CA1336729C - Poly(arylene sulfide)s and preparation thereof - Google Patents
Poly(arylene sulfide)s and preparation thereofInfo
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- CA1336729C CA1336729C CA000554198A CA554198A CA1336729C CA 1336729 C CA1336729 C CA 1336729C CA 000554198 A CA000554198 A CA 000554198A CA 554198 A CA554198 A CA 554198A CA 1336729 C CA1336729 C CA 1336729C
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Abstract
Improved poly(arylene sulfide) copolymers of meta- and para-dihaloaromatic monomers are prepared by separately reacting the meta- and para- dihaloaromatic monomers with the sulfur source under polymerization conditions. Preferably, the meta-dihaloaromatic monomer is reacted under polymerization conditions prior to the addition of the para-dihaloaromatic monomer. This method avoids the problem of sluggish meta-dihaloaromatic monomer reactivity and produces poly(arylene sulfide) copolymers of reduced melt flow and/or improved polymer quality when compared to poly(arylene sulfide) copolymers prepared by contacting both the meta- and para- dihaloaromatic monomers together initially.
Description
PO~Y(ARYLENE SULFIDE)S AND PREPARATION THEREOF
Field of the Invention This invention relates to a process for the production of poly(arylene sulfide) copolymers. In one aspect, this invention relates to the process of producing high molecular weight poly(arylene sulfide) copolymers of reduced melt flow.
Background of the Invention In the production of specialized fibers and thick films from arylene sulfide polymers, poly(arylene sulfide) meta- and para-difunctional copolymers are preferred. The poly(arylene sulfide) homopolymers which are presently available are not suitable for such applications because they tend to crystallize too rapidly which hinders certain processing steps such as stretching or drawing. This rapid crystallization of these homopolymers is indicated by melt crystallization temperatures of over 200C.
It is desirable that the poly(arylene sulfide) copolymers be of good polymer quality. For some specialized product applications it is also desirable that the poly(arylene sulfide) copolymers have as high molecular weight as possible. Poly(arylene sulfide) copolymers, made of para- and meta- dihaloaromatic monomers, from conventional polymerization processes are of poor polymer quality and do not have a molecular weight high enough to meet certain specialized product specifications. One method of producing poly(arylene sulfide) copolymers from meta- and para-dihaloaromatic monomers is disclosed in U.S. 3,869,434.
It would be beneficial if an improved method could be devised to produce higher molecular weight poly(arylene sulfide) copolymers from the meta- and para- dihaloaromatic monomers.
It would also be beneficial if a method could be devised to produce high quality poly(arylene sulfide) copolymers from meta- and para- dihaloaromatic monomers.
Objects of the Invention It is an object of the present invention to provide a process for improving the quality of poly(arylene sulfide) copolymers. It is a further object of the present invention to provide a process for increasing the molecular weight of poly(arylene sulfide) copolymers. It is yet a further object of this invention to provide high molecular weight poly(arylene sulfide) copolymers. It is still yet a further object of this invention to provide a process for producing good quality high molecular weight poly(arylene sulfide) copolymers from meta- and para- dihaloaromatic monomers.
Summary of the Invention In accordance with this invention, it has been discovered that the meta-dihaloaromatic monomer reacts much slower with the sulfur source in the polymerization process than the para-dihaloaromatic monomer, and is, therefore, not incorporated efficiently into the poly(arylene sulfide) copolymer.
Improved poly(arylene sulfide) meta- and para- difunctional aromatic copolymers (PAS meta-para-copolymers) made from meta- and para-dihaloaromatic monomers, are prepared by separately reacting the meta-and para- dihaloaromatic monomers with the sulfur source under polymerization conditions. More specifically, improved PAS
meta-para-copolymers are produced by prereacting the meta-dihaloaromatic monomer with the sulfur source in the polar organic medium under polymerization conditions prior to the addition of the para-dihaloaromatic monomer.
This method produces improved PAS meta-para-copolymers of higher molecular weight when compared to PAS meta-para-copolymers prepared by contacting both the meta- and para- dihaloaromatic monomers together initially.
- 1 3367~9 Detailed Description of the Invention According to the present invention when producing high quality and/or high molecular weight PAS meta-para-copolymers it is important to avoid the problem of the sluggish reactivity of the meta-dihaloaromatic monomer (meta-monomer). To avoid this problem, it is essential that the meta-monomer polymerization be conducted substantially in the absence of the more active para-dihaloaromatic monomer (para-monomer) so as to avoid competing for incorporation into the polymer.
In accordance with the present invention it is also preferred that at least one polyhaloaromatic monomer having more than two halogen substituents per molecule be employed in the polymerization process.
The more preferred method for avoiding the sluggish meta-monomer reactivity is to prereact the meta-monomer in essentially the absence of the para-monomer. This prereaction of the meta-monomer forms poly(meta-arylene sulfide) blocks (meta-blocks). The para-monomer is then added under polymerization conditions to grow onto these meta-blocks thereby forming a high molecular weight PAS
meta-para-copolymer of improved quality.
In accordance with this more preferred aspect of the present invention an improved high molecular weight poly(arylene sulfide) copolymer is prepared by contacting under polymerization conditions a mixture of about 0.01 to 90 mole percent of at least one meta-dihalobenzene monomer, 0 to 10 mole percent of at least one polyhalobenzene monomer having more than two halogen substituents, and an alkali metal sulfide, in a polar organic medium, for a sufficient length of time to form poly(meta-arylene sulfide) blocks; followed by the addition of about 1 to 99.99 mole percent of at least one para-dihalobenzene monomer under polymerization conditions for a sufficient length of time to grow para-dihalobenzene onto the poly(meta-arylene sulfide) blocks thereby producing a poly(arylene sulfide) copolymer. The mole percent of each monomer is based on the total of each of the three monomers present in the final block copolymer.
The most preferred method according to the present invention is to prereact the meta-monomer and a polyhaloaromatic monomer with a sulfur source under polymerization conditions, followed by the addition of the _ 4 para-monomer under polymerization conditions, thereby producing a branched high molecular weight PAS meta-para-copolymer of improved polymer quality.
There are less preferred polymerization methods that avoid the sluggish meta-monomer reactivity. One method includes separately preforming meta- and para- blocks, then joining these blocks together to form the PAS meta-para-copolymer. Another method includes prereacting the para-monomer to form para-blocks then growing the meta-monomer under polymerization conditions onto the para-blocks to form the PAS
meta-para-copolymer. Though these two less preferred methods avoid the polymerization of the meta-monomer in the presence of the para-monomer, it is believed that too many unincorporated meta-blocks would be present in the final product. This is believed to be so since in the first less preferred method joining prereacted blocks would not be efficient and in the other less preferred method the sluggish meta-monomer would more likely form small meta-blocks (meta-oligomers) than grow onto the prereacted para-blocks.
In the most preferred method of the present invention it is preferred that all of the sulfur and polyhaloaromatic monomer be present initially when the meta-monomer is prereacted. However, it is possible to add only part of the sulfur and polyhaloaromatic monomer when the meta-monomer is prereacted and then add the remainder when the para-monomer is introduced into the reaction mixture.
According to the present invention it is possible to avoid the sluggish meta-monomer reactivity without producing a high molecular weight copolymer. A lower molecular weight PAS meta-para-copolymer can be produced by terminating the invention polymerization process prior to completion. This lower molecular weight copolymer is within the scope of the present invention since meta-monomer would still be incorporated efficiently into the copolymer.
1 33 b 7 2 9 The meta-monomers are preferably selected from m-dihalobenzenes of the formula X R
R ~ X
R R
wherein X is halogen and each R can be the same or different and is selected from the group consisting of hydrogen, alkyl having one to 20 carbon atoms, cyclo alkyl having 5 to 20 carbon atoms, aryl having 6 to 24 carbon atoms, alkyl aryl having 7 to 24 carbon atoms, and aryl alkyl having 7 to 24 carbon atoms. Examples of suitable m-dihalobenzenes include m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 1-chloro-3-bromobenzene, 1-chloro-3-iodobenzene, 1-bromo-3-iodobenzene, and the like, and mixtures of any two or more thereof. The m-dihalobenzene presently preferred due to its effectiveness and availability is m-dichlorobenzene (mDCB).
The para-monomers are preferably selected from p-dihalobenzenes of the formula R R
X~
R R
wherein X and R are as above. Examples of suitable p-dihal-obenzenes include p-dichlorobenzene, p-dibromobenzene, p-di-iodobenzene, l-chloro-4-bromobenzene, 1-chloro-4-iodobenzene, 1-bromo-4-iodobenzene, 2,4-dichlorotoluene, 2,5-dichloro-p-xylene, and the like, and mixtures of any two or more thereof 2,5-dichloro-p-xylene, 1-ethyl-4-isopropyl-2,5-dibromobenz-ene, 1,2,4,5-tetramethyl-2,6-dichlorobenzene, 1-butyl-4-cyc-lohexyl-2,5-dibromobenzene, 1-hexyl-3-dodecyl-2,5-dichloro-benzene, 1-octadecyl-2,5-diiodobenzene, 1-phenyl-2-chloro-5-bromobenzene, l-(p-tolyl)-2,5-dibromobenzene, 1-benzyl-2,5-dichlorobenzene, l-octyl-4-(3-methylcyclopentyl)-2,5-dichlo-robenzene. The p-dihalobenzene presently preferred due to its effectiveness and availability is p-dichlorobenzene (pDCB).
X
- 6 l 336~9 Polyhaloaromatic monomers are preferably polyhalobenzenes selected from the formula (X)n wherein X and R are as above n is > 3, and m is < 3 and n~m=6. Examples of some polyhaloaromatic compounds having more than two halogen substituents per molecule include 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3-dichloro-5-bromobenzene, 1,2,4-triiodobenzene, 1,2-dibromo-4-iodo-10 benzene, 2,4,6-trichlorotoluene, 1,2,3,5-tetrabromobenzene, hexa-chlorobenzene, 1,3,5-trichloro-2,4,6-trimethylbenzene, 2,2',4,4'-tetra-chlorobiphenyl, 2,3',5,5'-tetraiodobiphenyl, 2,2',6,6'-tetra-bromo-3,3',5,5'-tetramethylbiphenyl, 1,2,3,4-tetrachloronaphthalene, 1,2,4-tribromo-6-methylnaphthalene, and the like, and mixtures of any two or more thereof. The polyhaloaromatic presently preferred due to its effectiveness and availability is 1,2,4-trichlorobenzene (hereinafter TCB).
The monomers will be employed in a total amount of at least about 0.9 mole per mole of sulfur (alkali metal sulfide) to an amount not greater than about 2 moles per mole of sulfur (alkali metal sulfide).
The meta-monomer will comprise from about 0.01 to 90 mole percent and preferably from about 1 to 20 mole percent of the total quantity of the monomers employed. The para-monomer will comprise from about 1 to 99.99 mole percent preferably from about 10 to 99.9 mole percent and more preferably from about 80 to 99 mole percent of the total quantity of the monomers employed. The mole percent of the polyhaloaromatic monomers having more than two halogen substituents per molecule will comprise from about 0 to about 10 mole percent and preferably from about 0.1 to 2 mole percent based on the total of each of the three monomers present in the final block copolymer.
According to the present invention the final polymers will be block copolymers having para- and meta- difunctional aromatic blocks.
Preferably the PAS meta-para-copolymers will be made of reoccurring units (a) (R
R
and reoccurring units (b) ~ R R
~ /
R
and optionally units (c) (~m ~_ wherein each R can be the same or different and is selected from the group consisting of hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 20 carbon atoms, aryl having 6 to 24 carbon atoms, 20 alkyl aryl having 7 to 24 carbon atoms and aryl alkyl having 7 to 24 carbon atoms. Wherein z is > 2, m is < 3, and m+z=5.
_ 8 l 336729 Preferably the units of (c) will be represented by / R S
~S-~ R R J
where P is a continuing polymer chain.
More preferably the block copolymers of the present invention are poly(phenylene sulfide) (PPS) block copolymers.
The polar organic mediums are solvents for the haloaromatic compounds and the alkali metal sulfides used in the production of arylene sulfide polymers. Examples of such polar organic solvents include amides, including lactams, and sulfones. Specific examples of such polar organic solvents include hexamethylphosphoramide, tetramethylurea, N,N'-ethylenedipyrrolidone, N-methyl-2-pyrrolidone, pyrrolidone, caprolactam, N-ethylcaprolactam, sulfolane, N,N'-dimethylacetamide, low molecular weight polyamides, and the like, and mixtures of any two or more thereof. The polar organic solvent presently preferred is N-methyl-2-pyrrolidone (NMP).
The amount of the polar organic solvent such as the organic amide can vary over a wide range. Preferably, the polar organic solvent will be employed in an amount within the range of about 100 grams to about 2500 grams per gram-mole of sulfur.
The sulfur source used in the present invention can be any source of sulfur where the sulfur is efficiently incorporated into the backbone of the polymer. Specific examples of the sulfur source can be, for example, alkali metal sulfide, a metalthiocarboxylate, a metalthiosulfate, a thioamide, elemental sulfur, carbon disulfide or carbon oxysulfide, a thiocarbomate, a xanthate, a trithiocarbonate, an activated mercaptan or sulfide, or the like or mixtures any any two or more thereof. The preferred sulfur source is an alkali metal sulfide.
Sodium sulfide in hydrated form being preferred.
~ g If desired, the alkali metal sulfides can be produced in situ, e.g., from the alkali metal hydroxides and the alkali metal bisulfides.
The alkali metal sulfide can also be prepared from hydrogen sulfide.
Although the reaction temperatures at which the two separate monomer polymerizations are conducted can vary over a wide range, generally they will be within the range of about 125C to about 450C.
Preferably, temperatures within the range of about 175C to about 350C
will be employed.
The two mixtures are subjected to polymerization conditions for a period dependent, in part, on the temperatures employed. Generally, a total period of polymerization for the two polymerizations will be within the range of about 10 minutes to about 72 hours, preferably within the range of about 1 to about 8 hours. In the most preferred process, the meta-monomer is prereacted under polymerization conditions for about 1 hour prior to the addition of the para-monomer.
The pressure need only be sufficient to maintain the monomers and the polar organic solvent substantially in the liquid phase and to retain the sulfur source therein.
The PAS meta-para-copolymers can be recovered from the polymerization mixture by conventional procedures such as evaporation of the solvent followed by washing with water, or by dilution of the polymerization mixture with water, or other organic solvent, followed by filtration and water washing of the polymer.
The molecular weight of the PAS meta-para-copolymer prepared according to the present invention is assessed by noting the melt flow after being retained in the barrel of a melt index apparatus under ASTM
D1238 conditions for about 5 minutes at 600F. The molecular weight is inversely related to the melt flow of the polymer. The melt flow is determined by adding a 5 kilogram weight to the barrel of the melt index apparatus and weighing the amount of material extruded during a period of time and is reported in grams per 10 minutes.
It is preferred that the PAS meta-para-copolymers have a melt flow within the range of about 1 to 10,000 g/10 minutes, preferably about 30 to 500 g/10 minutes, and more preferably about 50 to 180 g/10 minutes.
`-- 10 1 ~36729 According to the present invention lt is preferred that the melt crystallization temperature of the PAS meta-para-copolymers be below about 200C.
The polymers of the present invention are preferably used in the manufacture of film, preferably thick film. The polymers of the present invention can also be used in other applications and can be blended with fillers, pigments, stabilizers, plasticizers, and the like.
The polymers can be cured by heating to a temperature within the range of from about 125C. to about 500C. and preferably between about 200C. and about 350C., for about 5 minutes to about 20 hours and preferably for about 10 minutes to about 6 hours. Preferably, this heating will be carried out in the presence of air or other free oxygen-containing gas.
Curing promoters can be employed.
Prior to the present invention it was expected that a polymer could not be made by prereacting the meta-monomer with the total amount of alkali metal sulfide followed by the addition of the para-monomer.
This was believed because prior to the present invention, it was expected that any meta-block polymer made would be degraded. The results in the present examples show that this is not the case.
Examples The following are examples illustrating the process of the present invention. Particular materials employed, species, and conditions are intended to be further illustrative of this invention and not limitative of the reasonable scope thereof.
Example I
A control run was carried out in which PPS copolymer was prepared by contacting, under polymerization conditions, meta- and para-difunctional aromatic monomers together initially.
To a two gallon reactor were charged 572.6g of sodium hydrosulfide ~6.00 moles/58.74% pure NaSH x H20), 254g of sodium hydroxide (6.35 moles/100% pure NaOH pellets from Mallinckrodt), 147.6g of sodium acetate (1.80 moles/100% pure sodium acetate from Niocet Corporation), and 1600cc of NMP (16.56 moles/99.5% pure NMP from BASF).
The mixture was purged with nitrogen, stirred at 250 RPM, and heated to 160C and held for 4 minutes. Dehydration was started and a total of 360 -cc of water and NMP were distilled off while reaching 200C. To the reactor were also charged 808.5g of hot pDCB (5.5 moles/100% pure pDCB
from PPG Chemical), 88.2g of hot mDCB (0.6 moles/100% pure mDCB from Ishihara Chemical), 2.17g of hot TCB (0.012 moles/100% pure TCB from MCB
Chemical), and 325cc of hot NMP. An after charge reactor pressure of 50 psig was established with nitrogen gas. The reactor temperature was raised to 235C and held for two hours. The reactor temperature was then raised to 265C and held for three hours with a ~xi presure of 170 psig. The stirrer RPM was raised to 600 and 250 cc of hot deionized water were charged slowly to the reactor. The reactor contents were then allowed to cool overnight. The next morning 2250 cc of deionized water were charged to the reactor and the stirrer RPM was held at 250 for ten minutes. A solid polymer was recovered then water washed, acetone washed, and dried in a forced air oven at 110C.
This run yielded 593.4g (91.4%) of dried PPS copolymer with the following characteristics:
A melt flow of 184.68 g/10 minutes, an ash content of 1.23 weight percent, and a melt crystallization temperature (Tmc~ of 147C.
Example II
This control run was conducted as in Example I, except that instead of 360 cc, 370 cc of H20 and NMP were distilled off and when the 2250 cc of deionized water were added the stirrer locked up and the polymer had to be ground in a Waring Blendor prior to washing and drying.
The run yielded 489.lg (75.97%) of dried PPS copolymer with the 25 following characteristics: A melt flow of 219 g/10 minutes, an ash content of 0.96 weight percent, and a Tmc of 154C.
Example III
This control run was conducted as in Example II and yielded 544.9g (83.97%) of PPS copolymer with the following characteristics: A
30 melt flow of 203.64 g/10 minutes, an ash content of 1.14 weight percent, and a Tmc of 170C.
Example IV
According to the present invention a run was carried out in which PPS block copolymer was prepared by prereacting under polymerization conditions meta- difunctional aromatic monomer.
1 3367~9 32260CA
To a two gallon reactor were charged 568.5g of sodium hydrosulfide (6.00 moles/59.17% pure NaSH x H20), 254g of sodium hydroxide (6.35 moles/100% pure NaOH pellets from Mallinckrodt Chemical Co.), 147.6g of sodium acetate (1.80 moles/100% pure sodium acetate from Niocet Coporation), 1600cc of NMP (16.56 moles/99.5% pure NMP from BASF).
The mixture was then heated with nitrogen and stirred at 250 RPM, and heated to 160C and held for five minutes. Dehydration was started and a total of 360cc of water and NMP were distilled off while reaching 200C.
To the reactor were also charged 88.2g of hot mDCB (0.6 moles/100% pure mDCB from Ishihara Chemical), 2.17g hot TCB (0.012 moles/100% pure TCB
from MCB Chemical), and 50cc of hot NMP. An after charge reactor pressure of 50 psig was established. The reactor temperature was raised to 235C and held for 1 hour. This was followed by the addition of 808.5g of hot pDCB (5.5 moles/100% pure pDCB from PPG Chemical), and 235cc of hot NMP. An after charge reactor pressure of 75 psig was established and the reactor was held at 235C for an additional hour.
The reactor temperature was then raised to 265C and held for 3 hours with a maximum pressure of 150 psig. The stirrer RPM was raised to 600 and 250cc of hot deionized water were charged slowly to the reactor. The reactor contents were then allowed to cool overnight. The next morning 2250cc of deionized water were charged to the reactor and the stirrer RPM
was held at 250 for 10 minutes. A solid polymer was recovered, then water washed, acetone washed, and dried in a forced air oven at 110C.
This run yielded 563.9g (86.89%) of dried PPS block copolymer with a melt flow of 120.71 g/10 minutes and a Tmc of 170C.
Example V
This run was conducted as in Example IV except that two pressures were different. The after charge reactor pressure after the addition of pDCB and NMP was 100 psig and the ~xi reactor pressure after the temperature was raised to 265C was 180 psig. This run yielded 413.6g (63.73%) of dried PPS block copolymer (some polymer was lost before workup) with a melt flow of 133.99 g/10 minutes.
13 l 336729 Example VI
This run was conducted as in Example V except that the maximum reactor pressure, after the reactor was raised to 265C, was not measured.
This run yielded 571.5g (88.06%) of dried PPS block copolymer with a melt flow of 94.11 g/10 minutes.
Example VII
This run was conducted as in Example VI except that the after charge reactor pressure after the addition of pDCB and NMP was not measured and the ~xi reactor pressure after the reactor was raised to 265C was measured at 100 psig.
This run yielded 559g (86.14%) of dried PPS block copolymer with a melt flow of 154 g/10 minutes.
The above examples show that by prereacting the mDCB prior to the addition of the pDCB, the problem of sluggish mDCB monomer reactivity is avoided. The PPS block copolymers prepared in the four invention examples (IV-VII) above have an improved melt flow of about 120 g/10 minutes as compared to the melt flow of about 200 g/10 minutes for the PPS copolymers which are prepared by reacting mDCB and pDCB together initially. This reduction in melt flow shows that the mDCB is incorporated more efficiently into the copolymer by following the process of the present invention.
All polymers produced in the control and invention examples above are good meta-para-copolymers and, therefore, have acceptable melt crystallization temperatures for use in fiber and film applications.
However, only the meta-para-copolymers produced in invention Examples IV-VII are high molecular weight meta-para-copolymers. These high molecular weight meta-para-copolymers will provide fibers and films of improved quality.
Field of the Invention This invention relates to a process for the production of poly(arylene sulfide) copolymers. In one aspect, this invention relates to the process of producing high molecular weight poly(arylene sulfide) copolymers of reduced melt flow.
Background of the Invention In the production of specialized fibers and thick films from arylene sulfide polymers, poly(arylene sulfide) meta- and para-difunctional copolymers are preferred. The poly(arylene sulfide) homopolymers which are presently available are not suitable for such applications because they tend to crystallize too rapidly which hinders certain processing steps such as stretching or drawing. This rapid crystallization of these homopolymers is indicated by melt crystallization temperatures of over 200C.
It is desirable that the poly(arylene sulfide) copolymers be of good polymer quality. For some specialized product applications it is also desirable that the poly(arylene sulfide) copolymers have as high molecular weight as possible. Poly(arylene sulfide) copolymers, made of para- and meta- dihaloaromatic monomers, from conventional polymerization processes are of poor polymer quality and do not have a molecular weight high enough to meet certain specialized product specifications. One method of producing poly(arylene sulfide) copolymers from meta- and para-dihaloaromatic monomers is disclosed in U.S. 3,869,434.
It would be beneficial if an improved method could be devised to produce higher molecular weight poly(arylene sulfide) copolymers from the meta- and para- dihaloaromatic monomers.
It would also be beneficial if a method could be devised to produce high quality poly(arylene sulfide) copolymers from meta- and para- dihaloaromatic monomers.
Objects of the Invention It is an object of the present invention to provide a process for improving the quality of poly(arylene sulfide) copolymers. It is a further object of the present invention to provide a process for increasing the molecular weight of poly(arylene sulfide) copolymers. It is yet a further object of this invention to provide high molecular weight poly(arylene sulfide) copolymers. It is still yet a further object of this invention to provide a process for producing good quality high molecular weight poly(arylene sulfide) copolymers from meta- and para- dihaloaromatic monomers.
Summary of the Invention In accordance with this invention, it has been discovered that the meta-dihaloaromatic monomer reacts much slower with the sulfur source in the polymerization process than the para-dihaloaromatic monomer, and is, therefore, not incorporated efficiently into the poly(arylene sulfide) copolymer.
Improved poly(arylene sulfide) meta- and para- difunctional aromatic copolymers (PAS meta-para-copolymers) made from meta- and para-dihaloaromatic monomers, are prepared by separately reacting the meta-and para- dihaloaromatic monomers with the sulfur source under polymerization conditions. More specifically, improved PAS
meta-para-copolymers are produced by prereacting the meta-dihaloaromatic monomer with the sulfur source in the polar organic medium under polymerization conditions prior to the addition of the para-dihaloaromatic monomer.
This method produces improved PAS meta-para-copolymers of higher molecular weight when compared to PAS meta-para-copolymers prepared by contacting both the meta- and para- dihaloaromatic monomers together initially.
- 1 3367~9 Detailed Description of the Invention According to the present invention when producing high quality and/or high molecular weight PAS meta-para-copolymers it is important to avoid the problem of the sluggish reactivity of the meta-dihaloaromatic monomer (meta-monomer). To avoid this problem, it is essential that the meta-monomer polymerization be conducted substantially in the absence of the more active para-dihaloaromatic monomer (para-monomer) so as to avoid competing for incorporation into the polymer.
In accordance with the present invention it is also preferred that at least one polyhaloaromatic monomer having more than two halogen substituents per molecule be employed in the polymerization process.
The more preferred method for avoiding the sluggish meta-monomer reactivity is to prereact the meta-monomer in essentially the absence of the para-monomer. This prereaction of the meta-monomer forms poly(meta-arylene sulfide) blocks (meta-blocks). The para-monomer is then added under polymerization conditions to grow onto these meta-blocks thereby forming a high molecular weight PAS
meta-para-copolymer of improved quality.
In accordance with this more preferred aspect of the present invention an improved high molecular weight poly(arylene sulfide) copolymer is prepared by contacting under polymerization conditions a mixture of about 0.01 to 90 mole percent of at least one meta-dihalobenzene monomer, 0 to 10 mole percent of at least one polyhalobenzene monomer having more than two halogen substituents, and an alkali metal sulfide, in a polar organic medium, for a sufficient length of time to form poly(meta-arylene sulfide) blocks; followed by the addition of about 1 to 99.99 mole percent of at least one para-dihalobenzene monomer under polymerization conditions for a sufficient length of time to grow para-dihalobenzene onto the poly(meta-arylene sulfide) blocks thereby producing a poly(arylene sulfide) copolymer. The mole percent of each monomer is based on the total of each of the three monomers present in the final block copolymer.
The most preferred method according to the present invention is to prereact the meta-monomer and a polyhaloaromatic monomer with a sulfur source under polymerization conditions, followed by the addition of the _ 4 para-monomer under polymerization conditions, thereby producing a branched high molecular weight PAS meta-para-copolymer of improved polymer quality.
There are less preferred polymerization methods that avoid the sluggish meta-monomer reactivity. One method includes separately preforming meta- and para- blocks, then joining these blocks together to form the PAS meta-para-copolymer. Another method includes prereacting the para-monomer to form para-blocks then growing the meta-monomer under polymerization conditions onto the para-blocks to form the PAS
meta-para-copolymer. Though these two less preferred methods avoid the polymerization of the meta-monomer in the presence of the para-monomer, it is believed that too many unincorporated meta-blocks would be present in the final product. This is believed to be so since in the first less preferred method joining prereacted blocks would not be efficient and in the other less preferred method the sluggish meta-monomer would more likely form small meta-blocks (meta-oligomers) than grow onto the prereacted para-blocks.
In the most preferred method of the present invention it is preferred that all of the sulfur and polyhaloaromatic monomer be present initially when the meta-monomer is prereacted. However, it is possible to add only part of the sulfur and polyhaloaromatic monomer when the meta-monomer is prereacted and then add the remainder when the para-monomer is introduced into the reaction mixture.
According to the present invention it is possible to avoid the sluggish meta-monomer reactivity without producing a high molecular weight copolymer. A lower molecular weight PAS meta-para-copolymer can be produced by terminating the invention polymerization process prior to completion. This lower molecular weight copolymer is within the scope of the present invention since meta-monomer would still be incorporated efficiently into the copolymer.
1 33 b 7 2 9 The meta-monomers are preferably selected from m-dihalobenzenes of the formula X R
R ~ X
R R
wherein X is halogen and each R can be the same or different and is selected from the group consisting of hydrogen, alkyl having one to 20 carbon atoms, cyclo alkyl having 5 to 20 carbon atoms, aryl having 6 to 24 carbon atoms, alkyl aryl having 7 to 24 carbon atoms, and aryl alkyl having 7 to 24 carbon atoms. Examples of suitable m-dihalobenzenes include m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 1-chloro-3-bromobenzene, 1-chloro-3-iodobenzene, 1-bromo-3-iodobenzene, and the like, and mixtures of any two or more thereof. The m-dihalobenzene presently preferred due to its effectiveness and availability is m-dichlorobenzene (mDCB).
The para-monomers are preferably selected from p-dihalobenzenes of the formula R R
X~
R R
wherein X and R are as above. Examples of suitable p-dihal-obenzenes include p-dichlorobenzene, p-dibromobenzene, p-di-iodobenzene, l-chloro-4-bromobenzene, 1-chloro-4-iodobenzene, 1-bromo-4-iodobenzene, 2,4-dichlorotoluene, 2,5-dichloro-p-xylene, and the like, and mixtures of any two or more thereof 2,5-dichloro-p-xylene, 1-ethyl-4-isopropyl-2,5-dibromobenz-ene, 1,2,4,5-tetramethyl-2,6-dichlorobenzene, 1-butyl-4-cyc-lohexyl-2,5-dibromobenzene, 1-hexyl-3-dodecyl-2,5-dichloro-benzene, 1-octadecyl-2,5-diiodobenzene, 1-phenyl-2-chloro-5-bromobenzene, l-(p-tolyl)-2,5-dibromobenzene, 1-benzyl-2,5-dichlorobenzene, l-octyl-4-(3-methylcyclopentyl)-2,5-dichlo-robenzene. The p-dihalobenzene presently preferred due to its effectiveness and availability is p-dichlorobenzene (pDCB).
X
- 6 l 336~9 Polyhaloaromatic monomers are preferably polyhalobenzenes selected from the formula (X)n wherein X and R are as above n is > 3, and m is < 3 and n~m=6. Examples of some polyhaloaromatic compounds having more than two halogen substituents per molecule include 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3-dichloro-5-bromobenzene, 1,2,4-triiodobenzene, 1,2-dibromo-4-iodo-10 benzene, 2,4,6-trichlorotoluene, 1,2,3,5-tetrabromobenzene, hexa-chlorobenzene, 1,3,5-trichloro-2,4,6-trimethylbenzene, 2,2',4,4'-tetra-chlorobiphenyl, 2,3',5,5'-tetraiodobiphenyl, 2,2',6,6'-tetra-bromo-3,3',5,5'-tetramethylbiphenyl, 1,2,3,4-tetrachloronaphthalene, 1,2,4-tribromo-6-methylnaphthalene, and the like, and mixtures of any two or more thereof. The polyhaloaromatic presently preferred due to its effectiveness and availability is 1,2,4-trichlorobenzene (hereinafter TCB).
The monomers will be employed in a total amount of at least about 0.9 mole per mole of sulfur (alkali metal sulfide) to an amount not greater than about 2 moles per mole of sulfur (alkali metal sulfide).
The meta-monomer will comprise from about 0.01 to 90 mole percent and preferably from about 1 to 20 mole percent of the total quantity of the monomers employed. The para-monomer will comprise from about 1 to 99.99 mole percent preferably from about 10 to 99.9 mole percent and more preferably from about 80 to 99 mole percent of the total quantity of the monomers employed. The mole percent of the polyhaloaromatic monomers having more than two halogen substituents per molecule will comprise from about 0 to about 10 mole percent and preferably from about 0.1 to 2 mole percent based on the total of each of the three monomers present in the final block copolymer.
According to the present invention the final polymers will be block copolymers having para- and meta- difunctional aromatic blocks.
Preferably the PAS meta-para-copolymers will be made of reoccurring units (a) (R
R
and reoccurring units (b) ~ R R
~ /
R
and optionally units (c) (~m ~_ wherein each R can be the same or different and is selected from the group consisting of hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 20 carbon atoms, aryl having 6 to 24 carbon atoms, 20 alkyl aryl having 7 to 24 carbon atoms and aryl alkyl having 7 to 24 carbon atoms. Wherein z is > 2, m is < 3, and m+z=5.
_ 8 l 336729 Preferably the units of (c) will be represented by / R S
~S-~ R R J
where P is a continuing polymer chain.
More preferably the block copolymers of the present invention are poly(phenylene sulfide) (PPS) block copolymers.
The polar organic mediums are solvents for the haloaromatic compounds and the alkali metal sulfides used in the production of arylene sulfide polymers. Examples of such polar organic solvents include amides, including lactams, and sulfones. Specific examples of such polar organic solvents include hexamethylphosphoramide, tetramethylurea, N,N'-ethylenedipyrrolidone, N-methyl-2-pyrrolidone, pyrrolidone, caprolactam, N-ethylcaprolactam, sulfolane, N,N'-dimethylacetamide, low molecular weight polyamides, and the like, and mixtures of any two or more thereof. The polar organic solvent presently preferred is N-methyl-2-pyrrolidone (NMP).
The amount of the polar organic solvent such as the organic amide can vary over a wide range. Preferably, the polar organic solvent will be employed in an amount within the range of about 100 grams to about 2500 grams per gram-mole of sulfur.
The sulfur source used in the present invention can be any source of sulfur where the sulfur is efficiently incorporated into the backbone of the polymer. Specific examples of the sulfur source can be, for example, alkali metal sulfide, a metalthiocarboxylate, a metalthiosulfate, a thioamide, elemental sulfur, carbon disulfide or carbon oxysulfide, a thiocarbomate, a xanthate, a trithiocarbonate, an activated mercaptan or sulfide, or the like or mixtures any any two or more thereof. The preferred sulfur source is an alkali metal sulfide.
Sodium sulfide in hydrated form being preferred.
~ g If desired, the alkali metal sulfides can be produced in situ, e.g., from the alkali metal hydroxides and the alkali metal bisulfides.
The alkali metal sulfide can also be prepared from hydrogen sulfide.
Although the reaction temperatures at which the two separate monomer polymerizations are conducted can vary over a wide range, generally they will be within the range of about 125C to about 450C.
Preferably, temperatures within the range of about 175C to about 350C
will be employed.
The two mixtures are subjected to polymerization conditions for a period dependent, in part, on the temperatures employed. Generally, a total period of polymerization for the two polymerizations will be within the range of about 10 minutes to about 72 hours, preferably within the range of about 1 to about 8 hours. In the most preferred process, the meta-monomer is prereacted under polymerization conditions for about 1 hour prior to the addition of the para-monomer.
The pressure need only be sufficient to maintain the monomers and the polar organic solvent substantially in the liquid phase and to retain the sulfur source therein.
The PAS meta-para-copolymers can be recovered from the polymerization mixture by conventional procedures such as evaporation of the solvent followed by washing with water, or by dilution of the polymerization mixture with water, or other organic solvent, followed by filtration and water washing of the polymer.
The molecular weight of the PAS meta-para-copolymer prepared according to the present invention is assessed by noting the melt flow after being retained in the barrel of a melt index apparatus under ASTM
D1238 conditions for about 5 minutes at 600F. The molecular weight is inversely related to the melt flow of the polymer. The melt flow is determined by adding a 5 kilogram weight to the barrel of the melt index apparatus and weighing the amount of material extruded during a period of time and is reported in grams per 10 minutes.
It is preferred that the PAS meta-para-copolymers have a melt flow within the range of about 1 to 10,000 g/10 minutes, preferably about 30 to 500 g/10 minutes, and more preferably about 50 to 180 g/10 minutes.
`-- 10 1 ~36729 According to the present invention lt is preferred that the melt crystallization temperature of the PAS meta-para-copolymers be below about 200C.
The polymers of the present invention are preferably used in the manufacture of film, preferably thick film. The polymers of the present invention can also be used in other applications and can be blended with fillers, pigments, stabilizers, plasticizers, and the like.
The polymers can be cured by heating to a temperature within the range of from about 125C. to about 500C. and preferably between about 200C. and about 350C., for about 5 minutes to about 20 hours and preferably for about 10 minutes to about 6 hours. Preferably, this heating will be carried out in the presence of air or other free oxygen-containing gas.
Curing promoters can be employed.
Prior to the present invention it was expected that a polymer could not be made by prereacting the meta-monomer with the total amount of alkali metal sulfide followed by the addition of the para-monomer.
This was believed because prior to the present invention, it was expected that any meta-block polymer made would be degraded. The results in the present examples show that this is not the case.
Examples The following are examples illustrating the process of the present invention. Particular materials employed, species, and conditions are intended to be further illustrative of this invention and not limitative of the reasonable scope thereof.
Example I
A control run was carried out in which PPS copolymer was prepared by contacting, under polymerization conditions, meta- and para-difunctional aromatic monomers together initially.
To a two gallon reactor were charged 572.6g of sodium hydrosulfide ~6.00 moles/58.74% pure NaSH x H20), 254g of sodium hydroxide (6.35 moles/100% pure NaOH pellets from Mallinckrodt), 147.6g of sodium acetate (1.80 moles/100% pure sodium acetate from Niocet Corporation), and 1600cc of NMP (16.56 moles/99.5% pure NMP from BASF).
The mixture was purged with nitrogen, stirred at 250 RPM, and heated to 160C and held for 4 minutes. Dehydration was started and a total of 360 -cc of water and NMP were distilled off while reaching 200C. To the reactor were also charged 808.5g of hot pDCB (5.5 moles/100% pure pDCB
from PPG Chemical), 88.2g of hot mDCB (0.6 moles/100% pure mDCB from Ishihara Chemical), 2.17g of hot TCB (0.012 moles/100% pure TCB from MCB
Chemical), and 325cc of hot NMP. An after charge reactor pressure of 50 psig was established with nitrogen gas. The reactor temperature was raised to 235C and held for two hours. The reactor temperature was then raised to 265C and held for three hours with a ~xi presure of 170 psig. The stirrer RPM was raised to 600 and 250 cc of hot deionized water were charged slowly to the reactor. The reactor contents were then allowed to cool overnight. The next morning 2250 cc of deionized water were charged to the reactor and the stirrer RPM was held at 250 for ten minutes. A solid polymer was recovered then water washed, acetone washed, and dried in a forced air oven at 110C.
This run yielded 593.4g (91.4%) of dried PPS copolymer with the following characteristics:
A melt flow of 184.68 g/10 minutes, an ash content of 1.23 weight percent, and a melt crystallization temperature (Tmc~ of 147C.
Example II
This control run was conducted as in Example I, except that instead of 360 cc, 370 cc of H20 and NMP were distilled off and when the 2250 cc of deionized water were added the stirrer locked up and the polymer had to be ground in a Waring Blendor prior to washing and drying.
The run yielded 489.lg (75.97%) of dried PPS copolymer with the 25 following characteristics: A melt flow of 219 g/10 minutes, an ash content of 0.96 weight percent, and a Tmc of 154C.
Example III
This control run was conducted as in Example II and yielded 544.9g (83.97%) of PPS copolymer with the following characteristics: A
30 melt flow of 203.64 g/10 minutes, an ash content of 1.14 weight percent, and a Tmc of 170C.
Example IV
According to the present invention a run was carried out in which PPS block copolymer was prepared by prereacting under polymerization conditions meta- difunctional aromatic monomer.
1 3367~9 32260CA
To a two gallon reactor were charged 568.5g of sodium hydrosulfide (6.00 moles/59.17% pure NaSH x H20), 254g of sodium hydroxide (6.35 moles/100% pure NaOH pellets from Mallinckrodt Chemical Co.), 147.6g of sodium acetate (1.80 moles/100% pure sodium acetate from Niocet Coporation), 1600cc of NMP (16.56 moles/99.5% pure NMP from BASF).
The mixture was then heated with nitrogen and stirred at 250 RPM, and heated to 160C and held for five minutes. Dehydration was started and a total of 360cc of water and NMP were distilled off while reaching 200C.
To the reactor were also charged 88.2g of hot mDCB (0.6 moles/100% pure mDCB from Ishihara Chemical), 2.17g hot TCB (0.012 moles/100% pure TCB
from MCB Chemical), and 50cc of hot NMP. An after charge reactor pressure of 50 psig was established. The reactor temperature was raised to 235C and held for 1 hour. This was followed by the addition of 808.5g of hot pDCB (5.5 moles/100% pure pDCB from PPG Chemical), and 235cc of hot NMP. An after charge reactor pressure of 75 psig was established and the reactor was held at 235C for an additional hour.
The reactor temperature was then raised to 265C and held for 3 hours with a maximum pressure of 150 psig. The stirrer RPM was raised to 600 and 250cc of hot deionized water were charged slowly to the reactor. The reactor contents were then allowed to cool overnight. The next morning 2250cc of deionized water were charged to the reactor and the stirrer RPM
was held at 250 for 10 minutes. A solid polymer was recovered, then water washed, acetone washed, and dried in a forced air oven at 110C.
This run yielded 563.9g (86.89%) of dried PPS block copolymer with a melt flow of 120.71 g/10 minutes and a Tmc of 170C.
Example V
This run was conducted as in Example IV except that two pressures were different. The after charge reactor pressure after the addition of pDCB and NMP was 100 psig and the ~xi reactor pressure after the temperature was raised to 265C was 180 psig. This run yielded 413.6g (63.73%) of dried PPS block copolymer (some polymer was lost before workup) with a melt flow of 133.99 g/10 minutes.
13 l 336729 Example VI
This run was conducted as in Example V except that the maximum reactor pressure, after the reactor was raised to 265C, was not measured.
This run yielded 571.5g (88.06%) of dried PPS block copolymer with a melt flow of 94.11 g/10 minutes.
Example VII
This run was conducted as in Example VI except that the after charge reactor pressure after the addition of pDCB and NMP was not measured and the ~xi reactor pressure after the reactor was raised to 265C was measured at 100 psig.
This run yielded 559g (86.14%) of dried PPS block copolymer with a melt flow of 154 g/10 minutes.
The above examples show that by prereacting the mDCB prior to the addition of the pDCB, the problem of sluggish mDCB monomer reactivity is avoided. The PPS block copolymers prepared in the four invention examples (IV-VII) above have an improved melt flow of about 120 g/10 minutes as compared to the melt flow of about 200 g/10 minutes for the PPS copolymers which are prepared by reacting mDCB and pDCB together initially. This reduction in melt flow shows that the mDCB is incorporated more efficiently into the copolymer by following the process of the present invention.
All polymers produced in the control and invention examples above are good meta-para-copolymers and, therefore, have acceptable melt crystallization temperatures for use in fiber and film applications.
However, only the meta-para-copolymers produced in invention Examples IV-VII are high molecular weight meta-para-copolymers. These high molecular weight meta-para-copolymers will provide fibers and films of improved quality.
Claims (20)
1. A process for preparing a poly(arylene sulfide) comprising:
(a) contacting under polymerization conditions a mixture of about 0.01 to 90 mole percent of at least one meta-dihalobenzene monomer of the formula , 0 to 10 mole percent of at least one polyhalobenzene monomer of the formula , and an alkali metal sulfide in a polar organic medium for a sufficient time to form a first polymerization admixture comprising poly(meta-arylene sulfide) blocks;
(b) charging to said first polymerization admixture of (a) about 1 to 99.99 mole percent of at least one para-dihalobenzene monomer of the formula and continuing polymerization for a sufficient time to form poly(para-arylene sulfide) blocks attached to said poly(meta-arylene sulfide) blocks of (a), thereby producing a second polymerization admixture comprising a block copolymer;
wherein the mole percent of each monomer employed is based on the total quantity of the monomers employed, X is halogen, n is ? 3, m is ? 3, n+m=6, and each R can be the same or different and is selected from the group consisting of hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 20 carbon atoms, aryl having 6 to 24 carbon atoms, alkyl aryl having 7 to 24 carbon atoms, and aryl alkyl having 7 to 24 carbon atoms.
(a) contacting under polymerization conditions a mixture of about 0.01 to 90 mole percent of at least one meta-dihalobenzene monomer of the formula , 0 to 10 mole percent of at least one polyhalobenzene monomer of the formula , and an alkali metal sulfide in a polar organic medium for a sufficient time to form a first polymerization admixture comprising poly(meta-arylene sulfide) blocks;
(b) charging to said first polymerization admixture of (a) about 1 to 99.99 mole percent of at least one para-dihalobenzene monomer of the formula and continuing polymerization for a sufficient time to form poly(para-arylene sulfide) blocks attached to said poly(meta-arylene sulfide) blocks of (a), thereby producing a second polymerization admixture comprising a block copolymer;
wherein the mole percent of each monomer employed is based on the total quantity of the monomers employed, X is halogen, n is ? 3, m is ? 3, n+m=6, and each R can be the same or different and is selected from the group consisting of hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 20 carbon atoms, aryl having 6 to 24 carbon atoms, alkyl aryl having 7 to 24 carbon atoms, and aryl alkyl having 7 to 24 carbon atoms.
2. A process according to claim 1 wherein additional polar organic medium is added in (b).
3. A process according to claim 1 further comprising adding hot water to said second polymerization admixture of (b) followed by cooling and recovering said block copolymer.
4. A process according to claim 1 wherein additional alkali metal sulfide is added in (b).
5. A process according to claim 1 wherein the alkali metal sulfide is prepared in aqueous solution by the reaction of an alkali metal hydroxide with an alkali metal bisulfide.
6. A process according to claim 1 wherein the mole percent of meta-dihalobenzene, polyhalobenzene, and para-dihalobenzene is about 1 to 20 mole percent, about 0.1 to 2 mole percent, and about 80 to 99 mole percent respectively based on the total quantity of the monomers employed.
7. A process according to claim 1 wherein said at least one meta-dihalobenzene monomer is selected from the group consisting of m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 1-chloro-3-bromobenzene, 1-chloro-3-iodobenzene, and mixtures of any two or more thereof;
said at least one poly-halobenzene monomer is selected from the group consisting of 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3-dichloro-5-bromobenzene, 2,4,6-trichlorotoluene, 1,2,3,5-tetra-bromobenzene, hexachlorobenzene, 1,3,5-trichloro-2,4,6-trimethylbenzene, 2,2'4,4'-tetrachlorobiphenyl, 2,2',6,6'-tetrabromo-3,3',5,5'-tetramethyl-biphenyl, 1,2,3,4-tetrachloronaphthalene, 1,2,4-tribromo-6-methyl-naphthalene, and mixtures thereof; and said at least one para-dihalobenzene monomer is selected from the group consisting of p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, 1-chloro-4-bromobenzene, 1-chloro-4-iodobenzene, 1-bromo-4-iodobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1-ethyl-4-isopropyl-2,5-dibromobenzene, 1,2,4,5-tetramethyl-3,6-di-chlorobenzene, 1-butyl-4-cyclohexyl-2,5-dibromobenzene, 1-hexyl-3-dodecyl-2,5-dichlorobenzene, 1-octadecyl-2,5-diidobenzene, 1-phenyl -2-chloro-5-bromobenzene, 1-(p-tolyl)-2,5-dibromobenzene, 1-benzyl-2,5-dichlorobenzene, 1-octyl-4-(3-methylcyclopentyl)-2,5-dichlorobenzene, and mixtures of any two or more thereof.
said at least one poly-halobenzene monomer is selected from the group consisting of 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3-dichloro-5-bromobenzene, 2,4,6-trichlorotoluene, 1,2,3,5-tetra-bromobenzene, hexachlorobenzene, 1,3,5-trichloro-2,4,6-trimethylbenzene, 2,2'4,4'-tetrachlorobiphenyl, 2,2',6,6'-tetrabromo-3,3',5,5'-tetramethyl-biphenyl, 1,2,3,4-tetrachloronaphthalene, 1,2,4-tribromo-6-methyl-naphthalene, and mixtures thereof; and said at least one para-dihalobenzene monomer is selected from the group consisting of p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, 1-chloro-4-bromobenzene, 1-chloro-4-iodobenzene, 1-bromo-4-iodobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1-ethyl-4-isopropyl-2,5-dibromobenzene, 1,2,4,5-tetramethyl-3,6-di-chlorobenzene, 1-butyl-4-cyclohexyl-2,5-dibromobenzene, 1-hexyl-3-dodecyl-2,5-dichlorobenzene, 1-octadecyl-2,5-diidobenzene, 1-phenyl -2-chloro-5-bromobenzene, 1-(p-tolyl)-2,5-dibromobenzene, 1-benzyl-2,5-dichlorobenzene, 1-octyl-4-(3-methylcyclopentyl)-2,5-dichlorobenzene, and mixtures of any two or more thereof.
8. A process according to claim 7 wherein said at least one meta-dihalobenzene monomer is m-dichlorobenzene, said at least one polyhalobenzene monomer is 1,2,4-trichlorobenzene, and said para-dihalobenzene monomer is p-dichlorobenzene.
9. A process according to claim 1 wherein said polar organic medium contains a polar organic amide solvent.
10. A process according to claim 9 wherein said polar organic amide is N-methyl-2-pyrrolidone.
11. A process according to claim 1 wherein said alkali metal sulfide is sodium sulfide.
12. A process for preparing a poly(arylene sulfide) copolymer comprising:
(a) contacting under polymerization conditions a reaction mixture of about 0.01 to 90 mole percent of m-dihalobenzene monomer, 0 to 10 mole percent trihalobenzene monomer, an alkali metal sulfide, and a polar organic medium, for sufficient time to form a first product mixture comprising poly(meta-arylene sulfide) blocks;
(b) charging under polymerization conditions to said first product mixture of (a) about 1 to 99.99 mole percent of p-dihalobenzene monomer for a sufficient time to form poly(para-arylene sulfide) blocks attached to said poly(meta-arylene sulfide) blocks of (a) thereby producing a second product mixture comprising a poly(arylene sulfide) block copolymer;
(c) recovering said poly(arylene sulfide) block copolymer of high molecular weight and low melt flow;
wherein the mole percent of each monomer employed is based on the total quantity of the monomers employed.
(a) contacting under polymerization conditions a reaction mixture of about 0.01 to 90 mole percent of m-dihalobenzene monomer, 0 to 10 mole percent trihalobenzene monomer, an alkali metal sulfide, and a polar organic medium, for sufficient time to form a first product mixture comprising poly(meta-arylene sulfide) blocks;
(b) charging under polymerization conditions to said first product mixture of (a) about 1 to 99.99 mole percent of p-dihalobenzene monomer for a sufficient time to form poly(para-arylene sulfide) blocks attached to said poly(meta-arylene sulfide) blocks of (a) thereby producing a second product mixture comprising a poly(arylene sulfide) block copolymer;
(c) recovering said poly(arylene sulfide) block copolymer of high molecular weight and low melt flow;
wherein the mole percent of each monomer employed is based on the total quantity of the monomers employed.
13. A process according to claim 12 wherein said m-dihalobenzene monomer is m-dichlorobenzene, said trihalobenzene monomer is 1,2,4-trichlorobenzene, said p-dihalobenzene monomer is p-dichlorobenzene, said alkali metal sulfide is sodium sulfide, and said polar organic medium is N-methyl-2-pyrrolidone.
14. A polymer composition comprising poly(arylene sulfide) block copolymer which contains recurring units (a), recurring units (b), and further comprises units of (c), wherein each R can be the same or different and is selected from the group consisting of hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 20 carbon atoms, aryl having 6 to 24 carbon atoms, alkyl aryl having 7 to 24 carbon atoms and aryl alkyl having 7 to 24 carbon atoms, z is ? 2, m is ? 3, and z+m=5.
15. A polymer composition according to claim 14 wherein said poly(arylene sulfide) block copolymer is poly(phenylene sulfide) block copolymer.
16. A poly(phenylene sulfide) block copolymer according to claim 15 wherein R is hydrogen and (c) is represented by where P = a continuing polymer chain.
17. A poly(phenylene sulfide) block copolymer according to claim 16 wherein the mole percent of said (a), (b), and (c) units are within the range of about 1 to 20, 10 to 99.9, and 0.1 to 2 respectively.
18. A poly(phenylene sulfide) block copolymer according to claim 17 wherein the mole percent of said (a), (b), and (c) units are within the range of about 1 to 20, 80 to 99, and 0.1 to 2 respectively.
l9. In a process for preparing a poly(arylene sulfide) copolymer by contacting under polymerization conditions at least one meta-dihalobenzene of the formula , at least one para-dihalobenzene monomer of the formula ,
l9. In a process for preparing a poly(arylene sulfide) copolymer by contacting under polymerization conditions at least one meta-dihalobenzene of the formula , at least one para-dihalobenzene monomer of the formula ,
19 0.1 to 10 mole percent of at least one polyhalobenz-ene monomer of the formula , and an alkali metal sulfide in a polar organic medium for a sufficient length of time to form a poly(arylene sulfide) co-polymer, the improvement comprising contacting essentially separate from each other under polymerization conditions said meta- and para-dihalobenzene monomers with at least a portion of said alkali metal sulfide in a polar organic medium to preform separately meta- and para-arylene sulfide polymer blocks, then admixing said meta- and para-arylene sulfide polymer blocks under polymerization conditions to join said blocks thereby forming said copolymer;
wherein X is halogen, n is ?3, m is ?3, n + m = 6, and each R can be the same or different and is selected from the group consisting of hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 20 carbon atoms, aryl having 6 to 24 carbon atoms, alkyl aryl having 7 to 24 carbon atoms, and aryl alkyl having 7 to 24 carbon atoms.
wherein X is halogen, n is ?3, m is ?3, n + m = 6, and each R can be the same or different and is selected from the group consisting of hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 20 carbon atoms, aryl having 6 to 24 carbon atoms, alkyl aryl having 7 to 24 carbon atoms, and aryl alkyl having 7 to 24 carbon atoms.
20. A process for preparing a poly(arylene sulfide) comprising:
(a) contacting under polymerization conditions a reaction mixture of about 1 to 99.99 mole percent of at least one para-dihalobenzene monomer of the formula 0 to 10 mole percent of at least one poly(halobenzene monomer) of the formula and an alkali metal sulfide in a polar organic medium for a sufficient time to form a first product mixture comprising poly(para-arylene sulfide) blocks;
(b) charging under polymerization conditions to said first product mixture of (a) about 0.01 to 90 mole percent of at least one meta-dihalobenzene monomer of the formula , 0 to 10 mole percent of at least one poly(halobenzene monomer) of the formula for a sufficient length of time to form poly(meta-arylene sulfide) blocks attached to said poly(para-arylene sulfide) blocks of (a) thereby producing a second product mixture comprising a poly(arylene sulfide) block copolymer;
wherein the mole percent of each monomer is based on the total quantity of the monomers employee, X is halogen, n is ? 3, m is ? 3, n+m=6, and each R can be the same or different and is selected from the group consisting of hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 20 carbon atoms, aryl having 6 to 24 carbon atoms, alkyl aryl having 7 to 24 carbon atoms, and aryl alkyl having 7 to 24 carbon atoms.
(a) contacting under polymerization conditions a reaction mixture of about 1 to 99.99 mole percent of at least one para-dihalobenzene monomer of the formula 0 to 10 mole percent of at least one poly(halobenzene monomer) of the formula and an alkali metal sulfide in a polar organic medium for a sufficient time to form a first product mixture comprising poly(para-arylene sulfide) blocks;
(b) charging under polymerization conditions to said first product mixture of (a) about 0.01 to 90 mole percent of at least one meta-dihalobenzene monomer of the formula , 0 to 10 mole percent of at least one poly(halobenzene monomer) of the formula for a sufficient length of time to form poly(meta-arylene sulfide) blocks attached to said poly(para-arylene sulfide) blocks of (a) thereby producing a second product mixture comprising a poly(arylene sulfide) block copolymer;
wherein the mole percent of each monomer is based on the total quantity of the monomers employee, X is halogen, n is ? 3, m is ? 3, n+m=6, and each R can be the same or different and is selected from the group consisting of hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 20 carbon atoms, aryl having 6 to 24 carbon atoms, alkyl aryl having 7 to 24 carbon atoms, and aryl alkyl having 7 to 24 carbon atoms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US27287A | 1987-01-02 | 1987-01-02 | |
| US000,272 | 1987-01-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1336729C true CA1336729C (en) | 1995-08-15 |
Family
ID=21690747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000554198A Expired - Fee Related CA1336729C (en) | 1987-01-02 | 1987-12-14 | Poly(arylene sulfide)s and preparation thereof |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS63221128A (en) |
| CA (1) | CA1336729C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2004884A1 (en) * | 1988-12-29 | 1990-06-29 | Guy Senatore | Arylene sulfide polymers and articles of manufacture |
-
1987
- 1987-12-14 CA CA000554198A patent/CA1336729C/en not_active Expired - Fee Related
- 1987-12-28 JP JP62336718A patent/JPS63221128A/en active Pending
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| JPS63221128A (en) | 1988-09-14 |
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