In a word, the case is that a branched structure is given to the aromatic polyester by simultaneous or gradual addition of poly-functional materials on synthesizing the aromatic polyester.But, when as the polyfunctional material, for example tri-functional materials such as trimellitic acid or its anhydride, benzene-1,3,5-tricarboxylic acid, or derivatives thereof, and tetra-funct,onal materials such as pyromellitic acid or its anhydride, benzophenone-3,4,3',4'-tetra-carboxylic acid or its anhydride, or derivatives thereof, i.e. polycarboxylic compounds are used ! there is obtained an effect to inhibit the anisotropy, but the thermal 1 stability becomes poor 5 SO that the thermal resistance, one of the characteristics of the aromatic polyes-ter, becomes poor to make it impossible to use the aromatic polyester.
Further, with pyrogallol and gallic acid, which are a tri-and tetra-functional compounds, respectively, there is a tendency that it is difficult for all the functional groups of the compounds to enter into reaction, or it is dif-ficult to obtain aromatic polyesters having reproducible structure and physical property. As a result ox a further study, the present inventors found that the problems shown above moldability and anisotropy) can be solved without doing a great damage to the various properties characterizing the aromatic polyester including the present mechanical and thermal properties and others. Thus, the present inventors attained to the present invention.
According to the present invention, there is provided the following method: In a method for producing aromatic polyesters by the polycondensation of A: one or more compounds selected from aromatic hydroxy-carboxylic acids and their functional derivatives, or A with B: one or more compounds selected from aromatic dicarboxylic acids and their functional derivatives and C: one or more compounds selected from aromatic diphenols and their functional derivatives, a method for producing aromatic polyesters characterized in that, on said polycondensation,
us another method, an improvement in moldability ar.d a reduction in anisotropv can also be achieved by introducing an aliphatic group such as ethylene glycol unit into the structure of the aromatic polyester, thereby decreasing the intermolecular coheslve force. In most cases, however, this brings about a reduction in thermal property to result in damaging the excellent property of the aromatic polyester.
In view of the present situation like this, the present inventors extensively studied to improve the moldability (flowability) of the aromatic polyester and inhibit the orientation on moiding, and as a result, found that this object can be attair:ed by imparting a branched structure to the aromatic polyester. In a word, the case is that a branched structure is given to the aromatic polyester by simultaneous or gradual addition of poly-functional materials on synthesizing the aromatic polyester.But, when as the polyfunctional material, for example tri-functional materials such as trimellitic acid or its anhydride, benzene-1,3,5-tricarboxylic acid, or derivatives thereof, and tetra-funct,onal materials such as pyromellitic acid or its anhydride, benzophenone-3,4,3',4'-tetra-carboxylic acid or its anhydride, or derivatives thereof, i.e. polycarboxylic compounds are used ! there is obtained an effect to inhibit the anisotropy, but the thermal 1 stability becomes poor 5 SO that the thermal resistance, one of the characteristics of the aromatic polyes-ter, becomes poor to make it impossible to use the aromatic polyester.
Further, with pyrogallol and gallic acid, which are a tri-and tetra-functional compounds, respectively, there is a tendency that it is difficult for all the functional groups of the compounds to enter into reaction, or it is dif-ficult to obtain aromatic polyesters having reproducible structure and physical property. As a result ox a further study, the present inventors found that the problems shown above moldability and anisotropy) can be solved without doing a great damage to the various properties characterizing the aromatic polyester including the present mechanical and thermal properties and others. Thus, the present inventors attained to the present invention.
According to the present invention, there is provided the following method: In a method for producing aromatic polyesters by the polycondensation of A: one or more compounds selected from aromatic hydroxy-carboxylic acids and their functional derivatives, or A with B: one or more compounds selected from aromatic dicarboxylic acids and their functional derivatives and C: one or more compounds selected from aromatic diphenols and their functional derivatives, a method for producing aromatic polyesters characterized in that, on said polycondensation,
- 4 ~L2~3~6 l D: one or more compounds selected from the group consisting of aromatic trihydroxy compounds, aromatic dihydroxy-monocarboxylic acids, aromatic monohydroxydicarboxylic acids and their functional derivatives, are added to the reaction system in one portion or gradually, followed by bringing these compounds into reaction.
In polymerization, it is well known that, by copolymerizing a compound havlng three or more functional groups, a branched structure is given to the polymer obtained, whereby the polymer acquires properties that polymers of linear structure lack. As described above, however, when a polyearboxylic compound is used, aromatic polyesters obtained by polymerization show a tendency to beeome poor in thermal stability, probably due to the residual unreacted carboxyl groups. When a compound is used in which the reactivity of the functional group is disturbed by steric hindrance, the effect is not sufficient or reproducibility is poor. Further, when aliphatic polyfunctional eompounds such as glycerin, trimethylol-ethane, ete. are used, the thermal stability and thermal resistanee of the resulting aromatic polyester come into question. As a result of a study with a series of these compounds, the present inventors found that, as a material which has little steric hindrance, is rich in reactivity and produces polymers having a good thermal stability, the compound D, for example a compound selected from 1,3,5-trihydroxybenzene ~phloroglucin), 3,5-dihydroxy-
In polymerization, it is well known that, by copolymerizing a compound havlng three or more functional groups, a branched structure is given to the polymer obtained, whereby the polymer acquires properties that polymers of linear structure lack. As described above, however, when a polyearboxylic compound is used, aromatic polyesters obtained by polymerization show a tendency to beeome poor in thermal stability, probably due to the residual unreacted carboxyl groups. When a compound is used in which the reactivity of the functional group is disturbed by steric hindrance, the effect is not sufficient or reproducibility is poor. Further, when aliphatic polyfunctional eompounds such as glycerin, trimethylol-ethane, ete. are used, the thermal stability and thermal resistanee of the resulting aromatic polyester come into question. As a result of a study with a series of these compounds, the present inventors found that, as a material which has little steric hindrance, is rich in reactivity and produces polymers having a good thermal stability, the compound D, for example a compound selected from 1,3,5-trihydroxybenzene ~phloroglucin), 3,5-dihydroxy-
- 5 12~3~t~
1 benzoic acid ~5-carboxyresorcinol, ~-resorcinolcarboxylic acid3, 5-hydrGxyisophthalic acid and their functional derivatives is effective, and thus attained to the present invention. As the amount of the compound D added, amounts of 0.3 to 10 mole % based on the compound A are preferred when the aromatic polyester is obtained from the compo~md A alone, and amounts of 0.3 to 10 mole % based on the compound C are preferred when the aromatic polyester is obtained from the compounds A, B and C. When the a~lount exceeds the above range, crosslinking proceeds pre-ferentially to make an improvement in moldability difficult, while when the amount is less than the above range, the effect is not clear.
As a polycondensation method for the aromatic polyester, solution polymerization, inter.acial polymeri-zation, suspension polymerization, bulk polymerization and the like are well known. But, because of the poor solubility of the polymer in organic solvents, suspension polymeriza-tion or bulk polymerization is preferred.
As examples of the compounds A, B and C used in the present invention, there may be given for example p-hydroxybenzoic acid, m-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, l-hydroxy-4-naphthoic acid, l-hydroxy-5-naphthoic acid, 2-hydroxy-7-naphthoic acid, terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, ~2~339~
4,4'~dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfone, 4,4'~dihydroxydiphenyl sulfide, 4,4'~dihydroxydiphenyl-methane, 2,2-bis(4-hydro~yphenyl)propane, 2,6-naphthalene-diol, 1,4-naphthalenediol, 1,5-naphthalenediol, these com-pounds having inac-tive substituents, and their functional derivatives. By combining these compounds wi-th the compound D, the objective aromatic polyester can be derived therefrom.
In the compounds A, B, C and D, it is preferred -tha-t the functional groups, which form -O- and -CO- bonds when the compounds are polycondensed, are not present in adjacent positions on aromatic nucleus.
With reference to the ratio among A, B and C, for example, the molar ratio of A to B is between 10 : 1 to 1 :
10 and that of B to C is between 10 : 9 to 9 : 10.
A me-thod how to use the compound D may be any of those in which D and the compound A, or D and the compounds A, B and C are simultaneously brought into polycondensation, and in which D is previously reacted with one of A, B and C, followed by polymerizing the whole. Also, a method in which D is gradually added to the polymerization system before the polymerization comes to an end, may be thought of.
The polymerization, when either suspension polymeriz-ation or bulk polymerization is employed, is preferably carried out at 200 to 400C, preferably 250 to 350C under normal or reduced pressure in an inert gas atmosphere. It is also possible to advance the polymerization using a catal-yst of which the residue has no adverse effect on the physical properties of -the aromatic polyester obtained, or which loses the activity by simple treatment.
The aroma-tic polyester thus obtained is a .~.
I? ,~
~2~i3~6 1 polymer superior in moldability as well as thermal resistance, mechanical properties and the like. The aromatic polyester obtained by the present invention can sufficiently satisfy mechanical properties and other physical ones even if blended with no fillers, but as need arises, it may be blended with stabilizers, coloring agents end various fillers so far as the characteristics ox the polymer are not damaged. As the filler, there may be given for example inorganic materials such as silica, powdered quartz, sand, fumed silica, silicon carbide, a]uminum oxide, glass fiber, tin oxide, iron Gxide, zinc oxide, carbon, graphite, titanium dioxide, etc., and heat-resistant organic pigments.
The present invention will be illustrated with reference to the following examples and comparative examples, which are however given for the purpose of illustration and not to be interpreted as limiting the invention thereto.
Example 1 To a polymerization vessel having an anchor-form mixing blade with a small clearance between the blade and its internal wall surface, were added 910.8 g (6O6 moles) of p-hydroxybenzoic acid, 547.8 g (3.3 moles) of tere-phthalic acid, 606.4 g (3.26 moles) of 4,4'-dihydroxy-25 diphenyl, 5.0 g (0.04 mole) of 1,3,5-trihydroxybenzene and 1,485 g (14.56 moles) of acetic anhydride. The resulting mixture, with stirring in a nitrogen atmosphere, was 1 heated to 150C and refluxed for 3 hours at this tempera-ture. Thereafter, while raising the temperature, acetic acid resulting from reaction was distilled off, and the temperature was finally raised to 310C under high shear.
The polymerization was continued for further two hours with powerful stirring, and the reaction mixture was then cooled to 200C to obtain 1,736 g (94.6%) of a polymer.
The polymer was pulverized so as to pass through a 0.5 mm~mesh screen and transferred to aluminum rotary oven. Thereafter, while rotating the whole system in a nitrogen stream and thoroughly stirring the powder, the powder was heated to 330C over 6 hours, treated at 330C
for 3 hours, cooled and taken out at 200C.
This polymer was granulated on a single-screw extruder VS-30-28 screw diameter, 30 mm; L/D, 28;
produced by Tanabe Plastic Machinery Co.) under a condition that the cylinder temperature be 350C and the number of rotations of the screw be 50 rpm, an then injection-a 7~r~ elk molded on Neomat N 47!28 injection molding machine produced by Sumitomo Shipbuilding & Machinery Co.). Various test pieces were molded, and the values of the respective physical properties were measured.
The result is shown in Table 1. The surface roughness of the molded product by orientation is inhibited, and the appearance is also smooth. Processability on mold-ing is also good, this being apparent from the large strength of the welded part.
Hereupon, as a mold for the evaluation of welded 33~;
1 parts, there was used a window frame-form mold having its gate at the center so as to produce welded parts, and the molded product produced by it was 3 mm in thickness, 12.5 mm in width and 64 mm in the outside length of each side.
The results of Examples 2, 3 and 4 and Comparative Example 1 were also showed in Table 1.
Examples 2, 3 and 4 The results of the systeTns wherein the amounts of 1,3,5-trihydroxybenzene are 0.5 mole %, 3 mole % and
1 benzoic acid ~5-carboxyresorcinol, ~-resorcinolcarboxylic acid3, 5-hydrGxyisophthalic acid and their functional derivatives is effective, and thus attained to the present invention. As the amount of the compound D added, amounts of 0.3 to 10 mole % based on the compound A are preferred when the aromatic polyester is obtained from the compo~md A alone, and amounts of 0.3 to 10 mole % based on the compound C are preferred when the aromatic polyester is obtained from the compounds A, B and C. When the a~lount exceeds the above range, crosslinking proceeds pre-ferentially to make an improvement in moldability difficult, while when the amount is less than the above range, the effect is not clear.
As a polycondensation method for the aromatic polyester, solution polymerization, inter.acial polymeri-zation, suspension polymerization, bulk polymerization and the like are well known. But, because of the poor solubility of the polymer in organic solvents, suspension polymeriza-tion or bulk polymerization is preferred.
As examples of the compounds A, B and C used in the present invention, there may be given for example p-hydroxybenzoic acid, m-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, l-hydroxy-4-naphthoic acid, l-hydroxy-5-naphthoic acid, 2-hydroxy-7-naphthoic acid, terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, ~2~339~
4,4'~dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfone, 4,4'~dihydroxydiphenyl sulfide, 4,4'~dihydroxydiphenyl-methane, 2,2-bis(4-hydro~yphenyl)propane, 2,6-naphthalene-diol, 1,4-naphthalenediol, 1,5-naphthalenediol, these com-pounds having inac-tive substituents, and their functional derivatives. By combining these compounds wi-th the compound D, the objective aromatic polyester can be derived therefrom.
In the compounds A, B, C and D, it is preferred -tha-t the functional groups, which form -O- and -CO- bonds when the compounds are polycondensed, are not present in adjacent positions on aromatic nucleus.
With reference to the ratio among A, B and C, for example, the molar ratio of A to B is between 10 : 1 to 1 :
10 and that of B to C is between 10 : 9 to 9 : 10.
A me-thod how to use the compound D may be any of those in which D and the compound A, or D and the compounds A, B and C are simultaneously brought into polycondensation, and in which D is previously reacted with one of A, B and C, followed by polymerizing the whole. Also, a method in which D is gradually added to the polymerization system before the polymerization comes to an end, may be thought of.
The polymerization, when either suspension polymeriz-ation or bulk polymerization is employed, is preferably carried out at 200 to 400C, preferably 250 to 350C under normal or reduced pressure in an inert gas atmosphere. It is also possible to advance the polymerization using a catal-yst of which the residue has no adverse effect on the physical properties of -the aromatic polyester obtained, or which loses the activity by simple treatment.
The aroma-tic polyester thus obtained is a .~.
I? ,~
~2~i3~6 1 polymer superior in moldability as well as thermal resistance, mechanical properties and the like. The aromatic polyester obtained by the present invention can sufficiently satisfy mechanical properties and other physical ones even if blended with no fillers, but as need arises, it may be blended with stabilizers, coloring agents end various fillers so far as the characteristics ox the polymer are not damaged. As the filler, there may be given for example inorganic materials such as silica, powdered quartz, sand, fumed silica, silicon carbide, a]uminum oxide, glass fiber, tin oxide, iron Gxide, zinc oxide, carbon, graphite, titanium dioxide, etc., and heat-resistant organic pigments.
The present invention will be illustrated with reference to the following examples and comparative examples, which are however given for the purpose of illustration and not to be interpreted as limiting the invention thereto.
Example 1 To a polymerization vessel having an anchor-form mixing blade with a small clearance between the blade and its internal wall surface, were added 910.8 g (6O6 moles) of p-hydroxybenzoic acid, 547.8 g (3.3 moles) of tere-phthalic acid, 606.4 g (3.26 moles) of 4,4'-dihydroxy-25 diphenyl, 5.0 g (0.04 mole) of 1,3,5-trihydroxybenzene and 1,485 g (14.56 moles) of acetic anhydride. The resulting mixture, with stirring in a nitrogen atmosphere, was 1 heated to 150C and refluxed for 3 hours at this tempera-ture. Thereafter, while raising the temperature, acetic acid resulting from reaction was distilled off, and the temperature was finally raised to 310C under high shear.
The polymerization was continued for further two hours with powerful stirring, and the reaction mixture was then cooled to 200C to obtain 1,736 g (94.6%) of a polymer.
The polymer was pulverized so as to pass through a 0.5 mm~mesh screen and transferred to aluminum rotary oven. Thereafter, while rotating the whole system in a nitrogen stream and thoroughly stirring the powder, the powder was heated to 330C over 6 hours, treated at 330C
for 3 hours, cooled and taken out at 200C.
This polymer was granulated on a single-screw extruder VS-30-28 screw diameter, 30 mm; L/D, 28;
produced by Tanabe Plastic Machinery Co.) under a condition that the cylinder temperature be 350C and the number of rotations of the screw be 50 rpm, an then injection-a 7~r~ elk molded on Neomat N 47!28 injection molding machine produced by Sumitomo Shipbuilding & Machinery Co.). Various test pieces were molded, and the values of the respective physical properties were measured.
The result is shown in Table 1. The surface roughness of the molded product by orientation is inhibited, and the appearance is also smooth. Processability on mold-ing is also good, this being apparent from the large strength of the welded part.
Hereupon, as a mold for the evaluation of welded 33~;
1 parts, there was used a window frame-form mold having its gate at the center so as to produce welded parts, and the molded product produced by it was 3 mm in thickness, 12.5 mm in width and 64 mm in the outside length of each side.
The results of Examples 2, 3 and 4 and Comparative Example 1 were also showed in Table 1.
Examples 2, 3 and 4 The results of the systeTns wherein the amounts of 1,3,5-trihydroxybenzene are 0.5 mole %, 3 mole % and
6 mole %, respectively, based on the total amount of 1,3,5-trihydroxybenzene and 4,4'-dihydroxydiphenyl, are shown in Table 1.
Comparative Example 1 The result of the system containing no 1,3,5-trihydroxybenzene is shown in Table 1. The orientation ofthe molded product is large the welding of parts to be welded being difficult, so that the strength of the welded part is also small.
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3-1-) a ox o l o 5-1 h l to ) tf) f a) 4~ _ m us o Q
a)u, _ _ ~i lo Us I
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_ O O O O o O O O O O
.~ I, O O U~O CO 00 ~~ O I-f CO ED Us Us - . . __ a) us @~
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1 Comparative Example 2 Using the same apparatus as used in Example 1, 910.8 g (6.6 moles) of p-hydro~ybenzoic acid, 531.2 g (3.2 moles) of -terephthalic acid, 613.8 g (3.3 moles3 of 4,4'-dihydroxydiphenyl, 19.2 g (0.1 mole of trimellitic anhydride and 1,485 g (14.56 moles) of acetic anhydride were added to the apparatus and treated in the same manner as in Example 1 to obtain 1,741 g (97.9 ?6) of a polymer.
Thereafter, the polymer was heat-treated, granulated and molded in the same manner. With a molding temperature of 390C, the tensile strength was 1,210 kg/cm2, tensile modulusj 3.9 x 104 ks/cm2; and bending strength of the welded part was 120 kg/cm . It can be seen from this result that the bending strength shows a somewhat improved value as compared with Comparative Example 1, but that the effect is small as compared with Examples 1, 2, 3 and 4.
Example 5 Using the following feed condition, a polymer was synthesized in the same manner as in Example 1: p-Hydroxy-20 benzoic acid, 910.8 g (6.6 moles); terephthalic acid, 547.8 g (3.3 moles3; 4,4'-dinydroxydiphenyl, 606.4 g (3.26 moles); 3,5-dihydroxybenzoic acid, 12.32 g (0.08 mole;
1 mole %, as phenol, based on 4,4'-dihydroxydiphenyl);
and acetic anhydride, 1,485 g (14.56 moles).
On producing a molded product by the same treat-ment and molding, it was found that the surface roughness by orientation was inhibited and the appearance was also 1 Good as compared with a case wherein 3,5-dihydroxybenzoic acid was not added, and that the molded product obtained at 390C had weli-balanced physical properties as shown by a tensile strength ox 1,030 kg/cm2, tensile modulus of 5 3 r 7 x 10 - kg/cm2 and a bendlny strength of welded part of 380 kg/cm2.
Comparative Example 1 The result of the system containing no 1,3,5-trihydroxybenzene is shown in Table 1. The orientation ofthe molded product is large the welding of parts to be welded being difficult, so that the strength of the welded part is also small.
3~tj oc:~ oo oo oo In O
3-1-) a ox o l o 5-1 h l to ) tf) f a) 4~ _ m us o Q
a)u, _ _ ~i lo Us I
l or En K
_ O O O O o O O O O O
.~ I, O O U~O CO 00 ~~ O I-f CO ED Us Us - . . __ a) us @~
,a o . o o o o a a) a) a _ O - O w O
o on En o o o o o o o o o o . O JO OD~9 01` cr~1`
f - -O Sx~ a) I In O O
v pa) . . . .
S `.~:: N E3 O l O
O I-" _ rl R _ _ __ _~
l er I h X O
I
lZ~383~
1 Comparative Example 2 Using the same apparatus as used in Example 1, 910.8 g (6.6 moles) of p-hydro~ybenzoic acid, 531.2 g (3.2 moles) of -terephthalic acid, 613.8 g (3.3 moles3 of 4,4'-dihydroxydiphenyl, 19.2 g (0.1 mole of trimellitic anhydride and 1,485 g (14.56 moles) of acetic anhydride were added to the apparatus and treated in the same manner as in Example 1 to obtain 1,741 g (97.9 ?6) of a polymer.
Thereafter, the polymer was heat-treated, granulated and molded in the same manner. With a molding temperature of 390C, the tensile strength was 1,210 kg/cm2, tensile modulusj 3.9 x 104 ks/cm2; and bending strength of the welded part was 120 kg/cm . It can be seen from this result that the bending strength shows a somewhat improved value as compared with Comparative Example 1, but that the effect is small as compared with Examples 1, 2, 3 and 4.
Example 5 Using the following feed condition, a polymer was synthesized in the same manner as in Example 1: p-Hydroxy-20 benzoic acid, 910.8 g (6.6 moles); terephthalic acid, 547.8 g (3.3 moles3; 4,4'-dinydroxydiphenyl, 606.4 g (3.26 moles); 3,5-dihydroxybenzoic acid, 12.32 g (0.08 mole;
1 mole %, as phenol, based on 4,4'-dihydroxydiphenyl);
and acetic anhydride, 1,485 g (14.56 moles).
On producing a molded product by the same treat-ment and molding, it was found that the surface roughness by orientation was inhibited and the appearance was also 1 Good as compared with a case wherein 3,5-dihydroxybenzoic acid was not added, and that the molded product obtained at 390C had weli-balanced physical properties as shown by a tensile strength ox 1,030 kg/cm2, tensile modulus of 5 3 r 7 x 10 - kg/cm2 and a bendlny strength of welded part of 380 kg/cm2.
Claims (3)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a method for producing aromatic polyesters by the polycondensation of A: one or more compounds selected from aromatic hydroxy-carboxylic acids and their functional derivatives, or A with B: one or more compounds selected from aromatic dicarboxylic acids and their functional derivatives and C: one or more compounds selected from aromatic diphenols and their functional derivatives, a method for producing aromatic polyesters which comprises, on said polycondensation, adding D: one or more compounds selected from the group consisting of aromatic trihydroxy compounds, aromatic dihydroxy-monocarboxylic acids, aromatic monohydroxydicarboxylic acids and their functional derivatives, to the reaction system in one portion or gradually, followed by bringing these compounds into reaction.
2. A method for producing aromatic polyesters according to Claim 1, wherein the amount of the compound D
is 0.3 to 10 mole % based on the compound A when the aromatic polyester comprises the compound A alone, and said amount is 0.3 to 10 mole % based on the compound C when the aromatic polyester is obtained from the compounds A, B and C.
is 0.3 to 10 mole % based on the compound A when the aromatic polyester comprises the compound A alone, and said amount is 0.3 to 10 mole % based on the compound C when the aromatic polyester is obtained from the compounds A, B and C.
3. A method for producing aromatic polyesters according to Claim 1 or 2, wherein the compound A is a compound selected from p-hydroxybenzoic acid, m-hydroxybenzoic acid, 1-hydroxy-5-naphthoic acid, 2-hydroxy-6-naphthoic acid, 1-hydroxy-A-naphthoic acid and their functional derivatives, the compound B is a compound selected from terephthalic acid, isophthalic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid and their functional derivatives, the compound C is a compound selected from hydroquinone, resorcinol, 4,4'-dihydroxy-diphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-diphenyl sulfone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and their functional derivatives, and the compound D is a compound selected from 1,3,5-trihydroxybenzene, 5-carboxyresorcinol, 5-hydroxyisophthalic acid and their functional derivatives.
A. A method for producing aromatic polyesters according to Claim 1, wherein, when the aromatic polyester of the present invention is derived from the compounds A, B, C and D, a relation that the molar ratio of A to B is between 10 : 1 to 1 : 10 and that of B to C is between 10 : 9 to 9 : 10 is satisfied.
A. A method for producing aromatic polyesters according to Claim 1, wherein, when the aromatic polyester of the present invention is derived from the compounds A, B, C and D, a relation that the molar ratio of A to B is between 10 : 1 to 1 : 10 and that of B to C is between 10 : 9 to 9 : 10 is satisfied.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP231290/82 | 1982-12-27 | ||
| JP57231290A JPS59120626A (en) | 1982-12-27 | 1982-12-27 | Production of aromatic polyester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1208396A true CA1208396A (en) | 1986-07-22 |
Family
ID=16921283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000443144A Expired CA1208396A (en) | 1982-12-27 | 1983-12-13 | Method for producing aromatic polyesters |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4542203A (en) |
| JP (1) | JPS59120626A (en) |
| CA (1) | CA1208396A (en) |
| DE (1) | DE3346549C2 (en) |
| FR (1) | FR2538403B1 (en) |
| GB (1) | GB2132626B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5969079A (en) | 1985-09-05 | 1999-10-19 | The Boeing Company | Oligomers with multiple chemically functional end caps |
| US4600765A (en) * | 1984-02-17 | 1986-07-15 | Owens-Corning Fiberglas Corporation | Melt processable optically anisotropic polymers |
| JPS60186525A (en) * | 1984-03-06 | 1985-09-24 | Mitsubishi Chem Ind Ltd | Production of copolymerized polyester having melt anisotropy |
| US5618907A (en) | 1985-04-23 | 1997-04-08 | The Boeing Company | Thallium catalyzed multidimensional ester oligomers |
| GB2199334B (en) * | 1987-01-02 | 1990-08-01 | Mitsubishi Chem Ind | Process for producing a copolyester |
| JPH0196211A (en) * | 1987-10-08 | 1989-04-14 | Kuraray Co Ltd | Wholly aromatic polyester |
| US5817744A (en) | 1988-03-14 | 1998-10-06 | The Boeing Company | Phenylethynyl capped imides |
| JP2590585B2 (en) * | 1990-03-26 | 1997-03-12 | 東レ株式会社 | Copolyester resin |
| US5270402A (en) * | 1990-06-22 | 1993-12-14 | E. I. Du Pont De Nemours And Company | Hyperbranched polyesters |
| US5136014A (en) * | 1990-06-22 | 1992-08-04 | E. I. Du Pont De Nemours And Company | Hyperbranched polyesters |
| US5183862A (en) * | 1990-06-22 | 1993-02-02 | E. I. Du Pont De Nemours And Company | Hyperbranched polyesters |
| JP5036106B2 (en) | 2001-06-15 | 2012-09-26 | 上野製薬株式会社 | Thermotropic liquid crystal polymer |
| WO2007116818A1 (en) * | 2006-03-30 | 2007-10-18 | Toray Industries, Inc. | Dendritic polyester, method for producing the same, and thermoplastic resin composition |
| FR3060009B1 (en) * | 2016-12-13 | 2019-01-25 | Saint-Gobain Isover | THERMOSHURIC ORGANIC FOAMS AND PROCESS FOR PRODUCING THE SAME |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3515696A (en) * | 1963-08-16 | 1970-06-02 | Kuraray Co | Polyesters from hydroxyalkoxybenzoic acids,polyols and polycarboxylic acids |
| FR1492430A (en) * | 1965-09-01 | 1967-08-18 | Gen Electric | Thermoplastic composition based on polycarbonate, process and substance for its preparation |
| US3772250A (en) * | 1970-12-08 | 1973-11-13 | Carborundum Co | Branched aromatic polyesters containing cyanuryl nucleus radicals |
| US3857814A (en) * | 1970-12-08 | 1974-12-31 | Carborundum Co | Branched aromatic polyesters and cross-linked derivatives thereof |
| JPS4841449A (en) * | 1971-10-04 | 1973-06-18 | ||
| US3884876A (en) * | 1973-08-31 | 1975-05-20 | Carborundum Co | Partially crosslinked linear aromatic polyesters |
| JPS5125400A (en) * | 1974-08-26 | 1976-03-01 | Kiichi Ishimaru | Kosotatemono niokeru hijojikinkyuhinansopi |
| US4161470A (en) * | 1977-10-20 | 1979-07-17 | Celanese Corporation | Polyester of 6-hydroxy-2-naphthoic acid and para-hydroxy benzoic acid capable of readily undergoing melt processing |
| JPS54118494A (en) * | 1978-03-07 | 1979-09-13 | Sumitomo Chem Co Ltd | Preparation of polyarylene ester |
| JPS54148883A (en) * | 1978-05-15 | 1979-11-21 | Toyobo Co Ltd | Printed polyester film |
| JPS6040386B2 (en) * | 1978-06-28 | 1985-09-10 | 東洋紡績株式会社 | composite polyester film |
| US4256624A (en) * | 1979-07-02 | 1981-03-17 | Celanese Corporation | Polyester of 6-hydroxy-2-naphthoic acid, aromatic diol, and aromatic diacid capable of undergoing melt processing |
| DE3071755D1 (en) * | 1980-01-24 | 1986-10-16 | Ici Plc | Anisotropic melt-forming polymer |
| JPS5761046A (en) * | 1980-09-30 | 1982-04-13 | Asahi Chem Ind Co Ltd | Aromatic polyamide-polyester resin composition |
| US4390683A (en) * | 1980-10-09 | 1983-06-28 | Mitsui Petrochemical Industries Ltd. | Stretched film structure of the poly-1,3-phenylene terephthalate type |
| US4410683A (en) * | 1981-12-09 | 1983-10-18 | E. I. Du Pont De Nemours And Company | Aromatic, melt-processible (co)polyesters |
-
1982
- 1982-12-27 JP JP57231290A patent/JPS59120626A/en active Pending
-
1983
- 1983-12-13 CA CA000443144A patent/CA1208396A/en not_active Expired
- 1983-12-14 GB GB08333310A patent/GB2132626B/en not_active Expired
- 1983-12-20 FR FR8320369A patent/FR2538403B1/en not_active Expired
- 1983-12-22 DE DE3346549A patent/DE3346549C2/en not_active Expired - Fee Related
-
1984
- 1984-07-30 US US06/636,017 patent/US4542203A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| GB2132626B (en) | 1986-07-09 |
| DE3346549A1 (en) | 1984-06-28 |
| DE3346549C2 (en) | 1995-10-26 |
| JPS59120626A (en) | 1984-07-12 |
| US4542203A (en) | 1985-09-17 |
| FR2538403B1 (en) | 1986-09-26 |
| GB8333310D0 (en) | 1984-01-18 |
| GB2132626A (en) | 1984-07-11 |
| FR2538403A1 (en) | 1984-06-29 |
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